Structural evolution and catalytic mechanisms of perovskite oxides in electrocatalysis

Jia-Wei Zhao; Yunxiang Li; Deyan Luan; Xiong Wen (David) Lou

doi:10.1126/sciadv.adq4696

. 2024 Sep 25;10(39):eadq4696. doi: 10.1126/sciadv.adq4696

Structural evolution and catalytic mechanisms of perovskite oxides in electrocatalysis

Jia-Wei Zhao ^1,², Yunxiang Li ¹, Deyan Luan ¹, Xiong Wen (David) Lou ^1,^*

PMCID: PMC11804782 PMID: 39321283

Abstract

Electrocatalysis plays a pivotal role in driving the progress of modern technologies and industrial processes such as energy conversion and emission reduction. Perovskite oxides, an important family of electrocatalysts, have garnered substantial attention in diverse catalytic reactions because of their highly tunable composition and structure, as well as their considerable activity and stability. This review delves into the mechanisms of electrocatalytic reactions that use perovskite oxides as electrocatalysts, while also providing a comprehensive summary of the potential key factors that influence catalytic activity across various reactions. Furthermore, this review offers an overview of advanced characterizations used for studying catalytic mechanisms and proposes approaches to designing highly efficient perovskite oxide electrocatalysts.

The catalytic mechanisms of reactions and the surface evolution of perovskite oxide–based electrocatalysts are reviewed.

INTRODUCTION

The global challenges of energy and environment are further compounded by rapid population growth (1–3). In 2022, the global energy supply reached 632 exajoules (EJ), with ~80% derived from nonrenewable fossil fuels like coal, oil, and natural gas (4). With the continuous rise in population and industrialization, projections indicate that under “stated policies” or “announced pledges” scenarios, renewable energy supply is expected to grow from 75 EJ to either 227 or 327 EJ by 2050 (4). As the adoption of renewables continues, particularly the deployment increase in wind power and solar power, questions arise about how to build a reliable energy grid considering the intermittency of these power sources (5–8).

Electrocatalytic systems have emerged as effective means to convert readily available reactants into fuels and chemicals using electricity from intermittent solar and wind energy (Fig. 1). Currently, electrocatalytic reactions primarily include chemical transformations involving oxygen (O), carbon (C), and nitrogen (N) (9, 10). Key reactions such as the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are pivotal for green hydrogen production (10, 11), while the oxygen reduction reaction (ORR) serves as a critical half-reaction in fuel cells and metal-air batteries (12, 13). In addition, the carbon dioxide reduction reaction (CO₂RR) and nitrogen reduction reaction (NRR) enable the production of value-added products such as ethylene and ammonia, respectively (14–17). Theoretically, these electrocatalytic reactions could enable the effective utilization and conversion of intermittent sustainable energy sources for large-scale industrial deployments (18). Nevertheless, this approach is still limited by the unsatisfactory performance and/or high cost of electrocatalysts. Despite numerous works focusing on catalyst design, there is still a considerable gap between fundamental research and practical applications (19–21). Therefore, designing efficient, stable, and low-cost electrocatalysts is imperative.

Fig. 1. — Electrocatalysis has led to notable advancements in various emerging technologies and industries, such as energy conversion and emission reduction. Demonstrated here are a range of applications, encompassing wind-solar and electricity-driven electrocatalysis, for the purposes of energy storage, energy conversion, and the chemical production.

There are many types of electrocatalysts, including oxides, (oxy)hydroxides, metals, sulfides, and metal-organic frameworks (3, 22). Because of the complexity of different electrocatalytic reactions, studying catalytic mechanisms requires exploring catalysts with simple and controllable structures. This allows researchers to systematically investigate the correlation between the structure, activity, and stability of catalysts and summarize meaningful activity descriptors. Perovskite oxides, characterized by the typical ABO₃ formula, are one of the most widely applied and chemically diverse families of crystals. Calcium titanate (CaTiO₃) was the first one found in this family and was named “perovskite” after the Russian mineralogist Lev Perovski (23). The A-site typically consists of an alkaline-earth metal or rare-earth metal element, such as La, Sr, Ba, and Ca, that forms a 12-fold coordination structure with O. The B-site usually consists of a transition-metal element like Fe, Co, Ni, and Mn, that forms a sixfold coordination octahedral structure with O (Fig. 2, center) (24).

Fig. 2. — (**Center**) ABO₃ perovskite crystal structure. The blue, gray, and orange spheres represent the A-site, B-site, and O, respectively. (**Outer left**) Electrochemical reduction reactions (ORR and HER) and the key factors. (**Outer right**) Electrochemical oxidation reaction (OER) and key factors. (**Outer bottom**) Other reactions include NRR, CO₂RR, and UOR. The deep blue, dark gray, red, and white spheres represent N, C, O, and H, respectively.

The A- and B-sites of perovskite oxides can be easily controlled by using different metal precursors or changing their proportions, resulting in a vast range of variations in perovskite oxides. Currently, more than 1000 types of perovskite oxides have been identified, with potentially about 60,000 different types (25). This feature allows perovskite oxide electrocatalysts to be applied in a wide range of catalytic reactions. High-quality multicrystal particles of perovskite oxides can be obtained through solid-phase calcination and the Pechini method, while single-crystal films of perovskite oxides can be grown using techniques such as laser epitaxy and chemical deposition (19, 26). This allows the synthesized perovskite oxide catalysts to closely approach the theoretical model, facilitating the combination of theoretical calculation methods like density functional theory (DFT) and ab initio molecular dynamics (AIMD) to study the underlying mechanisms (19). Furthermore, perovskite oxides synthesized at high temperatures typically exhibit high chemical stability and maintain their bulk structure under appropriate electrocatalytic conditions (24, 27).

Currently, perovskite oxides are mainly used in O-related electrochemical reactions, including OER, ORR, and HER (28–30), and also show promising catalytic properties in other reactions such as NRR, CO₂RR, urea oxidation reaction (UOR), and methanol oxidation reaction (MOR) (Fig. 2) (31–34). While some studies have systematically investigated perovskite oxides and summarized activity descriptors, many descriptors are limited by structural evolution caused by complex electrocatalytic processes (26, 35, 36). For example, the surface evolution of perovskite oxides during the OER process make descriptors based on initial structures inaccurate (37). Furthermore, perovskite oxides exhibit distinct catalytic mechanisms across various electrocatalytic reactions, with the pivotal determinants of performance differing accordingly. Designing high-performing perovskite oxide electrocatalysts necessitates adherence to principles derived from a holistic comprehension of catalytic mechanisms and critical factors unique to these materials. However, there has been a scarcity of comprehensive reviews elucidating the diverse mechanisms and key factors governing perovskite oxides, resulting in a lack of applicable methodologies to guide the design of efficient perovskite oxide electrocatalysts (38–49). Therefore, a review is needed to summarize the catalytic mechanisms and key factors affecting the performance of perovskite oxides across various catalytic reactions. Herein, we focus on the mechanisms of perovskite oxide electrocatalysis and provide a research framework. Through this framework, researchers can analyze and identify the mechanisms and influencing factors in the research and design of perovskite oxide electrocatalysts, potentially extending them to numerous other reactions in photocatalysis and thermocatalysis.

PEROVSKITE OXIDES IN OER

OER mechanisms

Currently, three primary mechanisms are widely recognized for the OER, namely, the adsorbate evolution mechanism (AEM), lattice oxygen mechanism (LOM), and oxide path mechanism (OPM) (Fig. 3A) (50–52). Among them, AEM is considered to be the main mechanism. Taking an acidic medium as an example, a H₂O molecule in the electrolyte first adsorbs at the B-site, followed by dehydrogenation and an electron loss process to form OH_ads. A new H₂O molecule then couples with the OH_ads, losing a proton and an electron to form O_ads. Similar processes lead to the formation of OOH_ads and O_2ads, lastly releasing O₂ from the B-sites. Through the efforts of researchers, it is found that the formation of O_ads or OOH_ads is the rate-determining step for OER in many metal oxides (53). The other two mechanisms, LOM and OPM, are closely related to these two steps. The LOM process bypasses the formation of O_ads by coupling OH_ads with lattice oxygen, but some researchers also proposed that O_ads is formed first and then coupled with lattice oxygen to release O₂, thus avoiding the formation of OOH_ads (54). The first two steps of the OPM are consistent with the AEM, i.e., OH_ads and O_ads, but the adjacent O_ads species directly couple to release O₂, bypassing the OOH_ads step (55). The total energy of the four steps of OER is 4.92 eV (56). For the AEM, the total energy of the O_ads and OOH_ads steps is ~3.1 eV according to linear relationships, posing a challenge in surpassing the limiting overpotential of 0.32 V (53, 57). In contrast, LOM and OPM can circumvent this limitation by bypassing the formation of O_ads or OOH_ads. However, it is important to note that both LOM and OPM have rate-determining steps, although the specific step for each remains uncertain. Furthermore, LOM requires the participation of lattice oxygen, which may depend on the B─O bonding properties or the presence of oxygen vacancies. OPM heavily relies on a high coverage of adjacent O_ads species to achieve O─O coupling. To date, only a few catalysts have been reported to adhere to the LOM process, while the OPM process is even rarer (58). Even for catalysts with the LOM process, the AEM process coexists and accounts for a significant proportion from previous reports, which may be influenced by the conditions of the differential electrochemical mass spectrometry (DEMS) test (59–61). The mechanism of OER has not been well resolved, and more advanced characterization techniques are needed.

Fig. 3. — (A) Three possible mechanisms of OER, including AEM, LOM, and OPM. The deep blue, red, and white spheres represent lattice O, electrolyte O, and H, respectively. (B and C) Surface leaching and reconstruction that may occur on perovskite oxides during the OER. The deep blue, dark gray, and red spheres represent A-site, B-site, and O, respectively. (D) Summary of OER performance of different perovskite oxides. The left region and the right region represent La-based perovskite and other metal-based perovskite, respectively. The OER current density of different perovskite oxides was calculated at 1.60 V versus reversible hydrogen electrode (RHE). B, S, L, P, F, C, N, M, and I: Ba, Sr, La, Pr, Fe, Co, Ni, Mn, and Ir (19, 26, 29, 35, 37, 68, *108*, *174*–*176*).

Surface evolution during OER

Before analyzing the key factors of perovskite oxides in OER, it is necessary to consider the surface evolution that occur during the OER process. The element leaching phenomenon is widely observed over perovskite oxides (Fig. 3B). The most probable leaching site in perovskite oxides is the A-site, which includes elements such as La, Sr, and Ba. Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ and La_xSr_1−xCo_0.8Fe_0.2O_3−δ perovskite oxides are the most representative examples, both exhibiting Sr leaching (62–64). This leaching phenomenon can be predicted using a Pourbaix diagram, where many A-sites tend to dissolve near the oxygen stability line, whether in an acidic or alkaline medium (62, 65, 66).

In general, the A-site is not directly involved in adsorbate bonding, and its leaching tends to promote the OER catalytic performance of perovskite oxides by exposing the active B-site, forming BO_xH_y/ABO₃ heterostructure, modulating electronic structures, or altering conductivity (19, 62–64). In addition to A-site leaching, B-site leaching has a more pronounced impact on the stability and activity of the perovskite oxides because the B-site is the crucial catalytic site directly involved in adsorbate bonding. In alkaline OER, taking SrRuO₃ as an example, significant Ru leaching occurs, leading to discoloration of the electrolyte. As the number of catalytic sites decreases because of the dissolution of Ru, the OER performance gradually declines (67). In acidic medium, most transition metals at B-sites are unstable, which also results in significant leaching at the B-site, ultimately causing the dissolution of the catalyst in the electrolyte. All of the above situations can lead to the disruption of the overall structure of perovskite oxides. For perovskite oxides with inactive B-sites (AB_actB_inactO₃), the leaching of inactive B-site metals (B_inact) may promote the surface reconstruction process of the catalyst and thus enhance performance (68–70). For example, in LaNi_0.5Li_0.5O₃ and SrIr_0.1Co_0.9O₃, the leaching of Li and Co does not lead to the destruction of the entire structure. Ultimately, the formation of LaNi_xO_y and IrO_x on the surface plays a crucial role in catalytic activity (68, 69). Furthermore, there is a particular type of oxygen leaching, which can occur in two ways: simultaneous leaching with the A-site or B-site (dissolution of A/B─O_x), or independent oxidation of lattice oxygen (58, 71). The latter case leads to oxygen leaching and is highly related to the LOM process. Similar to A-site and B-site leaching, oxygen leaching is not always beneficial as it can enhance activity while reducing the stability of the catalyst (72).

In addition to the leaching process, perovskite oxides undergo surface reconstruction during the OER process (Fig. 3C) (73, 74). Leaching and reconstruction are usually interrelated. That is, leaching can lead to reconstruction, and the reconstruction process inevitably involves leaching (64). Because catalytic reactions are surface reactions that heavily rely on the catalyst’s surface structure (even a few atomic layers), the newly formed phases resulting from the reconstruction process directly determine the activity and stability of OER (75). Most research reports indicate that amorphous (oxy) hydroxide phases, such as BO_xH_y, form on the perovskite oxides after surface reconstruction (37, 64). Because of the high activity of Ni-, Co-, and Fe-based (oxy)hydroxides during OER, perovskite oxides containing these metals at the B-site generally exhibit good activity after surface reconstruction (76). In addition to the intrinsic activity of the reconstructed phase derived from B-site, the bulk structure of perovskites also has a great impact on activity. For example, LaNiO₃ as a semimetallic perovskite has good conductivity and can serve as a support to facilitate electron transfer after surface reconstruction. This resolves the conductivity issue of pure NiO_xH_y catalyst and further enhances the performance. Focusing on the leaching process and the newly formed phases after reconstruction for perovskite oxides will contribute to a clearer understanding of the catalytic mechanisms. Here, the activity of typical perovskite oxides and their change ratio (the ratio of current density before and after activation) are summarized (Fig. 3D). We classify these typical cases into La-based perovskites and other-based perovskites because the former ones usually exhibit higher stability during OER (37). It can be observed that the change ratios for La-based perovskite oxides are all around 1, while the change ratios for other perovskite oxides range from 0.3 to 13 and are generally higher than those of La-based perovskite oxides. Most of these perovskite oxides with high change ratios undergo noticeable leaching or simultaneous leaching and reconstruction. The A-site greatly influences the surface structural stability of perovskite oxides; thus, one of the most direct methods to enhance the OER performance of perovskite oxides is to control the A-site elements or the A/B stoichiometric ratio.

Key factors affecting OER

We now focus on the key factors influencing their OER activity. Oxygen vacancy is an important factor. Perovskite oxides tend to form oxygen vacancies during synthesis, leading to two possible catalytic sites, namely, BO₅ and BO₄ sites (Fig. 4A) (28, 77). Before investigating the mechanisms at the BO₅ or BO₄ catalytic sites, it is necessary to consider the local structure change of the perovskite oxides. Perovskite oxides synthesized through calcination or subjected to posttreatments may exhibit distorted octahedral configurations, causing the Jahn-Teller effect (78). Distortions in the BO₅ or BO₄ structures can alter the electronic arrangement of e_g and t_2g orbitals, thereby affecting the adsorption energy of adsorbates (79). These distortions can also impact catalyst stability. Therefore, the Jahn-Teller effect is an important factor influencing perovskite oxides. Back to catalytic sites, O atoms in the electrolyte (from H₂O or OH⁻) can adsorb at the B-site or fill the oxygen vacancies. The BO₅ sites typically follow the AEM, as the leaching of lattice oxygen is usually hindered. The case of BO₄ is more complex, where adsorbates can either undergo AEM using oxygen vacancies or B-site as catalytic sites or undergo the LOM process starting from the adsorption at the B-site and subsequently filling in oxygen vacancies (58). Because oxygen vacancies are dynamic during the OER process, accompanied by lattice oxygen evolution and refilling, it is sometimes necessary to consider this factor when studying perovskite oxides.

To determine other critical factors influencing the OER performance of perovskite oxides, we summarized the correlation between the 3d band center of different B-site metals (M 3d) in perovskite oxides and their catalytic activity (Fig. 4B). The results indicate that a negative shift in the M 3d band center of perovskite oxides with Fe, Co, Ni, and Mn metals at the B-site favors OER performance. As the M 3d band center becomes lower and moves away from the Fermi level, approaching the antibonding orbitals of adsorbed O_ads, the probability of electron filling in the antibonding orbitals increases, leading to weaker adsorption of O_ads (80). As a result, this may facilitate the formation of OOH_ads, thereby enhancing the activity of perovskite oxides with OOH_ads as the rate-determining step (53). In addition, the difficulty in O_ads adsorption may also induce the LOM pathway over perovskite oxides, thereby increasing the activity (36).

We also summarized the correlation between O 2p band center, M 3d–O 2p band center, and OER activity of perovskite oxides (Fig. 4C). The results demonstrate that the linear relationship between the O 2p band center, M 3d–O 2p band center, and activity is more prominently than that between M 3d band center and activity. When the O 2p band center is closer to the Fermi level, the M─O bond on the catalyst surface exhibits higher covalency, making lattice oxygen more prone to be oxidized to oxygen during OER (58, 72). This may be one of the reasons for improved activity. The most representative example is SrCoO_3−δ following the LOM process, which has a lower M 3d–O 2p band center and a higher O 2p band center, showing higher OER activity (Fig. 4C) (58, 81). Furthermore, the substantial evolution of lattice oxygen accompanies the leaching of A-site and B-site elements, ultimately leading to surface reconstruction of the catalyst. This is also a key factor contributing to high activity. A notable example is Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ, where sites rapidly leach and reconstruct during the OER process, forming nanosized amorphous Co/Fe (oxy)hydroxide on the surface (64, 82). Regardless of variations in M 3d and O 2p, non–(Fe, Co, Ni, Mn) perovskite oxides exhibit low OER activity. There are two reasons for this phenomenon. First, these catalysts have either excessively high or low M 3d band centers, leading to high-energy barriers for the formation of O_ads or OOH_ads intermediates during the OER process. Second, even if these catalysts have high O 2p band centers, their subsequent reconstruction does not form new active phases.

The above conclusions are drawn from non-noble transition metal perovskite oxides in alkaline OER. Although the mechanisms of acidic OER and alkaline OER are similar, the range of perovskite oxides for acidic OER is small because most perovskite oxides are unstable in acidic media. Only Ir-based perovskite oxides demonstrate excellent acidic OER performance through surface reconstruction (19, 70, 83–87). Research on perovskite oxides for acidic OER is currently limited, making it difficult to summarize activity descriptors for these perovskite oxides.

Catalyst design for OER

Our focus lies in the band centers of perovskite oxides, and we suggest a method for enhancing the OER performance of perovskite oxides by designing catalysts with relatively high O 2p band centers and highly active B-site metals featuring low M 3d band centers (Fig. 4D). In detail, considering the structural evolution of perovskite oxides during the OER, selecting B-site metals with high OER activity is an important step. These include non-noble metals such as Fe, Co, Ni, and Mn, as well as noble metals like Ir and Ru. Furthermore, for alkaline OER processes, perovskite oxides generally exhibit low initial activity and require activation. Therefore, perovskite oxides with surface leaching and reconstruction are more likely to achieve high activity. One of the most direct methods is to substitute A-site metal or dope A-site (e.g., replacing relatively stable La-based perovskite with Ca, Ba, Sr, etc.) and B-site doping (forming multimetallic sites such as NiFe and CoFe or doping inactive sites such as Si and Li to alter surface stability). In addition, doping at O-site (typically with S, N, or F) may also affect the surface leaching and reconstruction of perovskite oxides. Apart from that, different posttreatment methods such as annealing and etching can be used to modify the bulk or surface structure of perovskite oxides. For acidic OER, the current range of catalysts with high activity and stability is limited and mainly focused on noble metals. The main optimization strategy is to reduce the proportion of noble metals through A-site and B-site doping to save costs while maintaining high activity.

PEROVSKITE OXIDES IN ORR

ORR mechanisms

O₂ adsorption is the first step during the ORR process and generally exhibits three possible adsorption configurations on perovskite oxides: end-on, bidentate, and side-on (Fig. 5A) (88, 89). Because ORR (4 e⁻) is the reverse process of OER, there are many similarities in their mechanisms. The end-on adsorption mechanism corresponds to the AEM of OER, wherein one oxygen atom from the O₂ adsorbs onto the catalyst surface and subsequently reacts with hydrated hydrogen ions (H₃O⁺) in acidic media or H₂O in alkaline media to form OOH_ads, ultimately converting into water or OH⁻(90). The bidentate adsorption mechanism corresponds to the reverse process of LOM, in which O₂ adsorbs at the B-site and adjacent oxygen vacancies (91, 92). Last, the side-on adsorption mechanism is the reverse process of OPM, where two oxygen atoms of the O₂ adsorb simultaneously on the catalyst surface and directly dissociate to form two O_ads species (93). Unlike OER, the widely accepted mechanisms for ORR involve side-on adsorption and end-on adsorption, which might be attributed to notable differences in the rate-determining step between ORR and OER, such as the desorption of oxygen, which is an easy step in OER but the reverse step is usually difficult in ORR (22).

