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. 2026 Jun 14;21(11):e70841. doi: 10.1002/asia.70841

A Facile Immersion Strategy for Molybdate‐Modified Co/Co(OH)2@Cu Nanowires as High‐Efficiency and Durable Electrocatalysts for Alkaline Hydrogen Evolution

Fengye Zhang 1, Huiping You 1, Xiyuan Chen 1, Yangyang Wang 1, Xiaojuan Wang 1, Jing Zhang 1, Enlai Hu 1,✉, Yating Wan 2,✉, Zhongwei Chen 3,4,✉
PMCID: PMC13355136  PMID: 42289771

ABSTRACT

Developing efficient and durable earth‐abundant electrocatalysts for the alkaline hydrogen evolution reaction (HER) is limited by the sluggish water dissociation kinetics. Herein, a facile immersion strategy was proposed to synthesize molybdate species‐modified Co/Co(OH)2@Cu (MCC@Cu) nanowires as high‐efficiency alkaline HER electrocatalysts. The introduced molybdate species remarkably promotes the water dissociation process, enhances active site exposure, and improves charge transfer, as revealed by the in situ Raman tests and electrochemical analysis. As a result, the as‐prepared MCC@Cu nanowires have a low overpotential of 37 mV at 10 mA cm−2, which is much lower than that of the molybdate‐free one (184 mV). This work offers a facile and scalable method for the design of molybdate‐modified electrocatalysts toward alkaline HER.

Keywords: Co/Co(OH)2 , hydrogen evolution reaction, molybdate modification, water dissociation

A facile immersion strategy is proposed to synthesize molybdate species‐modified Co/Co(OH)2@Cu nanowires as high‐efficiency and durable alkaline HER electrocatalysts.

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1. Introduction

Green hydrogen, generated through electrochemical water splitting powered by renewable electricity, is considered a promising energy carrier because of its zero‐carbon emission and high energy density merits [1, 2, 3]. As compared to proton exchange membrane water electrolysis, alkaline water electrolysis has been widely used in industry [4], due to its cost‐effective profile and compatibility with non‐noble metal electrocatalysts. However, the water dissociation of the HER process is sluggish, which is based on the cleavage of the O─H bond of water molecules [5, 6, 7, 8]. This sluggish step significantly limits proton supply for the subsequent HER step, severely slowing the reaction kinetics [9]. As a result, a large overpotential is required to trigger the process. Consequently, considerable research efforts have been made to develop the active earth‐abundant‐based electrocatalysts to promote the alkaline HER [10, 11].

Among the various earth‐abundant‐based materials, cobalt‐based heterostructures have emerged as promising alkaline HER electrocatalysts [12, 13, 14], especially the metallic cobalt and cobalt hydroxide composite (Co/Co(OH)2) [15, 16]. With the synergy between the components, the HER performance of Co/Co(OH)2 can be enhanced by intermediate adsorption energy modulation and active site expansion. For example, Frederiksen et al. reported the application of Co/Co(OH)2 composite for alkaline HER [15]. Subsequently, Shi and coworkers demonstrated that the Co(111) and amorphous Co(OH)2 composite is favorable for hydrogen atom desorption and hydrogen formation, thus improving alkaline HER activity [16]. However, there still remains room for the enhancement of the HER performance of Co/Co(OH)2 [17].

In addition to heterostructure development, surface functionalization is another prominent approach to improve the HER performance of the Co/Mo‐based electrocatalysts [18, 19, 20, 21]. Molybdate species modification has been proven to have promising potential in HER performance enhancement. For instance, Li and coworkers found that the adsorption of molybdate species at the electrocatalyst surface regulates the Gibbs free energy for HER, achieving an overpotential of 78 mV at 100 mA cm−2 [22]. Furthermore, Jiang and coworkers revealed that molybdate species near the interface between Co(OH)2 and electrolyte improve both durability and activity in alkaline HER conditions [23]. Notably, the origin of the molybdate species can be attributed to either the electrocatalyst surface reconstruction or the addition of molybdate‐containing additives in the electrolyte. Despite this progress, the rational design for the synthesis of efficient cobalt‐based materials with molybdate species modified as highly active and stable HER electrocatalysts remains urgent but highly demanding.

Herein, a facile immersion strategy was proposed to synthesize the molybdate species modified Co/Co(OH)2@Cu (MCC@Cu) nanowires as an efficient and durable alkaline HER electrocatalyst. Owing to the introduction of molybdate species, the water dissociation process was prominently accelerated, which was elucidated by the in situ electrochemical Raman measurements and Tafel slope results. As expected, the MCC@Cu nanowires only needed a low overpotential of 37 mV to reach a current density of 10 mA cm−2, while the overpotential was as high as 184 mV at the same current density for the molybdate‐free sample (CC@Cu nanowires). Moreover, the MCC@Cu nanowires could homogeneously output current for 280 h with current retention of 91.2%, much more durable than those of the CC@Cu nanowires. This work presents a facile and scalable strategy to molybdate‐modified HER electrocatalysts.

2. Results and Discussion

The synthesis process of molybdate‐modified Co(OH)2/Co@Cu (MCC@Cu) nanowires is illustrated in Figure 1. Typically, Cu(OH)2 nanowires are employed as the templates, which are synthesized according to the reported work [24]. In step I, the Cu(OH)2 nanowires are heated at 180°C for 2 h to obtain CuO nanowires. These CuO nanowires are then used as a working electrode to proceed electrodeposition for 1200 s at a constant current density of −0.25 A cm−2 (Step II). As a result, Co(OH)2/Co@Cu (CC@Cu) nanowires are obtained. The transformation of CuO to Cu can be attributed to the high cathodic current, which can create a reductive condition. Moreover, an alkaline condition can also be created under such cathodic current through hydrogen generation, facilitating the formation of Co(OH)2. The obtained CC@Cu nanowires are then immersed in the saturated sodium molybdate solution for 6 min to achieve molybdate species modified Co(OH)2/Co@Cu core‐shell (MCC@Cu) nanowires (Step III).

FIGURE 1.

FIGURE 1

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Schematic illustration of the synthesis process of MCC@Cu nanowires.

The formation process of the MCC@Cu nanowires was monitored by field scanning electron microscopy (FESEM) and x‐ray diffraction (XRD). As shown in Figure S1A,B, the Cu(OH)2 template has a shape in a nanowire with smooth surfaces. The XRD analysis (Figure S1C) demonstrated that the template can be assigned to orthorhombic Cu(OH)2 (JCPDS card No 04‐009‐4366). After the heat‐treated process as described above in step I, the Cu(OH)2 nanowires transform to monoclinic CuO (JCPDS card No. 01‐080‐1917) nanowires (Figure S2). The CuO nanowires still have a smooth surface. After the electrodeposition process, the CuO becomes metallic Cu, and the nanowires are covered by a layer of interconnected nanosheets, as revealed by the XRD and FESEM observation (Figure S3A–C). The existence of Co(OH)2 in the product was evidenced by the Raman spectrum. As shown in Figure S3D, the peak at 520 cm−1 corresponds to the characterization of the Co─O bond for Co(OH)2 [17, 25]. The molybdate modification was achieved upon the soaking process, with morphology and crystal retained, as revealed by FESEM images (Figure 2A–C) and XRD pattern (Figure S4A). Raman spectrum (Figure S4B) illustrated the retention of Co(OH)2 species and the successful modification of molybdate species. The two newly appeared peaks at 327 and 911 cm−1 are attributed to Co─O−Mo and Mo−O bonds stretching, respectively [26, 27]. To further exclude the formation of cobalt molybdate, we calcined MCC@Cu nanowires and pure Na2MoO4 at 500°C under N2. XRD pattern (Figure S5) showed no crystalline molybdate peaks for MCC@Cu, confirming that the molybdate species are adsorbed on the surface of the electrocatalyst. A transmission electron microscopy (TEM) image was recorded to further elucidate the microstructure of MCC@Cu nanowires. As shown in Figure 2D, the nanowires were covered by a layer of nanosheets, consistent with the FESEM results. High‐resolution TEM image (Figure 2E) of the nanosheet part displayed clear lattice fringes with an interplanar spacing of 0.20 nm, corresponding to the (111) plane of metallic cobalt. The amorphous part assigned to the Co(OH)2 was also observed (indexed with green arrow). Moreover, the selected area electron diffraction (SAED) pattern of MCC@Cu nanowires was consistent with the cubic cobalt (Figure 2F), with diffraction rings of (111), (200), and (220) [28].