Fig. 5. — (A) Three possible O₂ adsorption configurations during ORR, including end-on, bidentate, and side-on. The deep blue and red spheres represent lattice oxygen and electrolyte oxygen, respectively. (B) Schematic diagram of a gas diffusion electrode for ORR. (C and D) The roles of electronic structure and oxygen vacancies in ORR performance of perovskite oxides. The deep blue, dark gray, and red spheres represent A-site, B-site, and O, respectively. (E) The correlation between oxygen vacancy formation energy (eV) and ORR activity of perovskite oxides. (F) The correlation between band center and ORR activity of perovskite oxides. The red and blue triangles refer to the bottom x-axis and top x-axis data, respectively. The formation energy of oxygen vacancy, band center, and activity data for different perovskite oxide catalysts in (E) and (F) are collected from previous studies (*107*, *180*). (G) The influence of the conductive network on the ORR activity of perovskite oxides (*119*). (H) Illustration of oxygen species migration during ORR. (I) Influence of the conductive network on ORR.

Furthermore, for the 2 e⁻ ORR process, the peroxide intermediate could detach from the catalyst surface (OOH_ads → OOH⁻) and react in the electrolyte (OOH⁻ → OH⁻ + 1/2 O₂) (94–96). Perovskite oxide catalysts used for ORR are primarily in alkaline media, the detachment of OOH_ads may occur, resulting in low efficiency for the 2 e⁻ process. Identifying and quantifying the 4 e⁻ and 2 e⁻ pathways in ORR is important, and it is typically determined using techniques such as the electrochemical method (recording the current generated during the electrochemical reduction of hydrogen peroxide) or oxygen sensing method (measuring the oxygen produced over a certain period) (97–100). In addition to the differences in mechanism, ORR requires more complex test conditions compared to the OER as it involves a gas reactant (101). It is necessary to ensure a sufficient supply of O₂ to the catalysts’ surface. Therefore, ORR experiments are typically conducted using rotating ring-disk electrodes or gas diffusion electrodes (Fig. 5B), which facilitate mass transport (102, 103).

Key factors affecting ORR

From the perspective of catalytic sites, perovskite oxide surface consist of BO₅ or BO₄ sites, as described previously (104, 105). The electronic orbitals of the B-site in BO₅ or BO₄ sites split into multiple orbitals, the high-energy e_g orbitals and low-energy t_2g orbitals, to ensure minimum electron repulsion (Fig. 5C) (106). For both OER and ORR, adsorbates prefer a tilted configuration, allowing their π orbital to overlap with the e_g orbital of B-site, forming stable adsorption (9). Orbital descriptors for OER were proposed by researchers in 2011 (26). Subsequent studies revealed that surface reconstruction and amorphization may occur rapidly during the OER process for some perovskite oxides (37, 64, 82). This suggests that the origin of activity may not solely stem from the original perovskite oxide and thus indicates the limitations of the orbital descriptor for OER based on the initial structure of perovskite oxides. Descriptors related to the perovskite oxide orbital theory have also been reported for ORR in 2011 (107). Conversely, during the ORR process, although surface evolution may also occur for perovskite oxides, it is relatively more stable than in the case of OER. Therefore, there has been extensive research on orbital descriptors in the ORR, revealing that a moderate filling degree of the e_g orbitals is beneficial for the ORR process (105, 107–109).

Oxygen vacancies on perovskite oxides are quite important for ORR, which can influence the ORR performance in multiple ways (28, 110, 111) (Fig. 5D). These include providing adsorption sites for O₂, promoting the bidentate adsorption mechanism, altering the electronic structure and band center of perovskite oxides, and modifying conductivity (28). Oxygen vacancies also play a similar role in other fields, but there are differences. For example, in photocatalysis, oxygen vacancies mainly play roles in extending the light absorption range and promoting charge-carrier separation (112). We have summarized the relationship between the formation energy of oxygen vacancy and ORR performance for perovskite oxides (Fig. 5E). Although there is no obvious linear relationship, the presence of oxygen vacancies tends to enhance the activity of perovskite oxides with Mn, Co, Ni, Fe, and Cr. This suggests that oxygen vacancies could be a critical factor in determining the ORR performance of perovskite oxides. Beyond ORR, there are also numerous reports indicating the beneficial effect of oxygen vacancies on OER activity (113–115). While the rate-determining steps of ORR and OER are usually opposite, it is often observed that oxygen vacancies in the same type of perovskite can simultaneously enhance the activity of both ORR and OER. This suggests that the influence of oxygen vacancies on OER and ORR goes beyond a simple electronic modulation mechanism. It could also improve conductivity or increase exposure of active sites. We have also examined the correlation between the M 3d and O 2p band centers and ORR activity of some typical perovskite oxides (Fig. 5F). It can be observed that the O 2p center does not exhibit a clear linear relationship with ORR activity. This is because the potential range of ORR is insufficient to induce significant leaching or reconstruction of perovskite oxides, or the new reconstructed phases do not contribute to ORR activity. Similarly, the M 3d center does not show a distinct linear correlation with activity, further indicating the complexity of the rate-determining step in ORR, making it challenging to optimize adsorption energy to enhance the ORR activity.

For ORR activity of perovskite oxide catalysts, it is also essential to consider electron transfer factors. Integrating perovskite oxides with carbons represents an effective strategy for augmenting ORR performance (116–118). Intriguingly, the ORR activity of perovskite oxides can be enhanced more than 10 times after mixing with carbons (Fig. 5G) (119). However, this hybrid strategy does not exhibit a substantial influence on OER (120). Some researchers believe that the impressive enhancement in ORR activity involves synergistic catalytic effects between perovskite oxides and carbons (121, 122). A viewpoint, for example, is that O₂ is adsorbed on the carbon site, and the resulting peroxide species are subsequently transferred to the perovskite oxide surface for further reaction (Fig. 5H) (123, 124). Of course, it is also suggested that the primary role of carbon is to establish a continuous network throughout the perovskite oxide particles, enhancing conductivity and reducing the “dead region” (Fig. 5I) (125).

Catalyst design for ORR

For the design of perovskite oxide catalysts toward ORR, it is crucial to select B-site metals with high activity, tune the oxygen vacancy concentration and orbital (e_g) filling degree, and choose an appropriate conductive network to achieve highly efficient and stable ORR. Currently, non-noble metals such as Fe, Cr, Ni, Co, and Mn have shown potential in ORR activity. Noble metals like Pt and Pd present challenges in preparing high-performance oxides. For the filling degree of e_g orbitals, control can be achieved through doping and substitution at different sites or by modulating the electron distribution of the BO₆ octahedron associated with the Jahn-Teller effect. Oxygen vacancies, as an important factor, can be easily regulated by substituting A-sites or using nonstoichiometry method. Furthermore, using different atmospheres (such as N₂, Ar, H₂, etc.) may facilitate the migration of active lattice oxygen from the crystal surface, thus creating oxygen vacancies. Last, designing efficient electrolyzers and using efficient conductive carbon networks can significantly enhance ORR performance.

PEROVSKITE OXIDES IN HER

HER mechanisms

HER involves two typical mechanisms, namely, the Volmer-Heyrovsky and the Volmer-Tafel mechanisms (126). Perovskite oxides are commonly used for alkaline HER, and here, we illustrate the alkaline HER mechanism (Fig. 6A). The first step, known as the Volmer step, involves the dissociation of a water molecule followed by the H adsorption on the catalyst surface, resulting in the formation of H_ads. In the Heyrovsky mechanism, H_ads reacts with a water molecule in the electrolyte and releases H₂. In the Tafel mechanism, two adjacent H_ads species are required, similar to the OPM discussed earlier in OER, where two H_ads couple into H₂. The widely accepted method for determining the HER mechanism is to examine the Tafel slope, which represents the change in potential per decade of current density (127). The Tafel slope is theoretically derived from the Butler-Volmer equation for three limiting cases (128). The rate-determining steps for Tafel, Heyrovsky, and Volmer steps correspond to Tafel slopes of 29, 38, and 116 mV dec⁻¹, respectively.

Fig. 6. — (A) Volmer-Heyrovsky and Volmer-Tafel mechanisms of HER. The deep blue, red, and white spheres represent lattice oxygen, electrolyte oxygen, and H, respectively. (B to D) Pure perovskite oxides, perovskite oxides mixture, and reconstructed perovskite oxides for HER. The deep blue, dark gray, red, white, and other spheres represent A-site, B-site, O, H, and active phase, respectively. (E) Reaction pathways of two HER mechanisms on the surface of perovskite oxides. (F) Possible reaction pathways of HER over perovskite oxides with reconstructed surface. (G) Relationship between the ΔG_H of B-site metals and HER performance for perovskite oxides (30, *133*, *134*, *137*, *181*–*196*). The ΔG_H of metals and the activity data for different perovskite oxide catalysts are collected from previous studies (*197*–*199*). The gray horizontal bar represents the range of reported ΔG_H, and the dashed line indicates the midpoint of the gray bar. The red circles and blue triangles represent the catalysts with the highest reported HER activity and other perovskite oxide catalysts with lower activity, respectively. The gray dashed arrows represent possible surface structure of the corresponding perovskite oxides during HER.

Perovskite oxides are generally not considered ideal catalysts for HER because many metal oxides exhibit a relatively high-energy barrier of H adsorption. This characteristic renders the initial H adsorption step challenging, with the Volmer step becoming the rate-determining step (129–131). Despite this limitation of individual perovskite oxide catalysts, high HER activity can be achieved by forming two-phase mixtures through a hybrid method (Fig. 6, B and C) (132). However, in this approach, perovskite oxides are generally not the direct catalytic phase but serve as a support or cocatalyst. From the perspective of perovskite oxide catalyst design, this approach holds limited significance. Another scenario involves surface reconstruction processes of perovskite oxides, in which the B-site metal can be reduced to clusters or nanoparticles anchored on the surface under low-potential HER conditions (Fig. 6D) (133–137). In this case, if the B-site metal clusters or nanoparticles exhibit high HER activity, then the HER activity of perovskite oxides will be significantly enhanced. This strategy holds substantial promise for designing high-performance perovskite oxide HER catalysts.

Key factors affecting HER

We now turn to the factors influencing the HER activity of perovskite oxides. Compared to noble metals such as Pt and Ru, perovskite oxides typically have adjacent active sites with greater distance between the sites. The Tafel mechanism, which requires the simultaneous coupling of two H_ads at adjacent B-site, is theoretically challenging for perovskite oxides, making the Heyrovsky mechanism relatively easier to occur (Fig. 6E) (129). However, as mentioned earlier regarding surface reconstruction, the newly formed surface of perovskite oxides is far more complex than the original ABO₃ structure, and it is likely to form heterostructures such as B-cluster/ABO₃ by A-site and O leaching (Fig. 6F). In this case, two possible mechanisms emerge. The first one is the interfacial reaction between perovskite oxides and metal clusters. This phenomenon was found by researchers in 2011, where the interfacical reaction between Ni(OH)₂ and Pt significantly enhanced HER activity (138). In this way, perovskite oxides could preferentially adsorb OH species, while metal clusters are responsible for H adsorption, achieving synergistic water dissociation. In addition, HER can also occur on the surface of metal clusters, while perovskite oxides mainly serve as electron transfer support or modify the electronic structure of metal clusters.

We conduct an analysis of the HER activity of perovskite oxides based on different B-site metals and their corresponding ΔG_H values (Fig. 6G). Note that ΔG_H close to 0 eV suggests high HER performance due to the favorable adsorption and desorption of H species (139). It is clear that the overall activity trend follows the ΔG_H pattern of the B-site metals. This suggests that the HER performance of perovskite oxides greatly depends on the B-site metal, specifically the reconstructed B-site metal clusters or nanoparticles. Significant differences in HER performance can also be observed for perovskite oxides containing the same B-site, which may be attributed to variations in the surface stability of these perovskite oxides during the HER process. This approach is also suitable for screening HER catalysts in a wide range of materials with surface reconstruction. For example, layered perovskite oxide Sr₂RuO₄ and other oxides such as La₂Sr₂PtO_7+δ exhibit excellent HER activity because the ΔG_H values of Ru and Pt are close to 0 eV (140, 141).

Catalyst design for HER

Although perovskite oxides are not ideal catalysts for HER, their performance can be significantly enhanced through surface reduction and reconstruction. To design highly efficient perovskite oxides for HER, it is important to consider the ΔG_H or HER activity of clusters or nanoparticles derived from the B-site metals and then regulate the A-site to facilitate rapid reduction and activation of the B-site metals. The current research focuses on noble metal Ru-based perovskite oxides with high activity, particularly SrRuO₃, because of its relatively simple synthesis and its tendency to undergo reconstruction during the HER process. The present research direction aims to reduce the loading of Ru and control the structure of RuO_x after reconstruction. In addition to electrochemical reduction, high-activity Ru-based perovskite catalysts can be directionally synthesized through other reduction methods such as using a reducing atmosphere or reducing agents. For perovskite oxides featuring non-noble metal at the B-site, because of the intrinsic activity limits of the metal itself (ΔG_H is usually too high or too low), the most direct approach is to load high-activity sites such as Pt and Ru clusters to achieve synergistic catalysis.

PEROVSKITE OXIDES IN OTHER REACTIONS

Research progress in other reactions

In addition to O-related chemical transformations, perovskite oxides have wide applications in various other electrocatalytic reactions (9, 27). Because of the more complex catalytic mechanisms of these reactions compared to O-related chemical transformations, the following discussion primarily focuses on the research progress in the related field. For NRR, perovskite oxides primarily include those with Fe, Co, and Cr at the B-site (142–146). Given the similarities between N–N bond cleavage in NRR and O–O bond cleavage in ORR, oxygen vacancies in perovskite oxides have also demonstrated notable impacts on NRR and are currently the main strategy for enhancing performance (31, 147). Moreover, besides NRR, studies have also revealed a clear correlation between the concentration of oxygen vacancies and the activity of perovskite oxides in NO₃⁻ reduction reaction (148, 149). Because of the close potential between N-related reduction reactions and HER, it is possible that metal clusters or nanoparticles may also form on the surface of perovskite oxides. Further research and characterizations are required to ascertain how oxygen vacancies enhance activity, such as by modulating electronic structure, enhancing conductivity, or accelerating the surface reduction of perovskite oxides to metal clusters.

Perovskite oxides with Cu and Sn at the B-site are mainly used for CO₂RR (150, 151). Because of the challenge of synthesizing pure phases of Cu-based perovskite oxides, such as LaCuO₃, researchers often use layered perovskite La₂CuO₄ as the catalyst for CO₂RR (152–155). It has been found that La₂CuO₄ undergoes surface reduction to Cu₂O and Cu, ultimately forming a Cu(Cu₂O)/La₂CuO₄ heterostructure, which enables efficient CO₂RR (153). These findings further underscore the significance of the surface reconstruction behavior for the reduction reactions over perovskite oxides. In addition to these reduction reactions, there are some reports of small-molecule oxidation reactions such as UOR. Similar to the aforementioned reactions, only a small fraction of B-site metals exhibits high activity. For UOR, only Ni-based perovskite oxides show high activity (33). Notably, although the oxidation potential of urea is lower than that of OER, the Ni species at the B-sites may evolve into NiO_xH_y attached to perovskite oxide and contribute to UOR activity. This point is partially supported by the excellent UOR performance of NiOOH (156, 157). However, it is still challenging to conclusively determine whether the catalytic activity is due to the perovskite oxide itself or to the NiO_xH_y derived from surface reconstruction. In brief, perovskite oxides show great potential for N- and C-related electrocatalytic reactions. Further research is needed to elucidate the underlying mechanisms, especially the role of surface reconstruction and the influence of specific B-site metals on catalytic performance.

Surface evolution trends during reactions

We have illustrated a simplified Pourbaix diagram using LaCoO₃ as a representative example (Fig. 7A). Most perovskite oxides exhibit limited acid resistance (except Ir- and Ru-based ones) and decompose into metal ions below a certain pH value (158). At excessively high potentials, the surface of perovskite oxides can undergo structural transformations, such as the transition from corner-sharing BO₆ to edge-sharing BO₆. This phenomenon is particularly evident in the OER for many perovskite oxides (37). At moderate potentials, the surface structure of most perovskite oxides remains relatively stable. However, surface reduction to metallic clusters or nanoparticles can occur at very low potentials. This has been confirmed for perovskite oxides containing Ir, Ru, and Cu (136, 137, 153, 159).

We have summarized the potential ranges for different catalytic reactions and the possible surface evolution that may occur on perovskite oxides (Fig. 7, B and C), which provide insights into the surface transformation of perovskite oxides. For reduction reactions, it is crucial to investigate the valence states of the catalyst surface and the formation of metal clusters or nanoparticles. The performance improvement or deterioration after the formation of new phases can be analyzed from different perspectives, such as electronic effects and catalytic site changes, to elucidate the catalytic mechanism. Electronic effects involve changes in electron distribution and adsorption energy of adsorbates due to heterostructure modifications between the newly formed phases and perovskite oxides. Catalytic site changes involve the new active phase acting as the primary catalytic site or synergistic catalysis with perovskite oxides. In the case of reactions at moderate potentials, such as ORR, surface evolution should also be considered. Some researchers have observed the amorphization of perovskite oxide surface during ORR processes. This amorphization phenomenon involves more than simple reduction or oxidation and requires characterization of the resulting surface to reveal its composition, structure, and elemental valence states (160, 161). For oxidation reactions, it is necessary to examine the oxidation states of the catalyst surface. In many cases, the reconstruction of perovskite oxides does not necessarily increase the oxidation state of the B-site metal (37, 64, 83). In such instances, it is crucial to identify the structure and composition of newly formed surface using surface-sensitive characterization techniques. Only by understanding the true active components of perovskite oxides during catalysis can the mechanisms be validated. The surface reconstruction in most reactions remains unclear; we should shift our focus to the surface stability and structural transformations of perovskite oxides, which is also one of the key points emphasized in this review.

CHARACTERIZATIONS AND RESEARCH FRAMEWORK

Identifying active sites by characterizations

Identifying active sites and studying catalytic mechanisms rely on appropriate characterization techniques. Through these in situ/ex situ characterizations, molecular and atomic level information during electrocatalytic processes can be tracked to explain the observed activity and stability (162–164). In the following sections, we will introduce various types of in situ/ex situ characterization techniques, focusing on perovskite oxide catalysts from four aspects: bulk structure, surface/interface, electrolyte, and gas phase above the electrolyte (Fig. 8A).

Fig. 8. — (A) Overview of complementary characterization techniques related to the bulk structure of the catalyst, interface between the catalyst surface and electrolyte, electrolyte, and gas phase. GC-MS, gas chromatography–mass spectrometry; ICP, inductively coupled plasma; LC-MS, liquid chromatography–mass spectrometry; NMR, nuclear magnetic resonance; XRD, x-ray diffraction; XAS, x-ray absorption spectroscopy; FTIR, Fourier transform infrared spectroscopy; AFM, atomic force microscopy; XPS, x-ray photoelectron spectroscopy; SECM, scanning electrochemical microscopy; EPR, electron paramagnetic resonance; EDX, energy-dispersive x-ray spectroscopy; SIMS, secondary ion mass spectrometry. (B) Pathway for designing high-activity, high-stability, and low-cost perovskite oxide electrocatalysts. The deep blue, dark gray, and red spheres represent A-site, B-site, and O, respectively.

First, characterization of the bulk structure of perovskite oxides is essential because different perovskite phases, for example, the hexagonal phase and trigonal phase of SrIrO₃, exhibit significant differences in activity and stability (165). X-ray diffraction (XRD) and refined XRD are important techniques for analyzing the perovskite crystal structure. Oxygen vacancies are crucial characteristics of perovskite oxides, and electron paramagnetic resonance (EPR) is an effective method for preliminary assessment of the presence of oxygen vacancies (113). Oxygen vacancies can also be determined using techniques such as Mössbauer spectroscopy, x-ray photoelectron spectroscopy (XPS), and the iodometric titration method (77, 166, 167). In addition, energy-dispersive x-ray spectroscopy (EDX) and XPS can be used to roughly estimate the proportions of A-site and B-site elements in perovskite oxides (19). However, a more accurate method is to completely dissolve the perovskite oxide in acid and then use the inductively coupled plasma (ICP) method to determine the elemental content (63). Secondary ion mass spectrometry (SIMS) can identify the elements in the bulk and surface of perovskite oxides. For example, after conducting OER in electrolytes labeled with ¹⁸O, the oxygen isotope ratio in the shallow surface region and the bulk of perovskite oxides can be determined using SIMS (71, 157). These characterizations greatly assist in analyzing the composition and properties of the bulk phases of perovskite oxides and are crucial for understanding the structure of perovskite oxides before and after reactions.

Next is the most important aspect: surface/interface characterizations, which include a wide range of in situ techniques used for understanding surface evolution and catalytic mechanisms of perovskite oxides. In situ characterizations have substantial advantages over conventional methods as they allow real-time observation of structural evolution in the catalyst or changes in adsorbates during the reactions. In situ Raman spectroscopy and in situ Fourier transform infrared spectroscopy (FTIR) are commonly used to examine the coverage and concentration of intermediates or changes in the surface structure of the catalyst. For example, in situ Raman spectroscopy is used to monitor structural evolution and new phase evolution during the OER on perovskite oxides (168, 169). In situ XRD and in situ x-ray absorption spectroscopy (XAS) are effective methods for characterizing structural evolution in perovskites. In situ XRD provides information about phase transitions during catalysis, while in situ XAS reveals the coordination environment of B-site metals and oxygen, allowing for the determination of structural changes in the BO₆ structure of perovskite oxides. For example, a decrease in the coordination number of O surrounding B-site indicates the reduction of B-site metal, which may be attributed to lattice oxygen leaching (83).

In addition to these in situ characterizations, in situ atomic force microscopy (AFM) can monitor the surface reconstruction of catalysts, such as the Sr leaching on SrIrO₃ during the OER (86). Scanning electrochemical microscopy (SECM) can investigate the local information of the catalyst surface at the nanoscale, encompassing intermediates, active sites, and kinetic rates, such as identifying the active sites of CaMnO₃ during OER (170). In situ XPS plays a vital role in analyzing oxidation states, particularly in identifying reconstructed structures such as MOOH and metallic M (M refers to transition metals such as Co and Ni) (171). Notably, in situ characterizations require the assembly of specially designed in situ electrochemical cells. For spectrum-related in situ characterizations, quartz or thin films are used to minimize light scattering and absorption. Gaseous reactants or products involved in the catalytic reactions can interfere with in situ experiments. For example, in situ Raman spectroscopy can be greatly affected by the interference of bubbles, which impede the laser focusing and severely affect the signal acquisition. Moreover, because of the complexity of the in situ experimental cells, thorough cleaning is required before and after use to avoid potential impurities. Impurities in the electrolyte, such as Fe-based impurities, which can significantly enhance the OER performance of perovskite oxides, are easily overlooked (63).

Electrolyte characterizations focus on the detection of reaction products (such as the methanol and ammonia produced by CO₂RR and NRR, respectively) or leaching species of perovskite oxides during the catalytic processes. Among these characterizations, in situ ICP can serve as direct evidence of A-site or B-site leaching in perovskite oxides. Last, the gaseous products or volatile intermediates during the catalytic processes can be detected by characterizing the gas phase above the electrolyte. For example, gaseous OER products such as the ¹⁸O¹⁶O species in the LOM process and volatile intermediates such as NO, NOH, and NH₂OH in the NRR process can be characterized using DEMS (58, 63). These characterizations also greatly contribute to elucidating the catalytic mechanisms.

Research framework

Currently, perovskite oxide electrocatalysts face two key challenges: understanding the catalytic mechanisms and achieving highly efficient and stable performance. Addressing these challenges requires a comprehensive research framework (Fig. 8B). Machine learning has emerged as a promising approach for materials screening. Given the numerous structural possibilities of perovskite oxides, it is impractical to verify all of them experimentally. Machine learning combined with theoretical calculations enables the prediction of the structural stability of new perovskite oxides (25, 172). Moreover, simple descriptors such as M 3d band center, O 2p band center, and oxygen vacancy formation energy can be used to screen out potentially highly active perovskite oxide candidates. This approach has already been reported for other types of oxides, such as spinel oxides (173). Once the targeted perovskite oxides have been determined, appropriate synthesis and characterization methods are required. Many synthesis methods yield perovskite oxides that are not in a single phase, and the crystal structure may also vary under different quenching conditions. Therefore, rigorous characterizations are necessary to study the structural features of perovskite oxides, such as the crystal structure, the proportions of A-site and B-site elements, and the presence of oxygen vacancies.

After a comprehensive activity evaluation, the structural characterization of the perovskite oxide catalysts, especially the surface structure, needs to be re-evaluated. High-throughput theoretical calculations such as DFT and AIMD can be used to analyze enhanced activity or stability. To achieve a more accurate integration of theory and experiment, in addition to the original perovskite oxide structure, in situ characterization methods and Pourbaix diagram analysis should be combined to determine the potential surface structures of perovskite oxides during the catalytic processes, which can further guide theoretical calculations. Last, the assembly of devices for catalytic systems is necessary to evaluate the activity and stability of perovskite oxide catalysts under more realistic conditions.

CONCLUSIONS AND PERSPECTIVES

This review delves deeply into the mechanisms of perovskite oxides in electrocatalytic reactions and highlights potential key factors affecting the catalytic activity of various reactions. We have shown that structural evolution due to surface leaching or reconstruction of perovskite oxides require attention. In addition, this review outlines advanced characterization methods used to study catalytic mechanisms and proposes strategies for designing efficient perovskite oxide electrocatalysts.

Despite substantial achievements of perovskite oxide catalysts in several reactions, breakthroughs are still needed in the study of catalytic mechanisms and commercial applications. Taking the LOM of OER as an example, perovskite oxides, one of the earliest materials studied for this mechanism, have received extensive attention over the past 5 years. However, there are no definitive conclusions regarding the rate-determining step descriptor and transition states (from OH_ads to O₂), and related testing methods pose challenges in terms of detection precision. Moreover, the chemical transformation mechanisms involving C and N are more complex, relying on advancements in theoretical calculations and in situ characterizations. In terms of applications, perovskite oxides have shown high activity and stability in certain reactions (e.g., SrIrO₃ for acidic OER and SrRuO₃ for alkaline HER), but the performance of most non-noble metal perovskite oxides remains unsatisfactory, highlighting the need for further improvements in catalyst design.

The highly tunable structure of perovskites makes their synthesis exploration challenging. With the rapid development of artificial intelligence (AI) and machine learning, these technologies can be used in material design to simplify the prediction and screening process of materials. The B-site of perovskite oxides is the primary catalytic site, and AI tools and large databases (such as ChatGPT, despite many erroneous conclusions at the current stage) can identify high-activity transition metals for the B-site in specific reactions (e.g., Ni and Fe for OER, Pt and Ru for HER, and Cu for CO₂RR). Theoretical calculations combined with machine learning can effectively screen thermodynamically stable A-site, aiding in the prediction of ABO₃ stability and catalytic activity through Pourbaix diagrams and high-throughput theoretical calculations.

Improving in situ experiments is crucial for in-depth research on the mechanisms of perovskite oxides. Current important in situ characterizations such as XAS and Raman spectroscopy suffer from spatial resolution deficiencies. Because most perovskite oxides undergo changes in only a few surface atomic layers during catalysis, there may be errors in determining the active phase. It is necessary to develop spatially resolved XAS and high-precision in situ Raman mapping methods to accurately obtain the active phase. The combination of theoretical research and experimental characterizations will enrich the application of perovskite oxides in electrocatalysis, especially in C- and N-related chemical transformations. This will help build descriptors and study mechanisms while also potentially developing catalysts with high commercial value.

Acknowledgments

Funding: J.-W.Z. acknowledges the funding support from Hong Kong Innovation and Technology Commission via the Hong Kong Branch of National Precious Metals Material Engineering Research Center.

Author contributions: J.-W.Z., Y.L., D.L., and X.W.L. conceived the topic of this review. J.-W.Z. wrote the initial draft. Y.L., D.L., and X.W.L. made revisions. X.W.L. supervised the writing of the manuscript.

Competing interests: The authors declare that they have no competing interests.

Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials.

REFERENCES AND NOTES

1.Chu S., Majumdar A., Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012). [DOI] [PubMed] [Google Scholar]
2.Debe M. K., Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012). [DOI] [PubMed] [Google Scholar]
3.Wu H. B., Lou X. W. D., Metal-organic frameworks and their derived materials for electrochemical energy storage and conversion: Promises and challenges. Sci. Adv. 3, eaap9252 (2017). [DOI] [PMC free article] [PubMed] [Google Scholar]
4.IEA, World Energy Outlook (2023); www.iea.org/reports/world-energy-outlook-2023.
5.Pei Z., Zhang H., Luan D., Lou X. W. D., Electrocatalytic acidic oxygen evolution: From catalyst design to industrial applications. Matter 6, 4128–4144 (2023). [Google Scholar]
6.Seh Z. W., Kibsgaard J., Dickens C. F., Chorkendorff I., Nørskov J. K., Jaramillo T. F., Combining theory and experiment in electrocatalysis: Insights into materials design. Science 355, eaad4998 (2017). [DOI] [PubMed] [Google Scholar]
7.Lewis N. S., Nocera D. G., Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl. Acad. Sci. U.S.A. 103, 15729–15735 (2006). [DOI] [PMC free article] [PubMed] [Google Scholar]
8.US Department of Energy, DOE announces goal to cut solar costs by more than half by 2030 (2021); www.energy.gov/articles/doe-announces-goal-cut-solar-costs-more-half-2030.
9.Hwang J., Rao R. R., Giordano L., Katayama Y., Yu Y., Shao-Horn Y., Perovskites in catalysis and electrocatalysis. Science 358, 751–756 (2017). [DOI] [PubMed] [Google Scholar]
10.Xia B. Y., Yan Y., Li N., Wu H. B., Lou X. W., Wang X., A metal-organic framework-derived bifunctional oxygen electrocatalyst. Nat. Energy 1, 15006 (2016). [Google Scholar]
11.Xie J., Zhang H., Li S., Wang R., Sun X., Zhou M., Zhou J., Lou X. W. D., Xie Y., Defect-rich MoS₂ ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv. Mater. 25, 5807–5813 (2013). [DOI] [PubMed] [Google Scholar]
12.Tian X., Zhao X., Su Y.-Q., Wang L., Wang H., Dang D., Chi B., Liu H., Hensen E. J. M., Lou X. W. D., Xia B. Y., Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 366, 850–856 (2019). [DOI] [PubMed] [Google Scholar]
13.Tian X., Lu X. F., Xia B. Y., Lou X. W. D., Advanced electrocatalysts for the oxygen reduction reaction in energy conversion technologies. Joule 4, 45–68 (2020). [Google Scholar]
14.Liu S., Xiao J., Lu X. F., Wang J., Wang X., Lou X. W. D., Efficient electrochemical reduction of CO₂ to HCOOH over sub-2 nm SnO₂ quantum wires with exposed grain boundaries. Angew. Chem. Int. Ed. Engl. 58, 8499–8503 (2019). [DOI] [PubMed] [Google Scholar]
15.Appel A. M., Bercaw J. E., Bocarsly A. B., Dobbek H., DuBois D. L., Dupuis M., Ferry J. G., Fujita E., Hille R., Kenis P. J., Kerfeld C. A., Morris R. H., Peden C. H. F., Portis A. R., Ragsdale S. W., Rauchfuss T. B., Reek J. N. H., Seefeldt L. C., Thauer R. K., Waldrop G. L., Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO₂ fixation. Chem. Rev. 113, 6621–6658 (2013). [DOI] [PMC free article] [PubMed] [Google Scholar]
16.Chen J. G., Crooks R. M., Seefeldt L. C., Bren K. L., Bullock R. M., Darensbourg M. Y., Holland P. L., Hoffman B., Janik M. J., Jones A. K., Kanatzidis M. G., King P., Lancaster K. M., Lymar S. V., Pfromm P., Schneider W. F., Schrock R. R., Beyond fossil fuel-driven nitrogen transformations. Science 360, eaar6611 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]
17.Foster S. L., Bakovic S. I. P., Duda R. D., Maheshwari S., Milton R. D., Minteer S. D., Janik M. J., Renner J. N., Greenlee L. F., Catalysts for nitrogen reduction to ammonia. Nat. Catal. 1, 490–500 (2018). [Google Scholar]
18.Zhu P., Wang H., High-purity and high-concentration liquid fuels through CO₂ electroreduction. Nat. Catal. 4, 943–951 (2021). [Google Scholar]
19.Seitz L. C., Dickens C. F., Nishio K., Hikita Y., Montoya J., Doyle A., Kirk C., Vojvodic A., Hwang H. Y., Norskov J. K., Jaramillo T. F., A highly active and stable IrO_x/SrIrO₃ catalyst for the oxygen evolution reaction. Science 353, 1011–1014 (2016). [DOI] [PubMed] [Google Scholar]
20.Pei Z., Zhang H., Wu Z.-P., Lu X. F., Luan D., Lou X. W., Sci. Adv. 9, Atomically dispersed Ni activates adjacent Ce sites for enhanced electrocatalytic oxygen evolution activity, eadh1320 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]
21.Ren Y., Li S., Yu C., Zheng Y., Wang C., Qian B., Wang L., Fang W., Sun Y., Qiu J., NH₃ electrosynthesis from N₂ molecules: Progresses, challenges, and future perspectives. J. Am. Chem. Soc. 146, 6409–6421 (2024). [DOI] [PubMed] [Google Scholar]
22.Zhao Y., Adiyeri Saseendran D. P., Huang C., Triana C. A., Marks W. R., Chen H., Zhao H., Patzke G. R., Oxygen evolution/reduction reaction catalysts: From in situ monitoring and reaction mechanisms to rational design. Chem. Rev. 123, 6257–6358 (2023). [DOI] [PubMed] [Google Scholar]
23.M. De Graef, M. E. McHenry, Structure of Materials: An Introduction to Crystallography, Diffraction and Symmetry (Cambridge Univ. Press, 2012). [Google Scholar]
24.Peña M. A., Fierro J. L., Chemical structures and performance of perovskite oxides. Chem. Rev. 101, 1981–2018 (2001). [DOI] [PubMed] [Google Scholar]
25.Filip M. R., Giustino F., The geometric blueprint of perovskites. Proc. Natl. Acad. Sci. U.S.A. 115, 5397–5402 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]
26.Suntivich J., May K. J., Gasteiger H. A., Goodenough J. B., Shao-Horn Y., A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334, 1383–1385 (2011). [DOI] [PubMed] [Google Scholar]
27.Yin W.-J., Weng B., Ge J., Sun Q., Li Z., Yan Y., Oxide perovskites, double perovskites and derivatives for electrocatalysis, photocatalysis, and photovoltaics. Energ. Environ. Sci. 12, 442–462 (2019). [Google Scholar]
28.Ji Q., Bi L., Zhang J., Cao H., Zhao X. S., The role of oxygen vacancies of ABO₃ perovskite oxides in the oxygen reduction reaction. Energ. Environ. Sci. 13, 1408–1428 (2020). [Google Scholar]
29.Zhao J.-W., Shi Z.-X., Li C.-F., Ren Q., Li G.-R., Regulation of perovskite surface stability on the electrocatalysis of oxygen evolution reaction. ACS Mater. Lett. 3, 721–737 (2021). [Google Scholar]
30.Xu X., Chen Y., Zhou W., Zhu Z., Su C., Liu M., Shao Z., A perovskite electrocatalyst for efficient hydrogen evolution reaction. Adv. Mater. 28, 6442–6448 (2016). [DOI] [PubMed] [Google Scholar]
31.Chu K., Liu F., Zhu J., Fu H., Zhu H., Zhu Y., Zhang Y., Lai F., Liu T., A general strategy to boost electrocatalytic nitrogen reduction on perovskite oxides via the oxygen vacancies derived from A-site deficiency. Adv. Energy Mater. 11, 2003799 (2021). [Google Scholar]
32.Hwang J., Akkiraju K., Corchado-García J., Shao-Horn Y., A perovskite electronic structure descriptor for electrochemical CO₂ reduction and the competing H₂ evolution reaction. J. Phys. Chem. C 123, 24469–24476 (2019). [Google Scholar]
33.Forslund R. P., Mefford J. T., Hardin W. G., Alexander C. T., Johnston K. P., Stevenson K. J., Nanostructured LaNiO₃ perovskite electrocatalyst for enhanced urea oxidation. ACS Catal. 6, 5044–5051 (2016). [Google Scholar]
34.Lan A., Mukasyan A. S., Perovskite-based catalysts for direct methanol fuel cells. J. Phys. Chem. C 111, 9573–9582 (2007). [Google Scholar]
35.Grimaud A., May K. J., Carlton C. E., Lee Y.-L., Risch M., Hong W. T., Zhou J., Shao-Horn Y., Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution. Nat. Commun. 4, 2439 (2013). [DOI] [PubMed] [Google Scholar]
36.Yoo J. S., Rong X., Liu Y., Kolpak A. M., Role of lattice oxygen participation in understanding trends in the oxygen evolution reaction on perovskites. ACS Catal. 8, 4628–4636 (2018). [Google Scholar]
37.Risch M., Grimaud A., May K. J., Stoerzinger K. A., Chen T. J., Mansour A. N., Shao-Horn Y., Structural changes of cobalt-based perovskites upon water oxidation investigated by EXAFS. J. Phys. Chem. C 117, 8628–8635 (2013). [Google Scholar]
38.Song H. J., Yoon H., Ju B., Kim D.-W., Highly efficient perovskite-based electrocatalysts for water oxidation in acidic environments: A mini review. Adv. Energy Mater. 11, 2002428 (2021). [Google Scholar]
39.Sun C. W., Alonso J. A., Bian J. J., Recent advances in perovskite-type oxides for energy conversion and storage applications. Adv. Energy Mater. 11, 2000459 (2021). [Google Scholar]
40.Wang K., Han C., Shao Z. P., Qiu J. S., Wang S. B., Liu S. M., Perovskite oxide catalysts for advanced oxidation reactions. Adv. Funct. Mater. 31, 2102089 (2021). [Google Scholar]
41.Zeng Z., Xu Y., Zhang Z., Gao Z., Luo M., Yin Z., Zhang C., Xu J., Huang B., Luo F., Du Y., Yan C., Rare-earth-containing perovskite nanomaterials: Design, synthesis, properties and applications. Chem. Soc. Rev. 49, 1109–1143 (2020). [DOI] [PubMed] [Google Scholar]
42.Li X., Zhao H., Liang J., Luo Y., Chen G., Shi X., Lu S., Gao S., Hu J., Liu Q., A-site perovskite oxides: An emerging functional material for electrocatalysis and photocatalysis. J. Mater. Chem. A 9, 6650–6670 (2021). [Google Scholar]
43.Xu X., Pan Y., Zhong Y., Ran R., Shao Z., Ruddlesden-Popper perovskites in electrocatalysis. Mater. Horiz. 7, 2519–2565 (2020). [Google Scholar]
44.Zhang M., Jeerh G., Zou P., Lan R., Wang M., Wang H., Tao S., Recent development of perovskite oxide-based electrocatalysts and their applications in low to intermediate temperature electrochemical devices. Mater. Today 49, 351–377 (2021). [Google Scholar]
45.Hwang J., Feng Z., Charles N., Wang X. R., Lee D., Stoerzinger K. A., Muy S., Rao R. R., Lee D., Jacobs R., Morgan D., Han Y. S., Tuning perovskite oxides by strain: Electronic structure, properties, and functions in (electro)catalysis and ferroelectricity. Mater. Today 31, 100–118 (2019). [Google Scholar]
46.Liu Y., Huang H., Xue L., Sun J., Wang X., Xiong P., Zhu J., Recent advances in the heteroatom doping of perovskite oxides for efficient electrocatalytic reactions. Nanoscale 13, 19840–19856 (2021). [DOI] [PubMed] [Google Scholar]
47.Xu X., Wang W., Zhou W., Shao Z., Recent advances in novel nanostructuring methods of perovskite electrocatalysts for energy-related applications. Small Methods 2, 1800071 (2018). [Google Scholar]
48.Zhu Y., Zhou W., Shao Z., Perovskite/carbon composites: Applications in oxygen electrocatalysis. Small 13, 1603793 (2017). [DOI] [PubMed] [Google Scholar]
49.Ingavale S., Gopalakrishnan M., Enoch C. M., Pornrungroj C., Rittiruam M., Praserthdam S., Somwangthanaroj A., Nootong K., Pornprasertsuk R., Kheawhom S., Strategic design and insights into lanthanum and strontium perovskite oxides for oxygen reduction and oxygen evolution reactions. Small 20, 2308443 (2024). [DOI] [PubMed] [Google Scholar]
50.Song F., Bai L., Moysiadou A., Lee S., Hu C., Liardet L., Hu X., Transition metal oxides as electrocatalysts for the oxygen evolution reaction in alkaline solutions: An application-inspired renaissance. J. Am. Chem. Soc. 140, 7748–7759 (2018). [DOI] [PubMed] [Google Scholar]
51.Bockris J. O. M., Otagawa T., Mechanism of oxygen evolution on perovskites. J. Phys. Chem. 87, 2960–2971 (2002). [Google Scholar]
52.Wang X., Zhong H., Xi S., Lee W. S. V., Xue J., Understanding of oxygen redox in the oxygen evolution reaction. Adv. Mater. 34, e2107956 (2022). [DOI] [PubMed] [Google Scholar]
53.Man I. C., Su H. Y., Calle-Vallejo F., Hansen H. A., Martínez J. I., Inoglu N. G., Kitchin J., Jaramillo T. F., Nørskov J. K., Rossmeisl J., Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 3, 1159–1165 (2011). [Google Scholar]
54.Yoo J. S., Liu Y., Rong X., Kolpak A. M., Electronic origin and kinetic feasibility of the lattice oxygen participation during the oxygen evolution reaction on perovskites. J. Phys. Chem. Lett. 9, 1473–1479 (2018). [DOI] [PubMed] [Google Scholar]
55.Lin C., Li J.-L., Li X., Yang S., Luo W., Zhang Y., Kim S.-H., Kim D.-H., Shinde S. S., Li Y.-F., In-situ reconstructed Ru atom array on α-MnO₂ with enhanced performance for acidic water oxidation. Nat. Catal. 4, 1012–1023 (2021). [Google Scholar]
56.Tripkovic V., Hansen H. A., Garcia-Lastra J. M., Vegge T., Comparative DFT+U and HSE study of the oxygen evolution electrocatalysis on perovskite oxides. J. Phys. Chem. C 122, 1135–1147 (2018). [Google Scholar]
57.Huang Z.-F., Song J., Du Y., Xi S., Dou S., Nsanzimana J. M. V., Wang C., Xu Z. J., Wang X., Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts. Nat. Energy 4, 329–338 (2019). [Google Scholar]
58.Grimaud A., Diaz-Morales O., Han B., Hong W. T., Lee Y.-L., Giordano L., Stoerzinger K. A., Koper M. T. M., Shao-Horn Y., Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. Nat. Chem. 9, 457–465 (2017). [DOI] [PubMed] [Google Scholar]
59.Zhao J.-W., Zhang H., Li C. F., Zhou X., Wu J.-Q., Zeng F., Zhang J., Li G.-R., Key roles of surface Fe sites and Sr vacancies in the perovskite for an efficient oxygen evolution reaction via lattice oxygen oxidation. Energ. Environ. Sci. 15, 3912–3922 (2022). [Google Scholar]
60.Ferreira de Araújo J., Dionigi F., Merzdorf T., Oh H. S., Strasser P., Evidence of Mars-Van-Krevelen mechanism in the electrochemical oxygen evolution on Ni-based catalysts. Angew. Chem. Int. Ed. 60, 14981–14988 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]
61.Wu Y., Zhao Y., Zhai P., Wang C., Gao J., Sun L., Hou J., Triggering lattice oxygen activation of single-atomic Mo sites anchored on Ni-Fe oxyhydroxides nanoarrays for electrochemical water oxidation. Adv. Mater. 34, e2202523 (2022). [DOI] [PubMed] [Google Scholar]
62.Kim B.-J., Fabbri E., Abbott D. F., Cheng X., Clark A. H., Nachtegaal M., Borlaf M., Castelli I. E., Graule T., Schmidt T. J., Functional role of Fe-doping in Co-based perovskite oxide catalysts for oxygen evolution reaction. J. Am. Chem. Soc. 141, 5231–5240 (2019). [DOI] [PubMed] [Google Scholar]
63.Lopes P. P., Chung D. Y., Rui X., Zheng H., He H., Martins P. F. B. D., Strmcnik D., Stamenkovic V. R., Zapol P., Mitchell J. F., Klie R. F., Markovic N. M., Dynamically stable active sites from surface evolution of perovskite materials during the oxygen evolution reaction. J. Am. Chem. Soc. 143, 2741–2750 (2021). [DOI] [PubMed] [Google Scholar]
64.Fabbri E., Nachtegaal M., Binninger T., Cheng X., Kim B.-J., Durst J., Bozza F., Graule T., Schäublin R., Wiles L., Pertoso M., Danilovic N., Ayers K. E., Schmidt T. J., Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting. Nat. Mater. 16, 925–931 (2017). [DOI] [PubMed] [Google Scholar]
65.Raman A. S., Patel R., Vojvodic A., Surface stability of perovskite oxides under OER operating conditions: A first principles approach. Faraday Discuss. 229, 75–88 (2021). [DOI] [PubMed] [Google Scholar]
66.Kim B.-J., Fabbri E., Borlaf M., Abbott D. F., Castelli I. E., Nachtegaal M., Graule T., Schmidt T. J., Oxygen evolution reaction activity and underlying mechanism of perovskite electrocatalysts at different pH. Mater. Adv. 2, 345–355 (2021). [Google Scholar]
67.Akbashev A., Zhang L., Mefford J. T., Park J., Butz B., Luftman H., Chueh W. C., Vojvodic A., Activation of ultrathin SrTiO₃ with subsurface SrRuO₃ for the oxygen evolution reaction. Energ. Environ. Sci. 11, 1762–1769 (2018). [Google Scholar]
68.Yang C., Batuk M., Jacquet Q., Rousse G., Yin W., Zhang L., Hadermann J., Abakumov A. M., Cibin G., Chadwick A., Tarascon J.-M., Grimaud A., Revealing pH-dependent activities and surface instabilities for Ni-based electrocatalysts during the oxygen evolution reaction. ACS Energy Lett. 3, 2884–2890 (2018). [Google Scholar]
69.Chen Y., Li H., Wang J., Du Y., Xi S., Sun Y., Sherburne M., Ager J. W. III, Fisher A. C., Xu Z. J., Exceptionally active iridium evolved from a pseudo-cubic perovskite for oxygen evolution in acid. Nat. Commun. 10, 572 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]
70.Zhao J.-W., Yue K., Zhang H., Wei S.-Y., Zhu J., Wang D., Chen J., Fominski V. Y., Li G.-R., The formation of unsaturated IrO_x in SrIrO₃ by cobalt-doping for acidic oxygen evolution reaction. Nat. Commun. 15, 2928 (2024). [DOI] [PMC free article] [PubMed] [Google Scholar]
71.Liu J., Jia E., Stoerzinger K. A., Wang L., Wang Y., Yang Z., Shen D., Engelhard M. H., Bowden M. E., Zhu Z., Chambers S. A., Du Y., Dynamic lattice oxygen participation on perovskite LaNiO₃ during oxygen evolution reaction. J. Phys. Chem. C 124, 15386–15390 (2020). [Google Scholar]
72.Zhang N., Chai Y., Lattice oxygen redox chemistry in solid-state electrocatalysts for water oxidation. Energ. Environ. Sci. 14, 4647–4671 (2021). [Google Scholar]
73.Gao L., Cui X., Sewell C. D., Li J., Lin Z., Recent advances in activating surface reconstruction for the high-efficiency oxygen evolution reaction. Chem. Soc. Rev. 50, 8428–8469 (2021). [DOI] [PubMed] [Google Scholar]
74.Luo X., Tan X., Ji P., Chen L., Yu J., Mu S., Surface reconstruction-derived heterostructures for electrochemical water splitting. EnergyChem 5, 100091 (2022). [Google Scholar]
75.Badreldin A., Bouhali O., Abdel-Wahab A., Complimentary computational cues for water electrocatalysis: A DFT and ML perspective. Adv. Funct. Mater. 34, 2312425 (2024). [Google Scholar]
76.Chen G., Zhou W., Guan D., Sunarso J., Zhu Y., Hu X., Zhang W., Shao Z., Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ nanofilms with tunable oxidation state. Sci. Adv. 3, e1603206 (2017). [DOI] [PMC free article] [PubMed] [Google Scholar]
77.Kim N.-I., Sa Y. J., Yoo T. S., Choi S. R., Afzal R. A., Choi T., Seo Y.-S., Lee K.-S., Hwang J. Y., Choi W. S., Joo S. H., Park J.-Y., Oxygen-deficient triple perovskites as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions. Sci. Adv. 4, eaap9360 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]
78.Bak J., Bin Bae H., Chung S.-Y., Atomic-scale perturbation of oxygen octahedra via surface ion exchange in perovskite nickelates boosts water oxidation. Nat. Commun. 10, 2713 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]
79.Tong Y., Wu J., Chen P., Liu H., Chu W., Wu C., Xie Y., Vibronic superexchange in double perovskite electrocatalyst for efficient electrocatalytic oxygen evolution. J. Am. Chem. Soc. 140, 11165–11169 (2018). [DOI] [PubMed] [Google Scholar]
80.B. Hammer, J. K. Nørskov, “Theoretical surface science and catalysis—Calculations and concepts” in Advances in Catalysis (Elsevier, 2000), vol. 45, pp. 71–129. [Google Scholar]
81.Li X., Wang H., Cui Z., Li Y., Xin S., Zhou J., Long Y., Jin C., Goodenough J. B., Exceptional oxygen evolution reactivities on CaCoO₃ and SrCoO₃. Sci. Adv. 5, eaav6262 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]
82.May K. J., Carlton C. E., Stoerzinger K. A., Risch M., Suntivich J., Lee Y.-L., Grimaud A., Shao-Horn Y., Influence of oxygen evolution during water oxidation on the surface of perovskite oxide catalysts. J. Phys. Chem. Lett. 3, 3264–3270 (2012). [Google Scholar]
83.Wan G., Freeland J. W., Kloppenburg J., Petretto G., Nelson J. N., Kuo D.-Y., Sun C.-J., Wen J., Diulus J. T., Herman G. S., Dong Y., Kou R., Sun J., Chen S., Shen K. M., Schlom D. G., Rignanese G.-M., Hautier G., Fong D. D., Zhou H., Suntivich J., Amorphization mechanism of SrIrO₃ electrocatalyst: How oxygen redox initiates ionic diffusion and structural reorganization. Sci. Adv. 7, eabc7323 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]
84.Tang R., Nie Y., Kawasaki J. K., Kuo D.-Y., Petretto G., Hautier G., Rignanese G.-M., Shen K. M., Schlom D. G., Suntivich J., Oxygen evolution reaction electrocatalysis on SrIrO₃ grown using molecular beam epitaxy. J. Mater. Chem. A 4, 6831–6836 (2016). [Google Scholar]
85.Lee K., Osada M., Hwang H. Y., Hikita Y., Oxygen evolution reaction activity in IrO_x/SrIrO₃ catalysts: Correlations between structural parameters and the catalytic activity. J. Phys. Chem. Lett. 10, 1516–1522 (2019). [DOI] [PubMed] [Google Scholar]
86.Akbashev A. R., Roddatis V., Baeumer C., Liu T., Mefford J. T., Chueh W. C., Probing the stability of SrIrO₃ during active water electrolysis via operando atomic force microscopy. Energ. Environ. Sci. 16, 513–522 (2023). [Google Scholar]
87.Ben-Naim M., Liu Y., Stevens M. B., Lee K., Wette M. R., Boubnov A., Trofimov A. A., Ievlev A. V., Belianinov A., Davis R. C., Clemens B. M., Bare S. R., Hikita Y., Hwang H. Y., Higgins D. C., Sinclair R., Jaramillo T. F., Understanding degradation mechanisms in SrIrO₃ oxygen evolution electrocatalysts: Chemical and structural microscopy at the nanoscale. Adv. Funct. Mater. 31, 2101542 (2021). [Google Scholar]
88.Tong X., Zhan X., Rawach D., Chen Z., Zhang G., Sun S., Low-dimensional catalysts for oxygen reduction reaction. Prog. Nat. Sci. Mater. Int. 30, 787–795 (2020). [Google Scholar]
89.Risch M., Perovskite electrocatalysts for the oxygen reduction reaction in alkaline media. Catalysts 7, 154 (2017). [Google Scholar]
90.Kulkarni A., Siahrostami S., Patel A., Nørskov J. K., Understanding catalytic activity trends in the oxygen reduction reaction. Chem. Rev. 118, 2302–2312 (2018). [DOI] [PubMed] [Google Scholar]
91.Grimaud A., Hong W. T., Shao-Horn Y., Tarascon J.-M., Anionic redox processes for electrochemical devices. Nat. Mater. 15, 121–126 (2016). [DOI] [PubMed] [Google Scholar]
92.Aoki Y., Takase K., Kiuchi H., Kowalski D., Sato Y., Toriumi H., Kitano S., Habazaki H., In situ activation of a manganese perovskite oxygen reduction catalyst in concentrated alkaline media. J. Am. Chem. Soc. 143, 6505–6515 (2021). [DOI] [PubMed] [Google Scholar]
93.Nørskov J. K., Rossmeisl J., Logadottir A., Lindqvist L., Kitchin J. R., Bligaard T., Jonsson H., Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004). [DOI] [PubMed] [Google Scholar]
94.Schmidt T., Stamenkovic V., Ross P. Jr., Markovic N., Temperature dependent surface electrochemistry on Pt single crystals in alkaline electrolyte. Part 3. The oxygen reduction reaction. Phys. Chem. Chem. Phys. 5, 400–406 (2003). [Google Scholar]
95.Ross P. N. Jr., Oxygen reduction reaction on smooth single crystal electrodes in Handbook of Fuel Cells (2010), vol. 2, p. 465. [Google Scholar]
96.Ramaswamy N., Mukerjee S., Alkaline anion-exchange membrane fuel cells: Challenges in electrocatalysis and interfacial charge transfer. Chem. Rev. 119, 11945–11979 (2019). [DOI] [PubMed] [Google Scholar]
97.Hardin W. G., Mefford J. T., Slanac D. A., Patel B. B., Wang X., Dai S., Zhao X., Ruoff R. S., Johnston K. P., Stevenson K. J., Tuning the electrocatalytic activity of perovskites through active site variation and support interactions. Chem. Mater. 26, 3368–3376 (2014). [Google Scholar]
98.Ge X., Du Y., Li B., Hor T. S. A., Sindoro M., Zong Y., Zhang H., Liu Z., Intrinsically conductive perovskite oxides with enhanced stability and electrocatalytic activity for oxygen reduction reactions. ACS Catal. 6, 7865–7871 (2016). [Google Scholar]
99.Fabbri E., Mohamed R., Levecque P., Conrad O., R. d. Kötz, Schmidt T. J., Composite electrode boosts the activity of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ perovskite and carbon toward oxygen reduction in alkaline media. ACS Catal. 4, 1061–1070 (2014). [Google Scholar]
100.Beall C. E., Fabbri E., Schmidt T. J., Perovskite oxide based electrodes for the oxygen reduction and evolution reactions: The underlying mechanism. ACS Catal. 11, 3094–3114 (2021). [Google Scholar]
101.Mariano R. G., Wahab O. J., Rabinowitz J. A., Oppenheim J., Chen T., Unwin P. R., Dincǎ M., Thousand-fold increase in O₂ electroreduction rates with conductive MOFs. ACS Cent. Sci. 8, 975–982 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
102.Gridin V., Du J., Haller S., Theis P., Hofmann K., Wiberg G. K. H., Kramm U. I., Arenz M., GDE vs RDE: Impact of operation conditions on intrinsic catalytic parameters of FeNC catalyst for the oxygen reduction reaction. Electrochim. Acta 444, 142012 (2023). [Google Scholar]
103.Inaba M., Jensen A. W., Sievers G. W., Escudero-Escribano M., Zana A., Arenz M., Benchmarking high surface area electrocatalysts in a gas diffusion electrode: Measurement of oxygen reduction activities under realistic conditions. Energ. Environ. Sci. 11, 988–994 (2018). [Google Scholar]
104.Kim J. H., Yoo S., Murphy R., Chen Y., Ding Y., Pei K., Zhao B., Kim G., Choi Y., Liu M., Promotion of oxygen reduction reaction on a double perovskite electrode by a water-induced surface modification. Energ. Environ. Sci. 14, 1506–1516 (2021). [Google Scholar]
105.Li Q., Zhang D., Wu J., Dai S., Liu H., Lu M., Cui R., Liang W., Wang D., Xi P., Liu M., Li H., Huang L., Cation-deficient perovskites greatly enhance the electrocatalytic activity for oxygen reduction reaction. Adv. Mater. 36, 2309266 (2024). [DOI] [PubMed] [Google Scholar]
106.Wang X., Gao X. J., Qin L., Wang C., Song L., Zhou Y.-N., Zhu G., Cao W., Lin S., Zhou L., e_g occupancy as an effective descriptor for the catalytic activity of perovskite oxide-based peroxidase mimics. Nat. Commun. 10, 704 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]
107.Suntivich J., Gasteiger H. A., Yabuuchi N., Nakanishi H., Goodenough J. B., Shao-Horn Y., Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. Nat. Chem. 3, 546–550 (2011). [DOI] [PubMed] [Google Scholar]
108.Hua B., Sun Y.-F., Li M., Yan N., Chen J., Zhang Y.-Q., Zeng Y., Shalchi Amirkhiz B., Luo J.-L., Stabilizing double perovskite for effective bifunctional oxygen electrocatalysis in alkaline conditions. Chem. Mater. 29, 6228–6237 (2017). [Google Scholar]
109.Abe Y., Satoh I., Saito T., Kan D., Shimakawa Y., Oxygen reduction reaction catalytic activities of pure Ni-based perovskite-related structure oxides. Chem. Mater. 32, 8694–8699 (2020). [Google Scholar]
110.Huang H., Huang A., Liu D., Han W., Kuo C.-H., Chen H.-Y., Li L., Pan H., Peng S., Tailoring oxygen reduction reaction kinetics on perovskite oxides via oxygen vacancies for low-temperature and knittable zinc-air batteries. Adv. Mater. 35, e2303109 (2023). [DOI] [PubMed] [Google Scholar]
111.Yuasa M., Tachibana N., Shimanoe K., Oxygen reduction activity of carbon-supported La_1–xCaxMn_1–yFeyO₃ nanoparticles. Chem. Mater. 25, 3072–3079 (2013). [Google Scholar]
112.Shi L., Zhou W., Li Z., Koul S., Kushima A., Yang Y., Periodically ordered nanoporous perovskite photoelectrode for efficient photoelectrochemical water splitting. ACS Nano 12, 6335–6342 (2018). [DOI] [PubMed] [Google Scholar]
113.Zhu K., Shi F., Zhu X., Yang W., The roles of oxygen vacancies in electrocatalytic oxygen evolution reaction. Nano Energy 73, 104761 (2020). [Google Scholar]
114.Zhu Y., Zhang L., Zhao B., Chen H., Liu X., Zhao R., Wang X., Liu J., Chen Y., Liu M., Improving the activity for oxygen evolution reaction by tailoring oxygen defects in double perovskite oxides. Adv. Funct. Mater. 29, 1901783 (2019). [Google Scholar]
115.Badreldin A., Abusrafa A. E., Abdel-Wahab A., Oxygen-deficient perovskites for oxygen evolution reaction in alkaline media: A review. Emergent Mater. 3, 567–590 (2020). [Google Scholar]
116.Aoki Y., Tsuji E., Motohashi T., Kowalski D., Habazaki H., La_0.7Sr_0.3Mn_1–xNi_xO_3−δ electrocatalysts for the four-electron oxygen reduction reaction in concentrated alkaline media. J. Phys. Chem. C 122, 22301–22308 (2018). [Google Scholar]
117.Sunarso J., Torriero A. A., Zhou W., Howlett P. C., Forsyth M., Oxygen reduction reaction activity of La-based perovskite oxides in alkaline medium: A thin-film rotating ring-disk electrode study. J. Phys. Chem. C 116, 5827–5834 (2012). [Google Scholar]
118.Alegre C., Modica E., Aricò A., Baglio V., Bifunctional oxygen electrode based on a perovskite/carbon composite for electrochemical devices. J. Electroanal. Chem. 808, 412–419 (2018). [Google Scholar]
119.Malkhandi S., Trinh P., Manohar A. K., Jayachandrababu K., Kindler A., Prakash G. K. S., Narayanan S. R., Electrocatalytic activity of transition metal oxide-carbon composites for oxygen reduction in alkaline batteries and fuel cells. J. Electrochem. Soc. 160, F943–F952 (2013). [Google Scholar]
120.Nishio K., Molla S., Okugaki T., Nakanishi S., Nitta I., Kotani Y., Effects of carbon on oxygen reduction and evolution reactions of gas-diffusion air electrodes based on perovskite-type oxides. J. Power Sources 298, 236–240 (2015). [Google Scholar]
121.Mefford J. T., Kurilovich A. A., Saunders J., Hardin W. G., Abakumov A. M., Forslund R. P., Bonnefont A., Dai S., Johnston K. P., Stevenson K. J., Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La_1-xSr_xCoO_3-δ perovskite composite electrodes. Phys. Chem. Chem. Phys. 21, 3327–3338 (2019). [DOI] [PubMed] [Google Scholar]
122.Poux T., Bonnefont A., Kéranguéven G., Tsirlina G. A., Savinova E. R., Electrocatalytic oxygen reduction reaction on perovskite oxides: Series versus direct pathway. ChemPhysChem 15, 2108–2120 (2014). [DOI] [PubMed] [Google Scholar]
123.Hermann V., Dutriat D., Müller S., Comninellis C., Mechanistic studies of oxygen reduction at La_0.6Ca_0.4CoO₃-activated carbon electrodes in a channel flow cell. Electrochim. Acta 46, 365–372 (2000). [Google Scholar]
124.Li X., Qu W., Zhang J., Wang H., Electrocatalytic activities of La_0.6Ca_0.4CoO₃ and La_0.6Ca_0.4CoO₃-carbon composites toward the oxygen reduction reaction in concentrated alkaline electrolytes. J. Electrochem. Soc. 158, A597 (2011). [Google Scholar]
125.Chung D. Y., Park S., Lopes P. P., Stamenkovic V. R., Sung Y.-E., Markovic N. M., Strmcnik D., Electrokinetic analysis of poorly conductive electrocatalytic materials. ACS Catal. 10, 4990–4996 (2020). [Google Scholar]
126.Morales-Guio C. G., Stern L.-A., Hu X., Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem. Soc. Rev. 43, 6555–6569 (2014). [DOI] [PubMed] [Google Scholar]
127.Fletcher S., Tafel slopes from first principles. J. Solid State Electrochem. 13, 537–549 (2009). [Google Scholar]
128.Bockris J. M., Potter E., The mechanism of the cathodic hydrogen evolution reaction. J. Electrochem. Soc. 99, 169 (1952). [Google Scholar]
129.Zhu Y., Lin Q., Zhong Y., Tahini H. A., Shao Z., Wang H., Metal oxide-based materials as an emerging family of hydrogen evolution electrocatalysts. Energ. Environ. Sci. 13, 3361–3392 (2020). [Google Scholar]
130.Zhou K. L., Wang Z., Han C. B., Ke X., Wang C., Jin Y., Zhang Q., Liu J., Wang H., Yan H., Platinum single-atom catalyst coupled with transition metal/metal oxide heterostructure for accelerating alkaline hydrogen evolution reaction. Nat. Commun. 12, 3783 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]
131.Miu E. V., McKone J. R., Mpourmpakis G., The sensitivity of metal oxide electrocatalysis to bulk hydrogen intercalation: Hydrogen evolution on tungsten oxide. J. Am. Chem. Soc. 144, 6420–6433 (2022). [DOI] [PubMed] [Google Scholar]
132.Wang J., Gao Y., Ciucci F., Mechanochemical coupling of MoS₂ and perovskites for hydrogen generation. ACS Appl. Energy Mater. 1, 6409–6416 (2018). [Google Scholar]
133.Dai J., Zhu Y., Tahini H. A., Lin Q., Chen Y., Guan D., Zhou C., Hu Z., Lin H.-J., Chan T.-S., Chen C.-T., Smith S. C., Wang H., Zhou W., Shao Z., Single-phase perovskite oxide with super-exchange induced atomic-scale synergistic active centers enables ultrafast hydrogen evolution. Nat. Commun. 11, 5657 (2020). [DOI] [PMC free article] [PubMed] [Google Scholar]
134.Li Q., Wang D., Lu Q., Meng T., Yan M., Fan L., Xing Z., Yang X., Identifying the activation mechanism and boosting electrocatalytic activity of layered perovskite ruthenate. Small 16, e1906380 (2020). [DOI] [PubMed] [Google Scholar]
135.Pan S., Yang X., Sun J., Wang X., Zhu J., Fu Y., Competitive adsorption mechanism of defect-induced d-orbital single electrons in SrRuO₃ for alkaline hydrogen evolution reaction. Adv. Energy Mater. 13, 2301779 (2023). [Google Scholar]
136.Zhang L., Jang H., Li Z., Liu H., Kim M. G., Liu X., Cho J., SrIrO₃ modified with laminar Sr₂IrO₄ as a robust bifunctional electrocatalyst for overall water splitting in acidic media. Chem. Eng. J. 419, 129604 (2021). [Google Scholar]
137.Yu J., Wu X., Guan D., Hu Z., Weng S.-C., Sun H., Song Y., Ran R., Zhou W., Ni M., Shao Z., Monoclinic SrIrO₃: An easily synthesized conductive perovskite oxide with outstanding performance for overall water splitting in alkaline solution. Chem. Mater. 32, 4509–4517 (2020). [Google Scholar]
138.Subbaraman R., Tripkovic D., Strmcnik D., Chang K.-C., Uchimura M., Paulikas A. P., Stamenkovic V., Markovic N. M., Enhancing hydrogen evolution activity in water splitting by tailoring Li⁺-Ni(OH)₂-Pt interfaces. Science 334, 1256–1260 (2011). [DOI] [PubMed] [Google Scholar]
139.Greeley J., Jaramillo T. F., Bonde J., Chorkendorff I., Nørskov J. K., Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 5, 909–913 (2006). [DOI] [PubMed] [Google Scholar]
140.Dai J., Zhu Y., Chen Y., Wen X., Long M., Wu X., Hu Z., Guan D., Wang X., Zhou C., Lin Q., Sun Y., Weng S.-C., Wang H., Zhou W., Shao Z., Hydrogen spillover in complex oxide multifunctional sites improves acidic hydrogen evolution electrocatalysis. Nat. Commun. 13, 1189 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
141.Zhu Y., Tahini H. A., Hu Z., Dai J., Chen Y., Sun H., Zhou W., Liu M., Smith S. C., Wang H., Shao Z., Unusual synergistic effect in layered Ruddlesden−Popper oxide enables ultrafast hydrogen evolution. Nat. Commun. 10, 149 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]
142.Zhang S., Duan G., Qiao L., Tang Y., Chen Y., Sun Y., Wan P., Zhang S., Electrochemical ammonia synthesis from N₂ and H₂O catalyzed by doped LaFeO₃ perovskite under mild conditions. Ind. Eng. Chem. Res. 58, 8935–8939 (2019). [Google Scholar]
143.Liu Y., Kong X., Guo X., Li Q., Ke J., Wang R., Li Q., Geng Z., Zeng J., Enhanced N₂ electroreduction over LaCoO₃ by introducing oxygen vacancies. ACS Catal. 10, 1077–1085 (2020). [Google Scholar]
144.Yoon J. W., Chang H., Lee S.-J., Hwang Y. K., Hong D.-Y., Lee S.-K., Lee J. S., Jang S., Yoon T.-U., Kwac K., Jung Y., Pillai R. S., Faucher F., Vimont A., Daturi M., Férey G., Serre C., Maurin G., Bae Y.-S., Chang J.-S., Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites. Nat. Mater. 16, 526–531 (2017). [DOI] [PubMed] [Google Scholar]
145.Ohrelius M., Guo H., Xian H., Yu G., Alshehri A. A., Alzahrani K. A., Li T., Andersson M., Electrochemical synthesis of ammonia based on a perovskite LaCrO₃ catalyst. ChemCatChem 12, 731–735 (2020). [Google Scholar]
146.Hwang J., Rao R. R., Giordano L., Akkiraju K., Wang X. R., Crumlin E. J., Bluhm H., Shao-Horn Y., Regulating oxygen activity of perovskites to promote NO_x oxidation and reduction kinetics. Nat. Catal. 4, 663–673 (2021). [Google Scholar]
147.Zheng H., Zhang Y., Wang Y., Wu Z., Lai F., Chao G., Zhang N., Zhang L., Liu T., Perovskites with enriched oxygen vacancies as a family of electrocatalysts for efficient nitrate reduction to ammonia. Small 19, 2205625 (2023). [DOI] [PubMed] [Google Scholar]
148.Yang L.-H., Lin Z.-Q., Liao M.-T., Yang W.-J., Pan J.-X., Li W., Yang C., Wu Y.-J., Wang G.-Z., Lv S.-H., Engineering oxygen vacancies in perovskite oxides by in-situ electrochemical activation for highly efficient nitrate reduction. Appl. Surf. Sci. 639, 158208 (2023). [Google Scholar]
149.Chu K., Zong W., Xue G., Guo H., Qin J., Zhu H., Zhang N., Tian Z., Dong H., Miao Y.-E., Roeffaers M. B. J., Hofkens J., Lai F., Liu T., Cation substitution strategy for developing perovskite oxide with rich oxygen vacancy-mediated charge redistribution enables highly efficient nitrate electroreduction to ammonia. J. Am. Chem. Soc. 145, 21387–21396 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]
150.Pi Y., Guo J., Shao Q., Huang X., All-inorganic SrSnO₃ perovskite nanowires for efficient CO₂ electroreduction. Nano Energy 62, 861–868 (2019). [Google Scholar]
151.Zhang H., Xu Y., Lu M., Xie X., Huang L., Perovskite oxides for cathodic electrocatalysis of energy-related gases: From O₂ to CO₂ and N₂. Adv. Funct. Mater. 31, 2101872 (2021). [Google Scholar]
152.Mignard D., Barik R. C., Bharadwaj A. S., Pritchard C. L., Ragnoli M., Cecconi F., Miller H., Yellowlees L. J., Revisiting strontium-doped lanthanum cuprate perovskite for the electrochemical reduction of CO₂. J. CO2 Util. 5, 53–59 (2014). [Google Scholar]
153.Singh R. P., Arora P., Nellaiappan S., Shivakumara C., Irusta S., Paliwal M., Sharma S., Electrochemical insights into layered La₂CuO₄ perovskite: Active ionic copper for selective CO₂ electroreduction at low overpotential. Electrochim. Acta 326, 134952 (2019). [Google Scholar]
154.Chen S., Su Y., Deng P., Qi R., Zhu J., Chen J., Wang Z., Zhou L., Guo X., Xia B. Y., Highly selective carbon dioxide electroreduction on structure-evolved copper perovskite oxide toward methane production. ACS Catal. 10, 4640–4646 (2020). [Google Scholar]
155.Wang J., Cheng C., Huang B., Cao J., Li L., Shao Q., Zhang L., Huang X., Grain-boundary-engineered La₂CuO₄ perovskite nanobamboos for efficient CO₂ reduction reaction. Nano Lett. 21, 980–987 (2021). [DOI] [PubMed] [Google Scholar]
156.Gao X., Bai X., Wang P., Jiao Y., Davey K., Zheng Y., Qiao S.-Z., Boosting urea electrooxidation on oxyanion-engineered nickel sites via inhibited water oxidation. Nat. Commun. 14, 5842 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]
157.Zhang L., Wang L., Lin H., Liu Y., Ye J., Wen Y., Chen A., Wang L., Ni F., Zhou Z., Sun S., Li Y., Zhang B., Peng H., A lattice-oxygen-involved reaction pathway to boost urea oxidation. Angew. Chem. Int. Ed. 131, 16976–16981 (2019). [DOI] [PubMed] [Google Scholar]
158.Han B., Risch M., Lee Y.-L., Ling C., Jia H., Shao-Horn Y., Activity and stability trends of perovskite oxides for oxygen evolution catalysis at neutral pH. Phys. Chem. Chem. Phys. 17, 22576–22580 (2015). [DOI] [PubMed] [Google Scholar]
159.Zhang Y., Arpino K. E., Yang Q., Kikugawa N., Sokolov D. A., Hicks C. W., Liu J., Felser C., Li G., Observation of a robust and active catalyst for hydrogen evolution under high current densities. Nat. Commun. 13, 7784 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
160.Seok J., Molina Villarino A., Shi Z., Yang Y., Ahmadi M., Muller D. A., DiSalvo F. J., Abruña H. D., La-based perovskite oxide catalysts for alkaline oxygen reduction: The importance of electrochemical stability. J. Phys. Chem. C 126, 3098–3108 (2022). [Google Scholar]
161.Ignatans R., Mallia G., Ahmad E. A., Spillane L., Stoerzinger K. A., Shao-Horn Y., Harrison N. M., Tileli V., The effect of surface reconstruction on the oxygen reduction reaction properties of LaMnO₃. J. Phys. Chem. C 123, 11621–11627 (2019). [Google Scholar]
162.Shih A. J., Monteiro M. C., Dattila F., Pavesi D., Philips M., da Silva A. H., Vos R. E., Ojha K., Park S., van der Heijden O., Marcandalli G., Goyal A., Villalba M., Chen X., Gunasooriya G. T. K. K., Crum I. M., Mom R., López N., Koper M. T. M., Water electrolysis. Nat. Rev. Methods Primers 2, 84 (2022). [Google Scholar]
163.Kas R., Ayemoba O., Firet N. J., Middelkoop J., Smith W. A., Cuesta A., In-situ infrared spectroscopy applied to the study of the electrocatalytic reduction of CO₂: Theory, practice and challenges. ChemPhysChem 20, 2904–2925 (2019). [DOI] [PubMed] [Google Scholar]
164.Timoshenko J., Roldan Cuenya B., In situ/operando electrocatalyst characterization by X-ray absorption spectroscopy. Chem. Rev. 121, 882–961 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]
165.Yang L., Yu G., Ai X., Yan W., Duan H., Chen W., Li X., Wang T., Zhang C., Huang X., Chen J.-S., Zou X., Efficient oxygen evolution electrocatalysis in acid by a perovskite with face-sharing IrO₆ octahedral dimers. Nat. Commun. 9, 5236 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]
166.Mefford J. T., Rong X., Abakumov A. M., Hardin W. G., Dai S., Kolpak A. M., Johnston K. P., Stevenson K. J., Water electrolysis on La_1−xSr_xCoO_3−δ perovskite electrocatalysts. Nat. Commun. 7, 11053 (2016). [DOI] [PMC free article] [PubMed] [Google Scholar]
167.Forslund R. P., Hardin W. G., Rong X., Abakumov A. M., Filimonov D., Alexander C. T., Mefford J. T., Iyer H., Kolpak A. M., Johnston K. P., Stevenson K. J., Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La_0.5Sr_1.5Ni_1-xFe_xO_4±δ Ruddlesden-Popper oxides. Nat. Commun. 9, 3150 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]
168.Zhang J., Ye Y., Wang Z., Xu Y., Gui L., He B., Zhao L., Probing dynamic self-reconstruction on perovskite fluorides toward ultrafast oxygen evolution. Adv. Sci. 9, e2201916 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
169.Lu M., Zheng Y., Hu Y., Huang B., Ji D., Sun M., Li J., Peng Y., Si R., Xi P., Yan C.-H., Artificially steering electrocatalytic oxygen evolution reaction mechanism by regulating oxygen defect contents in perovskites. Sci. Adv. 8, eabq3563 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
170.Jin Z., Bard A. J., Surface interrogation of electrodeposited MnO_x and CaMnO₃ perovskites by scanning electrochemical microscopy: Probing active sites and kinetics for the oxygen evolution reaction. Angew. Chem. Int. Ed. 133, 807–812 (2021). [DOI] [PubMed] [Google Scholar]
171.Ali-Löytty H., Louie M. W., Singh M. R., Li L., Sanchez Casalongue H. G., Ogasawara H., Crumlin E. J., Liu Z., Bell A. T., Nilsson A., Friebel D., Ambient-pressure XPS study of a Ni–Fe electrocatalyst for the oxygen evolution reaction. J. Phys. Chem. C 120, 2247–2253 (2016). [Google Scholar]
172.Moon J., Beker W., Siek M., Kim J., Lee H. S., Hyeon T., Grzybowski B. A., Active learning guides discovery of a champion four-metal perovskite oxide for oxygen evolution electrocatalysis. Nat. Mater. 23, 108–115 (2024). [DOI] [PubMed] [Google Scholar]
173.Sun Y., Liao H., Wang J., Chen B., Sun S., Ong S. J. H., Xi S., Diao C., Du Y., Wang J.-O., Breese M. B. H., Li S., Zhang H., Xu Z. J., Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides. Nat. Catal. 3, 554–563 (2020). [Google Scholar]
174.Lee J. G., Hwang J., Hwang H. J., Jeon O. S., Jang J., Kwon O., Lee Y., Han B., Shul Y.-G., A new family of perovskite catalysts for oxygen-evolution reaction in alkaline media: BaNiO₃ and BaNi_0.83O_2.5. J. Am. Chem. Soc. 138, 3541–3547 (2016). [DOI] [PubMed] [Google Scholar]
175.Zhang R., Pearce P. E., Duan Y., Dubouis N., Marchandier T., Grimaud A., Importance of water structure and catalyst-electrolyte interface on the design of water splitting catalysts. Chem. Mater. 31, 8248–8259 (2019). [Google Scholar]
176.Kim J., Yin X., Tsao K.-C., Fang S., Yang H., Ca₂Mn₂O₅ as oxygen-deficient perovskite electrocatalyst for oxygen evolution reaction. J. Am. Chem. Soc. 136, 14646–14649 (2014). [DOI] [PubMed] [Google Scholar]
177.Jacobs R., Hwang J., Shao-Horn Y., Morgan D., Assessing correlations of perovskite catalytic performance with electronic structure descriptors. Chem. Mater. 31, 785–797 (2019). [Google Scholar]
178.Ashok A., Kumar A., Bhosale R. R., Almomani F., Malik S. S., Suslov S., Tarlochan F., Combustion synthesis of bifunctional LaMO₃ (M = Cr, Mn, Fe, Co, Ni) perovskites for oxygen reduction and oxygen evolution reaction in alkaline media. J. Electroanal. Chem. 809, 22–30 (2018). [Google Scholar]
179.Dias J. A., Andrade M. A. Jr., Santos H. S., Morelli M. R., Mascaro L. H., Lanthanum-based perovskites for catalytic oxygen evolution reaction. ChemElectroChem 7, 3173–3192 (2020). [Google Scholar]
180.Emery A. A., Wolverton C., High-throughput DFT calculations of formation energy, stability and oxygen vacancy formation energy of ABO₃ perovskites. Sci. Data 4, 170153 (2017). [DOI] [PMC free article] [PubMed] [Google Scholar]
181.Karki S. B., Ramezanipour F., Pseudocapacitive energy storage and electrocatalytic hydrogen-evolution activity of defect-ordered perovskites Sr_xCa_3–xGaMn₂O₈ (x = 0 and 1). ACS Appl. Energy Mater. 3, 10983–10992 (2020). [Google Scholar]
182.Togano H., Asai K., Oda S., Ikeno H., Kawaguchi S., Oka K., Wada K., Yagi S., Yamada I., Highly active hydrogen evolution catalysis on oxygen-deficient double-perovskite oxide PrBaCo₂O_6−δ. Mater. Chem. Front. 4, 1519–1529 (2020). [Google Scholar]
183.Islam Q. A., Majee R., Bhattacharyya S., Bimetallic nanoparticle decorated perovskite oxide for state-of-the-art trifunctional electrocatalysis. J. Mater. Chem. A 7, 19453–19464 (2019). [Google Scholar]
184.Wang J., Gao Y., Chen D., Liu J., Zhang Z., Shao Z., Ciucci F., Water splitting with an enhanced bifunctional double perovskite. ACS Catal. 8, 364–371 (2018). [Google Scholar]
185.Zhu Y., Zhou W., Zhong Y., Bu Y., Chen X., Zhong Q., Liu M., Shao Z., A perovskite nanorod as bifunctional electrocatalyst for overall water splitting. Adv. Energy Mater. 7, 1602122 (2017). [Google Scholar]
186.Liu Y., Dou Y., Li S., Xia T., Xie Y., Wang Y., Zhang W., Wang J., Huo L., Zhao H., Synergistic interaction of double/simple perovskite heterostructure for efficient hydrogen evolution reaction at high current density. Small Methods 5, e2000701 (2021). [DOI] [PubMed] [Google Scholar]
187.Bu Y., Jang H., Gwon O., Kim S. H., Joo S. H., Nam G., Kim S., Qin Y., Zhong Q., Kwak S. K., Synergistic interaction of perovskite oxides and N-doped graphene in versatile electrocatalyst. J. Mater. Chem. A 7, 2048–2054 (2019). [Google Scholar]
188.Dou Y., Xie Y., Hao X., Xia T., Li Q., Wang J., Huo L., Zhao H., Addressing electrocatalytic activity and stability of LnBaCo₂O_5+δ perovskites for hydrogen evolution reaction by structural and electronic features. Appl Catal B 297, 120403 (2021). [Google Scholar]
189.Ilanchezhiyan P., Kumar G. M., Siva C., Cho H., Tamilselvan S., Seal S., Kang T. W., Kim D. Y., Aid of cobalt ions in boosting the electrocatalytic oxygen and hydrogen evolution functions of NdFeO₃ perovskite nanostructures. J. Mater. Res. Technol. 11, 2246–2254 (2021). [Google Scholar]
190.Hua B., Li M., Zhang Y.-Q., Sun Y.-F., Luo J.-L., All-in-one perovskite catalyst: Smart controls of architecture and composition toward enhanced oxygen/hydrogen evolution reactions. Adv. Energy Mater. 7, 1700666 (2017). [Google Scholar]
191.Karki S. B., Andriotis A. N., Menon M., Ramezanipour F., Bifunctional water-splitting electrocatalysis achieved by defect order in LaA₂Fe₃O₈ (A= Ca, Sr). ACS Appl. Energy Mater. 4, 12063–12066 (2021). [Google Scholar]
192.Guan D., Zhou J., Huang Y.-C., Dong C.-L., Wang J.-Q., Zhou W., Shao Z., Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor. Nat. Commun. 10, 3755 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]
193.Ji D., Liu C., Yao Y., Luo L., Wang W., Chen Z., Cerium substitution in LaCoO₃ perovskite oxide as bifunctional electrocatalysts for hydrogen and oxygen evolution reactions. Nanoscale 13, 9952–9959 (2021). [DOI] [PubMed] [Google Scholar]
194.Sun Q., Dai Z., Zhang Z., Chen Z., Lin H., Gao Y., Chen D., Double perovskite PrBaCo₂O_5.5: An efficient and stable electrocatalyst for hydrogen evolution reaction. J. Power Sources 427, 194–200 (2019). [Google Scholar]
195.Hu C., Hong J., Huang J., Chen W., Segre C. U., Suenaga K., Zhao W., Huang F., Wang J., Surface decoration accelerates the hydrogen evolution kinetics of a perovskite oxide in alkaline solution. Energ. Environ. Sci. 13, 4249–4257 (2020). [Google Scholar]
196.Alom M. S., Kananke-Gamage C. C. W., Ramezanipour F., Perovskite oxides as electrocatalysts for hydrogen evolution reaction. ACS Omega 7, 7444–7451 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]
197.Nørskov J. K., Bligaard T., Logadottir A., Kitchin J. R., Chen J. G., Pandelov S., Stimming U., Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23 (2005). [Google Scholar]
198.Jain A., Ong S. P., Hautier G., Chen W., Richards W. D., Dacek S., Cholia S., Gunter D., Skinner D., Ceder G., Persson K. A., Commentary: The materials project: A materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013). [Google Scholar]
199.Chanussot L., Das A., Goyal S., Lavril T., Shuaibi M., Riviere M., Tran K., Heras-Domingo J., Ho C., Hu W., Palizhati A., Sriram A., Wood B., Yoon J., Parikh D., Zitnick C. L., Ulissi Z., Open catalyst 2020 (OC20) dataset and community challenges. ACS Catal. 11, 6059–6072 (2021). [Google Scholar]

[R1] 1.Chu S., Majumdar A., Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012). [DOI] [PubMed] [Google Scholar]

[R2] 2.Debe M. K., Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012). [DOI] [PubMed] [Google Scholar]

[R3] 3.Wu H. B., Lou X. W. D., Metal-organic frameworks and their derived materials for electrochemical energy storage and conversion: Promises and challenges. Sci. Adv. 3, eaap9252 (2017). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R4] 4.IEA, World Energy Outlook (2023); www.iea.org/reports/world-energy-outlook-2023.

[R5] 5.Pei Z., Zhang H., Luan D., Lou X. W. D., Electrocatalytic acidic oxygen evolution: From catalyst design to industrial applications. Matter 6, 4128–4144 (2023). [Google Scholar]

[R6] 6.Seh Z. W., Kibsgaard J., Dickens C. F., Chorkendorff I., Nørskov J. K., Jaramillo T. F., Combining theory and experiment in electrocatalysis: Insights into materials design. Science 355, eaad4998 (2017). [DOI] [PubMed] [Google Scholar]

[R7] 7.Lewis N. S., Nocera D. G., Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl. Acad. Sci. U.S.A. 103, 15729–15735 (2006). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R8] 8.US Department of Energy, DOE announces goal to cut solar costs by more than half by 2030 (2021); www.energy.gov/articles/doe-announces-goal-cut-solar-costs-more-half-2030.

[R9] 9.Hwang J., Rao R. R., Giordano L., Katayama Y., Yu Y., Shao-Horn Y., Perovskites in catalysis and electrocatalysis. Science 358, 751–756 (2017). [DOI] [PubMed] [Google Scholar]

[R10] 10.Xia B. Y., Yan Y., Li N., Wu H. B., Lou X. W., Wang X., A metal-organic framework-derived bifunctional oxygen electrocatalyst. Nat. Energy 1, 15006 (2016). [Google Scholar]

[R11] 11.Xie J., Zhang H., Li S., Wang R., Sun X., Zhou M., Zhou J., Lou X. W. D., Xie Y., Defect-rich MoS₂ ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution. Adv. Mater. 25, 5807–5813 (2013). [DOI] [PubMed] [Google Scholar]

[R12] 12.Tian X., Zhao X., Su Y.-Q., Wang L., Wang H., Dang D., Chi B., Liu H., Hensen E. J. M., Lou X. W. D., Xia B. Y., Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells. Science 366, 850–856 (2019). [DOI] [PubMed] [Google Scholar]

[R13] 13.Tian X., Lu X. F., Xia B. Y., Lou X. W. D., Advanced electrocatalysts for the oxygen reduction reaction in energy conversion technologies. Joule 4, 45–68 (2020). [Google Scholar]

[R14] 14.Liu S., Xiao J., Lu X. F., Wang J., Wang X., Lou X. W. D., Efficient electrochemical reduction of CO₂ to HCOOH over sub-2 nm SnO₂ quantum wires with exposed grain boundaries. Angew. Chem. Int. Ed. Engl. 58, 8499–8503 (2019). [DOI] [PubMed] [Google Scholar]

[R15] 15.Appel A. M., Bercaw J. E., Bocarsly A. B., Dobbek H., DuBois D. L., Dupuis M., Ferry J. G., Fujita E., Hille R., Kenis P. J., Kerfeld C. A., Morris R. H., Peden C. H. F., Portis A. R., Ragsdale S. W., Rauchfuss T. B., Reek J. N. H., Seefeldt L. C., Thauer R. K., Waldrop G. L., Frontiers, opportunities, and challenges in biochemical and chemical catalysis of CO₂ fixation. Chem. Rev. 113, 6621–6658 (2013). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R16] 16.Chen J. G., Crooks R. M., Seefeldt L. C., Bren K. L., Bullock R. M., Darensbourg M. Y., Holland P. L., Hoffman B., Janik M. J., Jones A. K., Kanatzidis M. G., King P., Lancaster K. M., Lymar S. V., Pfromm P., Schneider W. F., Schrock R. R., Beyond fossil fuel-driven nitrogen transformations. Science 360, eaar6611 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R17] 17.Foster S. L., Bakovic S. I. P., Duda R. D., Maheshwari S., Milton R. D., Minteer S. D., Janik M. J., Renner J. N., Greenlee L. F., Catalysts for nitrogen reduction to ammonia. Nat. Catal. 1, 490–500 (2018). [Google Scholar]

[R18] 18.Zhu P., Wang H., High-purity and high-concentration liquid fuels through CO₂ electroreduction. Nat. Catal. 4, 943–951 (2021). [Google Scholar]

[R19] 19.Seitz L. C., Dickens C. F., Nishio K., Hikita Y., Montoya J., Doyle A., Kirk C., Vojvodic A., Hwang H. Y., Norskov J. K., Jaramillo T. F., A highly active and stable IrO_x/SrIrO₃ catalyst for the oxygen evolution reaction. Science 353, 1011–1014 (2016). [DOI] [PubMed] [Google Scholar]

[R20] 20.Pei Z., Zhang H., Wu Z.-P., Lu X. F., Luan D., Lou X. W., Sci. Adv. 9, Atomically dispersed Ni activates adjacent Ce sites for enhanced electrocatalytic oxygen evolution activity, eadh1320 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R21] 21.Ren Y., Li S., Yu C., Zheng Y., Wang C., Qian B., Wang L., Fang W., Sun Y., Qiu J., NH₃ electrosynthesis from N₂ molecules: Progresses, challenges, and future perspectives. J. Am. Chem. Soc. 146, 6409–6421 (2024). [DOI] [PubMed] [Google Scholar]

[R22] 22.Zhao Y., Adiyeri Saseendran D. P., Huang C., Triana C. A., Marks W. R., Chen H., Zhao H., Patzke G. R., Oxygen evolution/reduction reaction catalysts: From in situ monitoring and reaction mechanisms to rational design. Chem. Rev. 123, 6257–6358 (2023). [DOI] [PubMed] [Google Scholar]

[R23] 23.M. De Graef, M. E. McHenry, Structure of Materials: An Introduction to Crystallography, Diffraction and Symmetry (Cambridge Univ. Press, 2012). [Google Scholar]

[R24] 24.Peña M. A., Fierro J. L., Chemical structures and performance of perovskite oxides. Chem. Rev. 101, 1981–2018 (2001). [DOI] [PubMed] [Google Scholar]

[R25] 25.Filip M. R., Giustino F., The geometric blueprint of perovskites. Proc. Natl. Acad. Sci. U.S.A. 115, 5397–5402 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R26] 26.Suntivich J., May K. J., Gasteiger H. A., Goodenough J. B., Shao-Horn Y., A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334, 1383–1385 (2011). [DOI] [PubMed] [Google Scholar]

[R27] 27.Yin W.-J., Weng B., Ge J., Sun Q., Li Z., Yan Y., Oxide perovskites, double perovskites and derivatives for electrocatalysis, photocatalysis, and photovoltaics. Energ. Environ. Sci. 12, 442–462 (2019). [Google Scholar]

[R28] 28.Ji Q., Bi L., Zhang J., Cao H., Zhao X. S., The role of oxygen vacancies of ABO₃ perovskite oxides in the oxygen reduction reaction. Energ. Environ. Sci. 13, 1408–1428 (2020). [Google Scholar]

[R29] 29.Zhao J.-W., Shi Z.-X., Li C.-F., Ren Q., Li G.-R., Regulation of perovskite surface stability on the electrocatalysis of oxygen evolution reaction. ACS Mater. Lett. 3, 721–737 (2021). [Google Scholar]

[R30] 30.Xu X., Chen Y., Zhou W., Zhu Z., Su C., Liu M., Shao Z., A perovskite electrocatalyst for efficient hydrogen evolution reaction. Adv. Mater. 28, 6442–6448 (2016). [DOI] [PubMed] [Google Scholar]

[R31] 31.Chu K., Liu F., Zhu J., Fu H., Zhu H., Zhu Y., Zhang Y., Lai F., Liu T., A general strategy to boost electrocatalytic nitrogen reduction on perovskite oxides via the oxygen vacancies derived from A-site deficiency. Adv. Energy Mater. 11, 2003799 (2021). [Google Scholar]

[R32] 32.Hwang J., Akkiraju K., Corchado-García J., Shao-Horn Y., A perovskite electronic structure descriptor for electrochemical CO₂ reduction and the competing H₂ evolution reaction. J. Phys. Chem. C 123, 24469–24476 (2019). [Google Scholar]

[R33] 33.Forslund R. P., Mefford J. T., Hardin W. G., Alexander C. T., Johnston K. P., Stevenson K. J., Nanostructured LaNiO₃ perovskite electrocatalyst for enhanced urea oxidation. ACS Catal. 6, 5044–5051 (2016). [Google Scholar]

[R34] 34.Lan A., Mukasyan A. S., Perovskite-based catalysts for direct methanol fuel cells. J. Phys. Chem. C 111, 9573–9582 (2007). [Google Scholar]

[R35] 35.Grimaud A., May K. J., Carlton C. E., Lee Y.-L., Risch M., Hong W. T., Zhou J., Shao-Horn Y., Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution. Nat. Commun. 4, 2439 (2013). [DOI] [PubMed] [Google Scholar]

[R36] 36.Yoo J. S., Rong X., Liu Y., Kolpak A. M., Role of lattice oxygen participation in understanding trends in the oxygen evolution reaction on perovskites. ACS Catal. 8, 4628–4636 (2018). [Google Scholar]

[R37] 37.Risch M., Grimaud A., May K. J., Stoerzinger K. A., Chen T. J., Mansour A. N., Shao-Horn Y., Structural changes of cobalt-based perovskites upon water oxidation investigated by EXAFS. J. Phys. Chem. C 117, 8628–8635 (2013). [Google Scholar]

[R38] 38.Song H. J., Yoon H., Ju B., Kim D.-W., Highly efficient perovskite-based electrocatalysts for water oxidation in acidic environments: A mini review. Adv. Energy Mater. 11, 2002428 (2021). [Google Scholar]

[R39] 39.Sun C. W., Alonso J. A., Bian J. J., Recent advances in perovskite-type oxides for energy conversion and storage applications. Adv. Energy Mater. 11, 2000459 (2021). [Google Scholar]

[R40] 40.Wang K., Han C., Shao Z. P., Qiu J. S., Wang S. B., Liu S. M., Perovskite oxide catalysts for advanced oxidation reactions. Adv. Funct. Mater. 31, 2102089 (2021). [Google Scholar]

[R41] 41.Zeng Z., Xu Y., Zhang Z., Gao Z., Luo M., Yin Z., Zhang C., Xu J., Huang B., Luo F., Du Y., Yan C., Rare-earth-containing perovskite nanomaterials: Design, synthesis, properties and applications. Chem. Soc. Rev. 49, 1109–1143 (2020). [DOI] [PubMed] [Google Scholar]

[R42] 42.Li X., Zhao H., Liang J., Luo Y., Chen G., Shi X., Lu S., Gao S., Hu J., Liu Q., A-site perovskite oxides: An emerging functional material for electrocatalysis and photocatalysis. J. Mater. Chem. A 9, 6650–6670 (2021). [Google Scholar]

[R43] 43.Xu X., Pan Y., Zhong Y., Ran R., Shao Z., Ruddlesden-Popper perovskites in electrocatalysis. Mater. Horiz. 7, 2519–2565 (2020). [Google Scholar]

[R44] 44.Zhang M., Jeerh G., Zou P., Lan R., Wang M., Wang H., Tao S., Recent development of perovskite oxide-based electrocatalysts and their applications in low to intermediate temperature electrochemical devices. Mater. Today 49, 351–377 (2021). [Google Scholar]

[R45] 45.Hwang J., Feng Z., Charles N., Wang X. R., Lee D., Stoerzinger K. A., Muy S., Rao R. R., Lee D., Jacobs R., Morgan D., Han Y. S., Tuning perovskite oxides by strain: Electronic structure, properties, and functions in (electro)catalysis and ferroelectricity. Mater. Today 31, 100–118 (2019). [Google Scholar]

[R46] 46.Liu Y., Huang H., Xue L., Sun J., Wang X., Xiong P., Zhu J., Recent advances in the heteroatom doping of perovskite oxides for efficient electrocatalytic reactions. Nanoscale 13, 19840–19856 (2021). [DOI] [PubMed] [Google Scholar]

[R47] 47.Xu X., Wang W., Zhou W., Shao Z., Recent advances in novel nanostructuring methods of perovskite electrocatalysts for energy-related applications. Small Methods 2, 1800071 (2018). [Google Scholar]

[R48] 48.Zhu Y., Zhou W., Shao Z., Perovskite/carbon composites: Applications in oxygen electrocatalysis. Small 13, 1603793 (2017). [DOI] [PubMed] [Google Scholar]

[R49] 49.Ingavale S., Gopalakrishnan M., Enoch C. M., Pornrungroj C., Rittiruam M., Praserthdam S., Somwangthanaroj A., Nootong K., Pornprasertsuk R., Kheawhom S., Strategic design and insights into lanthanum and strontium perovskite oxides for oxygen reduction and oxygen evolution reactions. Small 20, 2308443 (2024). [DOI] [PubMed] [Google Scholar]

[R50] 50.Song F., Bai L., Moysiadou A., Lee S., Hu C., Liardet L., Hu X., Transition metal oxides as electrocatalysts for the oxygen evolution reaction in alkaline solutions: An application-inspired renaissance. J. Am. Chem. Soc. 140, 7748–7759 (2018). [DOI] [PubMed] [Google Scholar]

[R51] 51.Bockris J. O. M., Otagawa T., Mechanism of oxygen evolution on perovskites. J. Phys. Chem. 87, 2960–2971 (2002). [Google Scholar]

[R52] 52.Wang X., Zhong H., Xi S., Lee W. S. V., Xue J., Understanding of oxygen redox in the oxygen evolution reaction. Adv. Mater. 34, e2107956 (2022). [DOI] [PubMed] [Google Scholar]

[R53] 53.Man I. C., Su H. Y., Calle-Vallejo F., Hansen H. A., Martínez J. I., Inoglu N. G., Kitchin J., Jaramillo T. F., Nørskov J. K., Rossmeisl J., Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 3, 1159–1165 (2011). [Google Scholar]

[R54] 54.Yoo J. S., Liu Y., Rong X., Kolpak A. M., Electronic origin and kinetic feasibility of the lattice oxygen participation during the oxygen evolution reaction on perovskites. J. Phys. Chem. Lett. 9, 1473–1479 (2018). [DOI] [PubMed] [Google Scholar]

[R55] 55.Lin C., Li J.-L., Li X., Yang S., Luo W., Zhang Y., Kim S.-H., Kim D.-H., Shinde S. S., Li Y.-F., In-situ reconstructed Ru atom array on α-MnO₂ with enhanced performance for acidic water oxidation. Nat. Catal. 4, 1012–1023 (2021). [Google Scholar]

[R56] 56.Tripkovic V., Hansen H. A., Garcia-Lastra J. M., Vegge T., Comparative DFT+U and HSE study of the oxygen evolution electrocatalysis on perovskite oxides. J. Phys. Chem. C 122, 1135–1147 (2018). [Google Scholar]

[R57] 57.Huang Z.-F., Song J., Du Y., Xi S., Dou S., Nsanzimana J. M. V., Wang C., Xu Z. J., Wang X., Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts. Nat. Energy 4, 329–338 (2019). [Google Scholar]

[R58] 58.Grimaud A., Diaz-Morales O., Han B., Hong W. T., Lee Y.-L., Giordano L., Stoerzinger K. A., Koper M. T. M., Shao-Horn Y., Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. Nat. Chem. 9, 457–465 (2017). [DOI] [PubMed] [Google Scholar]

[R59] 59.Zhao J.-W., Zhang H., Li C. F., Zhou X., Wu J.-Q., Zeng F., Zhang J., Li G.-R., Key roles of surface Fe sites and Sr vacancies in the perovskite for an efficient oxygen evolution reaction via lattice oxygen oxidation. Energ. Environ. Sci. 15, 3912–3922 (2022). [Google Scholar]

[R60] 60.Ferreira de Araújo J., Dionigi F., Merzdorf T., Oh H. S., Strasser P., Evidence of Mars-Van-Krevelen mechanism in the electrochemical oxygen evolution on Ni-based catalysts. Angew. Chem. Int. Ed. 60, 14981–14988 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R61] 61.Wu Y., Zhao Y., Zhai P., Wang C., Gao J., Sun L., Hou J., Triggering lattice oxygen activation of single-atomic Mo sites anchored on Ni-Fe oxyhydroxides nanoarrays for electrochemical water oxidation. Adv. Mater. 34, e2202523 (2022). [DOI] [PubMed] [Google Scholar]

[R62] 62.Kim B.-J., Fabbri E., Abbott D. F., Cheng X., Clark A. H., Nachtegaal M., Borlaf M., Castelli I. E., Graule T., Schmidt T. J., Functional role of Fe-doping in Co-based perovskite oxide catalysts for oxygen evolution reaction. J. Am. Chem. Soc. 141, 5231–5240 (2019). [DOI] [PubMed] [Google Scholar]

[R63] 63.Lopes P. P., Chung D. Y., Rui X., Zheng H., He H., Martins P. F. B. D., Strmcnik D., Stamenkovic V. R., Zapol P., Mitchell J. F., Klie R. F., Markovic N. M., Dynamically stable active sites from surface evolution of perovskite materials during the oxygen evolution reaction. J. Am. Chem. Soc. 143, 2741–2750 (2021). [DOI] [PubMed] [Google Scholar]

[R64] 64.Fabbri E., Nachtegaal M., Binninger T., Cheng X., Kim B.-J., Durst J., Bozza F., Graule T., Schäublin R., Wiles L., Pertoso M., Danilovic N., Ayers K. E., Schmidt T. J., Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting. Nat. Mater. 16, 925–931 (2017). [DOI] [PubMed] [Google Scholar]

[R65] 65.Raman A. S., Patel R., Vojvodic A., Surface stability of perovskite oxides under OER operating conditions: A first principles approach. Faraday Discuss. 229, 75–88 (2021). [DOI] [PubMed] [Google Scholar]

[R66] 66.Kim B.-J., Fabbri E., Borlaf M., Abbott D. F., Castelli I. E., Nachtegaal M., Graule T., Schmidt T. J., Oxygen evolution reaction activity and underlying mechanism of perovskite electrocatalysts at different pH. Mater. Adv. 2, 345–355 (2021). [Google Scholar]

[R67] 67.Akbashev A., Zhang L., Mefford J. T., Park J., Butz B., Luftman H., Chueh W. C., Vojvodic A., Activation of ultrathin SrTiO₃ with subsurface SrRuO₃ for the oxygen evolution reaction. Energ. Environ. Sci. 11, 1762–1769 (2018). [Google Scholar]

[R68] 68.Yang C., Batuk M., Jacquet Q., Rousse G., Yin W., Zhang L., Hadermann J., Abakumov A. M., Cibin G., Chadwick A., Tarascon J.-M., Grimaud A., Revealing pH-dependent activities and surface instabilities for Ni-based electrocatalysts during the oxygen evolution reaction. ACS Energy Lett. 3, 2884–2890 (2018). [Google Scholar]

[R69] 69.Chen Y., Li H., Wang J., Du Y., Xi S., Sun Y., Sherburne M., Ager J. W. III, Fisher A. C., Xu Z. J., Exceptionally active iridium evolved from a pseudo-cubic perovskite for oxygen evolution in acid. Nat. Commun. 10, 572 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R70] 70.Zhao J.-W., Yue K., Zhang H., Wei S.-Y., Zhu J., Wang D., Chen J., Fominski V. Y., Li G.-R., The formation of unsaturated IrO_x in SrIrO₃ by cobalt-doping for acidic oxygen evolution reaction. Nat. Commun. 15, 2928 (2024). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R71] 71.Liu J., Jia E., Stoerzinger K. A., Wang L., Wang Y., Yang Z., Shen D., Engelhard M. H., Bowden M. E., Zhu Z., Chambers S. A., Du Y., Dynamic lattice oxygen participation on perovskite LaNiO₃ during oxygen evolution reaction. J. Phys. Chem. C 124, 15386–15390 (2020). [Google Scholar]

[R72] 72.Zhang N., Chai Y., Lattice oxygen redox chemistry in solid-state electrocatalysts for water oxidation. Energ. Environ. Sci. 14, 4647–4671 (2021). [Google Scholar]

[R73] 73.Gao L., Cui X., Sewell C. D., Li J., Lin Z., Recent advances in activating surface reconstruction for the high-efficiency oxygen evolution reaction. Chem. Soc. Rev. 50, 8428–8469 (2021). [DOI] [PubMed] [Google Scholar]

[R74] 74.Luo X., Tan X., Ji P., Chen L., Yu J., Mu S., Surface reconstruction-derived heterostructures for electrochemical water splitting. EnergyChem 5, 100091 (2022). [Google Scholar]

[R75] 75.Badreldin A., Bouhali O., Abdel-Wahab A., Complimentary computational cues for water electrocatalysis: A DFT and ML perspective. Adv. Funct. Mater. 34, 2312425 (2024). [Google Scholar]

[R76] 76.Chen G., Zhou W., Guan D., Sunarso J., Zhu Y., Hu X., Zhang W., Shao Z., Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ nanofilms with tunable oxidation state. Sci. Adv. 3, e1603206 (2017). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R77] 77.Kim N.-I., Sa Y. J., Yoo T. S., Choi S. R., Afzal R. A., Choi T., Seo Y.-S., Lee K.-S., Hwang J. Y., Choi W. S., Joo S. H., Park J.-Y., Oxygen-deficient triple perovskites as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions. Sci. Adv. 4, eaap9360 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R78] 78.Bak J., Bin Bae H., Chung S.-Y., Atomic-scale perturbation of oxygen octahedra via surface ion exchange in perovskite nickelates boosts water oxidation. Nat. Commun. 10, 2713 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R79] 79.Tong Y., Wu J., Chen P., Liu H., Chu W., Wu C., Xie Y., Vibronic superexchange in double perovskite electrocatalyst for efficient electrocatalytic oxygen evolution. J. Am. Chem. Soc. 140, 11165–11169 (2018). [DOI] [PubMed] [Google Scholar]

[R80] 80.B. Hammer, J. K. Nørskov, “Theoretical surface science and catalysis—Calculations and concepts” in Advances in Catalysis (Elsevier, 2000), vol. 45, pp. 71–129. [Google Scholar]

[R81] 81.Li X., Wang H., Cui Z., Li Y., Xin S., Zhou J., Long Y., Jin C., Goodenough J. B., Exceptional oxygen evolution reactivities on CaCoO₃ and SrCoO₃. Sci. Adv. 5, eaav6262 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R82] 82.May K. J., Carlton C. E., Stoerzinger K. A., Risch M., Suntivich J., Lee Y.-L., Grimaud A., Shao-Horn Y., Influence of oxygen evolution during water oxidation on the surface of perovskite oxide catalysts. J. Phys. Chem. Lett. 3, 3264–3270 (2012). [Google Scholar]

[R83] 83.Wan G., Freeland J. W., Kloppenburg J., Petretto G., Nelson J. N., Kuo D.-Y., Sun C.-J., Wen J., Diulus J. T., Herman G. S., Dong Y., Kou R., Sun J., Chen S., Shen K. M., Schlom D. G., Rignanese G.-M., Hautier G., Fong D. D., Zhou H., Suntivich J., Amorphization mechanism of SrIrO₃ electrocatalyst: How oxygen redox initiates ionic diffusion and structural reorganization. Sci. Adv. 7, eabc7323 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R84] 84.Tang R., Nie Y., Kawasaki J. K., Kuo D.-Y., Petretto G., Hautier G., Rignanese G.-M., Shen K. M., Schlom D. G., Suntivich J., Oxygen evolution reaction electrocatalysis on SrIrO₃ grown using molecular beam epitaxy. J. Mater. Chem. A 4, 6831–6836 (2016). [Google Scholar]

[R85] 85.Lee K., Osada M., Hwang H. Y., Hikita Y., Oxygen evolution reaction activity in IrO_x/SrIrO₃ catalysts: Correlations between structural parameters and the catalytic activity. J. Phys. Chem. Lett. 10, 1516–1522 (2019). [DOI] [PubMed] [Google Scholar]

[R86] 86.Akbashev A. R., Roddatis V., Baeumer C., Liu T., Mefford J. T., Chueh W. C., Probing the stability of SrIrO₃ during active water electrolysis via operando atomic force microscopy. Energ. Environ. Sci. 16, 513–522 (2023). [Google Scholar]

[R87] 87.Ben-Naim M., Liu Y., Stevens M. B., Lee K., Wette M. R., Boubnov A., Trofimov A. A., Ievlev A. V., Belianinov A., Davis R. C., Clemens B. M., Bare S. R., Hikita Y., Hwang H. Y., Higgins D. C., Sinclair R., Jaramillo T. F., Understanding degradation mechanisms in SrIrO₃ oxygen evolution electrocatalysts: Chemical and structural microscopy at the nanoscale. Adv. Funct. Mater. 31, 2101542 (2021). [Google Scholar]

[R88] 88.Tong X., Zhan X., Rawach D., Chen Z., Zhang G., Sun S., Low-dimensional catalysts for oxygen reduction reaction. Prog. Nat. Sci. Mater. Int. 30, 787–795 (2020). [Google Scholar]

[R89] 89.Risch M., Perovskite electrocatalysts for the oxygen reduction reaction in alkaline media. Catalysts 7, 154 (2017). [Google Scholar]

[R90] 90.Kulkarni A., Siahrostami S., Patel A., Nørskov J. K., Understanding catalytic activity trends in the oxygen reduction reaction. Chem. Rev. 118, 2302–2312 (2018). [DOI] [PubMed] [Google Scholar]

[R91] 91.Grimaud A., Hong W. T., Shao-Horn Y., Tarascon J.-M., Anionic redox processes for electrochemical devices. Nat. Mater. 15, 121–126 (2016). [DOI] [PubMed] [Google Scholar]

[R92] 92.Aoki Y., Takase K., Kiuchi H., Kowalski D., Sato Y., Toriumi H., Kitano S., Habazaki H., In situ activation of a manganese perovskite oxygen reduction catalyst in concentrated alkaline media. J. Am. Chem. Soc. 143, 6505–6515 (2021). [DOI] [PubMed] [Google Scholar]

[R93] 93.Nørskov J. K., Rossmeisl J., Logadottir A., Lindqvist L., Kitchin J. R., Bligaard T., Jonsson H., Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 108, 17886–17892 (2004). [DOI] [PubMed] [Google Scholar]

[R94] 94.Schmidt T., Stamenkovic V., Ross P. Jr., Markovic N., Temperature dependent surface electrochemistry on Pt single crystals in alkaline electrolyte. Part 3. The oxygen reduction reaction. Phys. Chem. Chem. Phys. 5, 400–406 (2003). [Google Scholar]

[R95] 95.Ross P. N. Jr., Oxygen reduction reaction on smooth single crystal electrodes in Handbook of Fuel Cells (2010), vol. 2, p. 465. [Google Scholar]

[R96] 96.Ramaswamy N., Mukerjee S., Alkaline anion-exchange membrane fuel cells: Challenges in electrocatalysis and interfacial charge transfer. Chem. Rev. 119, 11945–11979 (2019). [DOI] [PubMed] [Google Scholar]

[R97] 97.Hardin W. G., Mefford J. T., Slanac D. A., Patel B. B., Wang X., Dai S., Zhao X., Ruoff R. S., Johnston K. P., Stevenson K. J., Tuning the electrocatalytic activity of perovskites through active site variation and support interactions. Chem. Mater. 26, 3368–3376 (2014). [Google Scholar]

[R98] 98.Ge X., Du Y., Li B., Hor T. S. A., Sindoro M., Zong Y., Zhang H., Liu Z., Intrinsically conductive perovskite oxides with enhanced stability and electrocatalytic activity for oxygen reduction reactions. ACS Catal. 6, 7865–7871 (2016). [Google Scholar]

[R99] 99.Fabbri E., Mohamed R., Levecque P., Conrad O., R. d. Kötz, Schmidt T. J., Composite electrode boosts the activity of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ perovskite and carbon toward oxygen reduction in alkaline media. ACS Catal. 4, 1061–1070 (2014). [Google Scholar]

[R100] 100.Beall C. E., Fabbri E., Schmidt T. J., Perovskite oxide based electrodes for the oxygen reduction and evolution reactions: The underlying mechanism. ACS Catal. 11, 3094–3114 (2021). [Google Scholar]

[R101] 101.Mariano R. G., Wahab O. J., Rabinowitz J. A., Oppenheim J., Chen T., Unwin P. R., Dincǎ M., Thousand-fold increase in O₂ electroreduction rates with conductive MOFs. ACS Cent. Sci. 8, 975–982 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R102] 102.Gridin V., Du J., Haller S., Theis P., Hofmann K., Wiberg G. K. H., Kramm U. I., Arenz M., GDE vs RDE: Impact of operation conditions on intrinsic catalytic parameters of FeNC catalyst for the oxygen reduction reaction. Electrochim. Acta 444, 142012 (2023). [Google Scholar]

[R103] 103.Inaba M., Jensen A. W., Sievers G. W., Escudero-Escribano M., Zana A., Arenz M., Benchmarking high surface area electrocatalysts in a gas diffusion electrode: Measurement of oxygen reduction activities under realistic conditions. Energ. Environ. Sci. 11, 988–994 (2018). [Google Scholar]

[R104] 104.Kim J. H., Yoo S., Murphy R., Chen Y., Ding Y., Pei K., Zhao B., Kim G., Choi Y., Liu M., Promotion of oxygen reduction reaction on a double perovskite electrode by a water-induced surface modification. Energ. Environ. Sci. 14, 1506–1516 (2021). [Google Scholar]

[R105] 105.Li Q., Zhang D., Wu J., Dai S., Liu H., Lu M., Cui R., Liang W., Wang D., Xi P., Liu M., Li H., Huang L., Cation-deficient perovskites greatly enhance the electrocatalytic activity for oxygen reduction reaction. Adv. Mater. 36, 2309266 (2024). [DOI] [PubMed] [Google Scholar]

[R106] 106.Wang X., Gao X. J., Qin L., Wang C., Song L., Zhou Y.-N., Zhu G., Cao W., Lin S., Zhou L., e_g occupancy as an effective descriptor for the catalytic activity of perovskite oxide-based peroxidase mimics. Nat. Commun. 10, 704 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R107] 107.Suntivich J., Gasteiger H. A., Yabuuchi N., Nakanishi H., Goodenough J. B., Shao-Horn Y., Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. Nat. Chem. 3, 546–550 (2011). [DOI] [PubMed] [Google Scholar]

[R108] 108.Hua B., Sun Y.-F., Li M., Yan N., Chen J., Zhang Y.-Q., Zeng Y., Shalchi Amirkhiz B., Luo J.-L., Stabilizing double perovskite for effective bifunctional oxygen electrocatalysis in alkaline conditions. Chem. Mater. 29, 6228–6237 (2017). [Google Scholar]

[R109] 109.Abe Y., Satoh I., Saito T., Kan D., Shimakawa Y., Oxygen reduction reaction catalytic activities of pure Ni-based perovskite-related structure oxides. Chem. Mater. 32, 8694–8699 (2020). [Google Scholar]

[R110] 110.Huang H., Huang A., Liu D., Han W., Kuo C.-H., Chen H.-Y., Li L., Pan H., Peng S., Tailoring oxygen reduction reaction kinetics on perovskite oxides via oxygen vacancies for low-temperature and knittable zinc-air batteries. Adv. Mater. 35, e2303109 (2023). [DOI] [PubMed] [Google Scholar]

[R111] 111.Yuasa M., Tachibana N., Shimanoe K., Oxygen reduction activity of carbon-supported La_1–xCaxMn_1–yFeyO₃ nanoparticles. Chem. Mater. 25, 3072–3079 (2013). [Google Scholar]

[R112] 112.Shi L., Zhou W., Li Z., Koul S., Kushima A., Yang Y., Periodically ordered nanoporous perovskite photoelectrode for efficient photoelectrochemical water splitting. ACS Nano 12, 6335–6342 (2018). [DOI] [PubMed] [Google Scholar]

[R113] 113.Zhu K., Shi F., Zhu X., Yang W., The roles of oxygen vacancies in electrocatalytic oxygen evolution reaction. Nano Energy 73, 104761 (2020). [Google Scholar]

[R114] 114.Zhu Y., Zhang L., Zhao B., Chen H., Liu X., Zhao R., Wang X., Liu J., Chen Y., Liu M., Improving the activity for oxygen evolution reaction by tailoring oxygen defects in double perovskite oxides. Adv. Funct. Mater. 29, 1901783 (2019). [Google Scholar]

[R115] 115.Badreldin A., Abusrafa A. E., Abdel-Wahab A., Oxygen-deficient perovskites for oxygen evolution reaction in alkaline media: A review. Emergent Mater. 3, 567–590 (2020). [Google Scholar]

[R116] 116.Aoki Y., Tsuji E., Motohashi T., Kowalski D., Habazaki H., La_0.7Sr_0.3Mn_1–xNi_xO_3−δ electrocatalysts for the four-electron oxygen reduction reaction in concentrated alkaline media. J. Phys. Chem. C 122, 22301–22308 (2018). [Google Scholar]

[R117] 117.Sunarso J., Torriero A. A., Zhou W., Howlett P. C., Forsyth M., Oxygen reduction reaction activity of La-based perovskite oxides in alkaline medium: A thin-film rotating ring-disk electrode study. J. Phys. Chem. C 116, 5827–5834 (2012). [Google Scholar]

[R118] 118.Alegre C., Modica E., Aricò A., Baglio V., Bifunctional oxygen electrode based on a perovskite/carbon composite for electrochemical devices. J. Electroanal. Chem. 808, 412–419 (2018). [Google Scholar]

[R119] 119.Malkhandi S., Trinh P., Manohar A. K., Jayachandrababu K., Kindler A., Prakash G. K. S., Narayanan S. R., Electrocatalytic activity of transition metal oxide-carbon composites for oxygen reduction in alkaline batteries and fuel cells. J. Electrochem. Soc. 160, F943–F952 (2013). [Google Scholar]

[R120] 120.Nishio K., Molla S., Okugaki T., Nakanishi S., Nitta I., Kotani Y., Effects of carbon on oxygen reduction and evolution reactions of gas-diffusion air electrodes based on perovskite-type oxides. J. Power Sources 298, 236–240 (2015). [Google Scholar]

[R121] 121.Mefford J. T., Kurilovich A. A., Saunders J., Hardin W. G., Abakumov A. M., Forslund R. P., Bonnefont A., Dai S., Johnston K. P., Stevenson K. J., Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La_1-xSr_xCoO_3-δ perovskite composite electrodes. Phys. Chem. Chem. Phys. 21, 3327–3338 (2019). [DOI] [PubMed] [Google Scholar]

[R122] 122.Poux T., Bonnefont A., Kéranguéven G., Tsirlina G. A., Savinova E. R., Electrocatalytic oxygen reduction reaction on perovskite oxides: Series versus direct pathway. ChemPhysChem 15, 2108–2120 (2014). [DOI] [PubMed] [Google Scholar]

[R123] 123.Hermann V., Dutriat D., Müller S., Comninellis C., Mechanistic studies of oxygen reduction at La_0.6Ca_0.4CoO₃-activated carbon electrodes in a channel flow cell. Electrochim. Acta 46, 365–372 (2000). [Google Scholar]

[R124] 124.Li X., Qu W., Zhang J., Wang H., Electrocatalytic activities of La_0.6Ca_0.4CoO₃ and La_0.6Ca_0.4CoO₃-carbon composites toward the oxygen reduction reaction in concentrated alkaline electrolytes. J. Electrochem. Soc. 158, A597 (2011). [Google Scholar]

[R125] 125.Chung D. Y., Park S., Lopes P. P., Stamenkovic V. R., Sung Y.-E., Markovic N. M., Strmcnik D., Electrokinetic analysis of poorly conductive electrocatalytic materials. ACS Catal. 10, 4990–4996 (2020). [Google Scholar]

[R126] 126.Morales-Guio C. G., Stern L.-A., Hu X., Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution. Chem. Soc. Rev. 43, 6555–6569 (2014). [DOI] [PubMed] [Google Scholar]

[R127] 127.Fletcher S., Tafel slopes from first principles. J. Solid State Electrochem. 13, 537–549 (2009). [Google Scholar]

[R128] 128.Bockris J. M., Potter E., The mechanism of the cathodic hydrogen evolution reaction. J. Electrochem. Soc. 99, 169 (1952). [Google Scholar]

[R129] 129.Zhu Y., Lin Q., Zhong Y., Tahini H. A., Shao Z., Wang H., Metal oxide-based materials as an emerging family of hydrogen evolution electrocatalysts. Energ. Environ. Sci. 13, 3361–3392 (2020). [Google Scholar]

[R130] 130.Zhou K. L., Wang Z., Han C. B., Ke X., Wang C., Jin Y., Zhang Q., Liu J., Wang H., Yan H., Platinum single-atom catalyst coupled with transition metal/metal oxide heterostructure for accelerating alkaline hydrogen evolution reaction. Nat. Commun. 12, 3783 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R131] 131.Miu E. V., McKone J. R., Mpourmpakis G., The sensitivity of metal oxide electrocatalysis to bulk hydrogen intercalation: Hydrogen evolution on tungsten oxide. J. Am. Chem. Soc. 144, 6420–6433 (2022). [DOI] [PubMed] [Google Scholar]

[R132] 132.Wang J., Gao Y., Ciucci F., Mechanochemical coupling of MoS₂ and perovskites for hydrogen generation. ACS Appl. Energy Mater. 1, 6409–6416 (2018). [Google Scholar]

[R133] 133.Dai J., Zhu Y., Tahini H. A., Lin Q., Chen Y., Guan D., Zhou C., Hu Z., Lin H.-J., Chan T.-S., Chen C.-T., Smith S. C., Wang H., Zhou W., Shao Z., Single-phase perovskite oxide with super-exchange induced atomic-scale synergistic active centers enables ultrafast hydrogen evolution. Nat. Commun. 11, 5657 (2020). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R134] 134.Li Q., Wang D., Lu Q., Meng T., Yan M., Fan L., Xing Z., Yang X., Identifying the activation mechanism and boosting electrocatalytic activity of layered perovskite ruthenate. Small 16, e1906380 (2020). [DOI] [PubMed] [Google Scholar]

[R135] 135.Pan S., Yang X., Sun J., Wang X., Zhu J., Fu Y., Competitive adsorption mechanism of defect-induced d-orbital single electrons in SrRuO₃ for alkaline hydrogen evolution reaction. Adv. Energy Mater. 13, 2301779 (2023). [Google Scholar]

[R136] 136.Zhang L., Jang H., Li Z., Liu H., Kim M. G., Liu X., Cho J., SrIrO₃ modified with laminar Sr₂IrO₄ as a robust bifunctional electrocatalyst for overall water splitting in acidic media. Chem. Eng. J. 419, 129604 (2021). [Google Scholar]

[R137] 137.Yu J., Wu X., Guan D., Hu Z., Weng S.-C., Sun H., Song Y., Ran R., Zhou W., Ni M., Shao Z., Monoclinic SrIrO₃: An easily synthesized conductive perovskite oxide with outstanding performance for overall water splitting in alkaline solution. Chem. Mater. 32, 4509–4517 (2020). [Google Scholar]

[R138] 138.Subbaraman R., Tripkovic D., Strmcnik D., Chang K.-C., Uchimura M., Paulikas A. P., Stamenkovic V., Markovic N. M., Enhancing hydrogen evolution activity in water splitting by tailoring Li⁺-Ni(OH)₂-Pt interfaces. Science 334, 1256–1260 (2011). [DOI] [PubMed] [Google Scholar]

[R139] 139.Greeley J., Jaramillo T. F., Bonde J., Chorkendorff I., Nørskov J. K., Computational high-throughput screening of electrocatalytic materials for hydrogen evolution. Nat. Mater. 5, 909–913 (2006). [DOI] [PubMed] [Google Scholar]

[R140] 140.Dai J., Zhu Y., Chen Y., Wen X., Long M., Wu X., Hu Z., Guan D., Wang X., Zhou C., Lin Q., Sun Y., Weng S.-C., Wang H., Zhou W., Shao Z., Hydrogen spillover in complex oxide multifunctional sites improves acidic hydrogen evolution electrocatalysis. Nat. Commun. 13, 1189 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R141] 141.Zhu Y., Tahini H. A., Hu Z., Dai J., Chen Y., Sun H., Zhou W., Liu M., Smith S. C., Wang H., Shao Z., Unusual synergistic effect in layered Ruddlesden−Popper oxide enables ultrafast hydrogen evolution. Nat. Commun. 10, 149 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R142] 142.Zhang S., Duan G., Qiao L., Tang Y., Chen Y., Sun Y., Wan P., Zhang S., Electrochemical ammonia synthesis from N₂ and H₂O catalyzed by doped LaFeO₃ perovskite under mild conditions. Ind. Eng. Chem. Res. 58, 8935–8939 (2019). [Google Scholar]

[R143] 143.Liu Y., Kong X., Guo X., Li Q., Ke J., Wang R., Li Q., Geng Z., Zeng J., Enhanced N₂ electroreduction over LaCoO₃ by introducing oxygen vacancies. ACS Catal. 10, 1077–1085 (2020). [Google Scholar]

[R144] 144.Yoon J. W., Chang H., Lee S.-J., Hwang Y. K., Hong D.-Y., Lee S.-K., Lee J. S., Jang S., Yoon T.-U., Kwac K., Jung Y., Pillai R. S., Faucher F., Vimont A., Daturi M., Férey G., Serre C., Maurin G., Bae Y.-S., Chang J.-S., Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites. Nat. Mater. 16, 526–531 (2017). [DOI] [PubMed] [Google Scholar]

[R145] 145.Ohrelius M., Guo H., Xian H., Yu G., Alshehri A. A., Alzahrani K. A., Li T., Andersson M., Electrochemical synthesis of ammonia based on a perovskite LaCrO₃ catalyst. ChemCatChem 12, 731–735 (2020). [Google Scholar]

[R146] 146.Hwang J., Rao R. R., Giordano L., Akkiraju K., Wang X. R., Crumlin E. J., Bluhm H., Shao-Horn Y., Regulating oxygen activity of perovskites to promote NO_x oxidation and reduction kinetics. Nat. Catal. 4, 663–673 (2021). [Google Scholar]

[R147] 147.Zheng H., Zhang Y., Wang Y., Wu Z., Lai F., Chao G., Zhang N., Zhang L., Liu T., Perovskites with enriched oxygen vacancies as a family of electrocatalysts for efficient nitrate reduction to ammonia. Small 19, 2205625 (2023). [DOI] [PubMed] [Google Scholar]

[R148] 148.Yang L.-H., Lin Z.-Q., Liao M.-T., Yang W.-J., Pan J.-X., Li W., Yang C., Wu Y.-J., Wang G.-Z., Lv S.-H., Engineering oxygen vacancies in perovskite oxides by in-situ electrochemical activation for highly efficient nitrate reduction. Appl. Surf. Sci. 639, 158208 (2023). [Google Scholar]

[R149] 149.Chu K., Zong W., Xue G., Guo H., Qin J., Zhu H., Zhang N., Tian Z., Dong H., Miao Y.-E., Roeffaers M. B. J., Hofkens J., Lai F., Liu T., Cation substitution strategy for developing perovskite oxide with rich oxygen vacancy-mediated charge redistribution enables highly efficient nitrate electroreduction to ammonia. J. Am. Chem. Soc. 145, 21387–21396 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R150] 150.Pi Y., Guo J., Shao Q., Huang X., All-inorganic SrSnO₃ perovskite nanowires for efficient CO₂ electroreduction. Nano Energy 62, 861–868 (2019). [Google Scholar]

[R151] 151.Zhang H., Xu Y., Lu M., Xie X., Huang L., Perovskite oxides for cathodic electrocatalysis of energy-related gases: From O₂ to CO₂ and N₂. Adv. Funct. Mater. 31, 2101872 (2021). [Google Scholar]

[R152] 152.Mignard D., Barik R. C., Bharadwaj A. S., Pritchard C. L., Ragnoli M., Cecconi F., Miller H., Yellowlees L. J., Revisiting strontium-doped lanthanum cuprate perovskite for the electrochemical reduction of CO₂. J. CO2 Util. 5, 53–59 (2014). [Google Scholar]

[R153] 153.Singh R. P., Arora P., Nellaiappan S., Shivakumara C., Irusta S., Paliwal M., Sharma S., Electrochemical insights into layered La₂CuO₄ perovskite: Active ionic copper for selective CO₂ electroreduction at low overpotential. Electrochim. Acta 326, 134952 (2019). [Google Scholar]

[R154] 154.Chen S., Su Y., Deng P., Qi R., Zhu J., Chen J., Wang Z., Zhou L., Guo X., Xia B. Y., Highly selective carbon dioxide electroreduction on structure-evolved copper perovskite oxide toward methane production. ACS Catal. 10, 4640–4646 (2020). [Google Scholar]

[R155] 155.Wang J., Cheng C., Huang B., Cao J., Li L., Shao Q., Zhang L., Huang X., Grain-boundary-engineered La₂CuO₄ perovskite nanobamboos for efficient CO₂ reduction reaction. Nano Lett. 21, 980–987 (2021). [DOI] [PubMed] [Google Scholar]

[R156] 156.Gao X., Bai X., Wang P., Jiao Y., Davey K., Zheng Y., Qiao S.-Z., Boosting urea electrooxidation on oxyanion-engineered nickel sites via inhibited water oxidation. Nat. Commun. 14, 5842 (2023). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R157] 157.Zhang L., Wang L., Lin H., Liu Y., Ye J., Wen Y., Chen A., Wang L., Ni F., Zhou Z., Sun S., Li Y., Zhang B., Peng H., A lattice-oxygen-involved reaction pathway to boost urea oxidation. Angew. Chem. Int. Ed. 131, 16976–16981 (2019). [DOI] [PubMed] [Google Scholar]

[R158] 158.Han B., Risch M., Lee Y.-L., Ling C., Jia H., Shao-Horn Y., Activity and stability trends of perovskite oxides for oxygen evolution catalysis at neutral pH. Phys. Chem. Chem. Phys. 17, 22576–22580 (2015). [DOI] [PubMed] [Google Scholar]

[R159] 159.Zhang Y., Arpino K. E., Yang Q., Kikugawa N., Sokolov D. A., Hicks C. W., Liu J., Felser C., Li G., Observation of a robust and active catalyst for hydrogen evolution under high current densities. Nat. Commun. 13, 7784 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R160] 160.Seok J., Molina Villarino A., Shi Z., Yang Y., Ahmadi M., Muller D. A., DiSalvo F. J., Abruña H. D., La-based perovskite oxide catalysts for alkaline oxygen reduction: The importance of electrochemical stability. J. Phys. Chem. C 126, 3098–3108 (2022). [Google Scholar]

[R161] 161.Ignatans R., Mallia G., Ahmad E. A., Spillane L., Stoerzinger K. A., Shao-Horn Y., Harrison N. M., Tileli V., The effect of surface reconstruction on the oxygen reduction reaction properties of LaMnO₃. J. Phys. Chem. C 123, 11621–11627 (2019). [Google Scholar]

[R162] 162.Shih A. J., Monteiro M. C., Dattila F., Pavesi D., Philips M., da Silva A. H., Vos R. E., Ojha K., Park S., van der Heijden O., Marcandalli G., Goyal A., Villalba M., Chen X., Gunasooriya G. T. K. K., Crum I. M., Mom R., López N., Koper M. T. M., Water electrolysis. Nat. Rev. Methods Primers 2, 84 (2022). [Google Scholar]

[R163] 163.Kas R., Ayemoba O., Firet N. J., Middelkoop J., Smith W. A., Cuesta A., In-situ infrared spectroscopy applied to the study of the electrocatalytic reduction of CO₂: Theory, practice and challenges. ChemPhysChem 20, 2904–2925 (2019). [DOI] [PubMed] [Google Scholar]

[R164] 164.Timoshenko J., Roldan Cuenya B., In situ/operando electrocatalyst characterization by X-ray absorption spectroscopy. Chem. Rev. 121, 882–961 (2021). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R165] 165.Yang L., Yu G., Ai X., Yan W., Duan H., Chen W., Li X., Wang T., Zhang C., Huang X., Chen J.-S., Zou X., Efficient oxygen evolution electrocatalysis in acid by a perovskite with face-sharing IrO₆ octahedral dimers. Nat. Commun. 9, 5236 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R166] 166.Mefford J. T., Rong X., Abakumov A. M., Hardin W. G., Dai S., Kolpak A. M., Johnston K. P., Stevenson K. J., Water electrolysis on La_1−xSr_xCoO_3−δ perovskite electrocatalysts. Nat. Commun. 7, 11053 (2016). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R167] 167.Forslund R. P., Hardin W. G., Rong X., Abakumov A. M., Filimonov D., Alexander C. T., Mefford J. T., Iyer H., Kolpak A. M., Johnston K. P., Stevenson K. J., Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La_0.5Sr_1.5Ni_1-xFe_xO_4±δ Ruddlesden-Popper oxides. Nat. Commun. 9, 3150 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R168] 168.Zhang J., Ye Y., Wang Z., Xu Y., Gui L., He B., Zhao L., Probing dynamic self-reconstruction on perovskite fluorides toward ultrafast oxygen evolution. Adv. Sci. 9, e2201916 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R169] 169.Lu M., Zheng Y., Hu Y., Huang B., Ji D., Sun M., Li J., Peng Y., Si R., Xi P., Yan C.-H., Artificially steering electrocatalytic oxygen evolution reaction mechanism by regulating oxygen defect contents in perovskites. Sci. Adv. 8, eabq3563 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R170] 170.Jin Z., Bard A. J., Surface interrogation of electrodeposited MnO_x and CaMnO₃ perovskites by scanning electrochemical microscopy: Probing active sites and kinetics for the oxygen evolution reaction. Angew. Chem. Int. Ed. 133, 807–812 (2021). [DOI] [PubMed] [Google Scholar]

[R171] 171.Ali-Löytty H., Louie M. W., Singh M. R., Li L., Sanchez Casalongue H. G., Ogasawara H., Crumlin E. J., Liu Z., Bell A. T., Nilsson A., Friebel D., Ambient-pressure XPS study of a Ni–Fe electrocatalyst for the oxygen evolution reaction. J. Phys. Chem. C 120, 2247–2253 (2016). [Google Scholar]

[R172] 172.Moon J., Beker W., Siek M., Kim J., Lee H. S., Hyeon T., Grzybowski B. A., Active learning guides discovery of a champion four-metal perovskite oxide for oxygen evolution electrocatalysis. Nat. Mater. 23, 108–115 (2024). [DOI] [PubMed] [Google Scholar]

[R173] 173.Sun Y., Liao H., Wang J., Chen B., Sun S., Ong S. J. H., Xi S., Diao C., Du Y., Wang J.-O., Breese M. B. H., Li S., Zhang H., Xu Z. J., Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides. Nat. Catal. 3, 554–563 (2020). [Google Scholar]

[R174] 174.Lee J. G., Hwang J., Hwang H. J., Jeon O. S., Jang J., Kwon O., Lee Y., Han B., Shul Y.-G., A new family of perovskite catalysts for oxygen-evolution reaction in alkaline media: BaNiO₃ and BaNi_0.83O_2.5. J. Am. Chem. Soc. 138, 3541–3547 (2016). [DOI] [PubMed] [Google Scholar]

[R175] 175.Zhang R., Pearce P. E., Duan Y., Dubouis N., Marchandier T., Grimaud A., Importance of water structure and catalyst-electrolyte interface on the design of water splitting catalysts. Chem. Mater. 31, 8248–8259 (2019). [Google Scholar]

[R176] 176.Kim J., Yin X., Tsao K.-C., Fang S., Yang H., Ca₂Mn₂O₅ as oxygen-deficient perovskite electrocatalyst for oxygen evolution reaction. J. Am. Chem. Soc. 136, 14646–14649 (2014). [DOI] [PubMed] [Google Scholar]

[R177] 177.Jacobs R., Hwang J., Shao-Horn Y., Morgan D., Assessing correlations of perovskite catalytic performance with electronic structure descriptors. Chem. Mater. 31, 785–797 (2019). [Google Scholar]

[R178] 178.Ashok A., Kumar A., Bhosale R. R., Almomani F., Malik S. S., Suslov S., Tarlochan F., Combustion synthesis of bifunctional LaMO₃ (M = Cr, Mn, Fe, Co, Ni) perovskites for oxygen reduction and oxygen evolution reaction in alkaline media. J. Electroanal. Chem. 809, 22–30 (2018). [Google Scholar]

[R179] 179.Dias J. A., Andrade M. A. Jr., Santos H. S., Morelli M. R., Mascaro L. H., Lanthanum-based perovskites for catalytic oxygen evolution reaction. ChemElectroChem 7, 3173–3192 (2020). [Google Scholar]

[R180] 180.Emery A. A., Wolverton C., High-throughput DFT calculations of formation energy, stability and oxygen vacancy formation energy of ABO₃ perovskites. Sci. Data 4, 170153 (2017). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R181] 181.Karki S. B., Ramezanipour F., Pseudocapacitive energy storage and electrocatalytic hydrogen-evolution activity of defect-ordered perovskites Sr_xCa_3–xGaMn₂O₈ (x = 0 and 1). ACS Appl. Energy Mater. 3, 10983–10992 (2020). [Google Scholar]

[R182] 182.Togano H., Asai K., Oda S., Ikeno H., Kawaguchi S., Oka K., Wada K., Yagi S., Yamada I., Highly active hydrogen evolution catalysis on oxygen-deficient double-perovskite oxide PrBaCo₂O_6−δ. Mater. Chem. Front. 4, 1519–1529 (2020). [Google Scholar]

[R183] 183.Islam Q. A., Majee R., Bhattacharyya S., Bimetallic nanoparticle decorated perovskite oxide for state-of-the-art trifunctional electrocatalysis. J. Mater. Chem. A 7, 19453–19464 (2019). [Google Scholar]

[R184] 184.Wang J., Gao Y., Chen D., Liu J., Zhang Z., Shao Z., Ciucci F., Water splitting with an enhanced bifunctional double perovskite. ACS Catal. 8, 364–371 (2018). [Google Scholar]

[R185] 185.Zhu Y., Zhou W., Zhong Y., Bu Y., Chen X., Zhong Q., Liu M., Shao Z., A perovskite nanorod as bifunctional electrocatalyst for overall water splitting. Adv. Energy Mater. 7, 1602122 (2017). [Google Scholar]

[R186] 186.Liu Y., Dou Y., Li S., Xia T., Xie Y., Wang Y., Zhang W., Wang J., Huo L., Zhao H., Synergistic interaction of double/simple perovskite heterostructure for efficient hydrogen evolution reaction at high current density. Small Methods 5, e2000701 (2021). [DOI] [PubMed] [Google Scholar]

[R187] 187.Bu Y., Jang H., Gwon O., Kim S. H., Joo S. H., Nam G., Kim S., Qin Y., Zhong Q., Kwak S. K., Synergistic interaction of perovskite oxides and N-doped graphene in versatile electrocatalyst. J. Mater. Chem. A 7, 2048–2054 (2019). [Google Scholar]

[R188] 188.Dou Y., Xie Y., Hao X., Xia T., Li Q., Wang J., Huo L., Zhao H., Addressing electrocatalytic activity and stability of LnBaCo₂O_5+δ perovskites for hydrogen evolution reaction by structural and electronic features. Appl Catal B 297, 120403 (2021). [Google Scholar]

[R189] 189.Ilanchezhiyan P., Kumar G. M., Siva C., Cho H., Tamilselvan S., Seal S., Kang T. W., Kim D. Y., Aid of cobalt ions in boosting the electrocatalytic oxygen and hydrogen evolution functions of NdFeO₃ perovskite nanostructures. J. Mater. Res. Technol. 11, 2246–2254 (2021). [Google Scholar]

[R190] 190.Hua B., Li M., Zhang Y.-Q., Sun Y.-F., Luo J.-L., All-in-one perovskite catalyst: Smart controls of architecture and composition toward enhanced oxygen/hydrogen evolution reactions. Adv. Energy Mater. 7, 1700666 (2017). [Google Scholar]

[R191] 191.Karki S. B., Andriotis A. N., Menon M., Ramezanipour F., Bifunctional water-splitting electrocatalysis achieved by defect order in LaA₂Fe₃O₈ (A= Ca, Sr). ACS Appl. Energy Mater. 4, 12063–12066 (2021). [Google Scholar]

[R192] 192.Guan D., Zhou J., Huang Y.-C., Dong C.-L., Wang J.-Q., Zhou W., Shao Z., Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor. Nat. Commun. 10, 3755 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R193] 193.Ji D., Liu C., Yao Y., Luo L., Wang W., Chen Z., Cerium substitution in LaCoO₃ perovskite oxide as bifunctional electrocatalysts for hydrogen and oxygen evolution reactions. Nanoscale 13, 9952–9959 (2021). [DOI] [PubMed] [Google Scholar]

[R194] 194.Sun Q., Dai Z., Zhang Z., Chen Z., Lin H., Gao Y., Chen D., Double perovskite PrBaCo₂O_5.5: An efficient and stable electrocatalyst for hydrogen evolution reaction. J. Power Sources 427, 194–200 (2019). [Google Scholar]

[R195] 195.Hu C., Hong J., Huang J., Chen W., Segre C. U., Suenaga K., Zhao W., Huang F., Wang J., Surface decoration accelerates the hydrogen evolution kinetics of a perovskite oxide in alkaline solution. Energ. Environ. Sci. 13, 4249–4257 (2020). [Google Scholar]

[R196] 196.Alom M. S., Kananke-Gamage C. C. W., Ramezanipour F., Perovskite oxides as electrocatalysts for hydrogen evolution reaction. ACS Omega 7, 7444–7451 (2022). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R197] 197.Nørskov J. K., Bligaard T., Logadottir A., Kitchin J. R., Chen J. G., Pandelov S., Stimming U., Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, J23 (2005). [Google Scholar]

[R198] 198.Jain A., Ong S. P., Hautier G., Chen W., Richards W. D., Dacek S., Cholia S., Gunter D., Skinner D., Ceder G., Persson K. A., Commentary: The materials project: A materials genome approach to accelerating materials innovation. APL Mater. 1, 011002 (2013). [Google Scholar]

[R199] 199.Chanussot L., Das A., Goyal S., Lavril T., Shuaibi M., Riviere M., Tran K., Heras-Domingo J., Ho C., Hu W., Palizhati A., Sriram A., Wood B., Yoon J., Parikh D., Zitnick C. L., Ulissi Z., Open catalyst 2020 (OC20) dataset and community challenges. ACS Catal. 11, 6059–6072 (2021). [Google Scholar]

PERMALINK

Structural evolution and catalytic mechanisms of perovskite oxides in electrocatalysis

Jia-Wei Zhao

Yunxiang Li

Deyan Luan

Xiong Wen (David) Lou

Roles

Abstract

INTRODUCTION

Fig. 1. The promise of electrocatalysis.

Fig. 2. Schematic illustration of the perovskite oxides in electrocatalysis.

PEROVSKITE OXIDES IN OER

OER mechanisms

Fig. 3. OER mechanisms of perovskite oxides.

Surface evolution during OER

Key factors affecting OER

Fig. 4. Key factors affecting OER of perovskite oxides.

Catalyst design for OER

PEROVSKITE OXIDES IN ORR

ORR mechanisms

Fig. 5. Perovskite oxides in ORR.

Key factors affecting ORR

Catalyst design for ORR

PEROVSKITE OXIDES IN HER

HER mechanisms

Fig. 6. Perovskite oxides in HER.

Key factors affecting HER

Catalyst design for HER

PEROVSKITE OXIDES IN OTHER REACTIONS

Research progress in other reactions

Surface evolution trends during reactions

Fig. 7. Perovskite oxides in other reactions.

CHARACTERIZATIONS AND RESEARCH FRAMEWORK

Identifying active sites by characterizations

Fig. 8. Characterizations and research framework of perovskite oxides.

Research framework

CONCLUSIONS AND PERSPECTIVES

Acknowledgments

REFERENCES AND NOTES

ACTIONS

PERMALINK

RESOURCES

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