FIGURE 2.

FIGURE 2

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(A–C) FESEM, (D) TEM, (E) HRTEM, and (F) SAED images of MCC@Cu nanowires.

X‐ray photoelectron spectroscopy (XPS) measurements were conducted to further reveal the surface chemical compositions and oxidation state of the MCC@Cu nanowires and CC@Cu nanowires. As presented by the survey result (Figure S6). Both MCC@Cu nanowires and CC@Cu nanowires exist Cu, Co, and O elements, with an additional peak of the Mo element in MCC@Cu nanowires. For the Cu 2p spectrum of MCC@Cu nanowires (Figure 3A), the peak at 932.7 eV corresponds to the Cu(0) species for metallic Cu, combined with the oxidized Cu species peak at 934.5 eV and satellite peak 944.5 eV [29, 30]. The high‐resolution Co 2p spectrum of MCC@Cu nanowires (Figure 3B) showed a peak at 781.0 eV for Co 2p3/2, consistent with the Co(II) species for Co(OH)2 [31, 32]. The corresponding satellite peak was situated at 785.7 eV [33]. Moreover, the typical peak of Co(0) species for metallic cobalt was observed at 778.1 eV [34]. As presented by the high‐resolution O 1s spectrum of MCC@Cu nanowires (Figure 3C), three kinds of peaks can be deconvoluted. The peaks at 533.3, 531.3, and 529.6 eV are ascribed to the adsorbed H2O, M‐OH, and M‐O species [31, 35], respectively. For the Mo 3d spectrum (Figure 3D), the peaks located at 235.4 and 232.2 eV are assigned to Mo(VI) species for the molybdate [36]. The presence of M─O and Mo(VI) species further proves that the immersed process successfully introduces molybdate species into the CC@Cu nanowires. The electronic interaction of molybdate modification was confirmed by the binding energy shift of Co and O species (Figure 3B,C). Compared to CC@Cu nanowires, the binding energies of Co(0), Co(II), M─O, and M‐OH in MCC@Cu nanowires shift to lower values. This indicates that electron density redistributes upon molybdate introduction, with electrons transferring from Co/Co(OH)2 to MoO4 2 − species.

FIGURE 3.

FIGURE 3

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XPS results of the prepared MCC@Cu nanowires and CC@Cu nanowires: (A) Cu 2p, (B) Co 2p, (C) O 1s, and (D) Mo 3d.

The HER performance of MCC@Cu nanowires was assessed in 1 M KOH solution using a conventional three‐electrode cell. The polarization curves (Figure S7) revealed that the optimal deposition time and immersion time were 1200 s and 6 min. The overpotential was determined to be only 37 mV (Figure 4A), which is 147 mV lower than that of CC@Cu nanowires and even comparable to the Pt/C benchmark (28 mV). Remarkably, such a performance greatly outperforms many other documented alkaline HER electrocatalysts (Figure 4B and Table S1). High current density performance is also crucial for practical industrial hydrogen production [37, 38]. The results show that MCC@Cu nanowires still maintain significantly better activity than CC@Cu nanowires at high current densities (Figure S8A,B). The high activity of MCC@Cu nanowires can be attributed to its improved kinetics, favorable electron transfer rate, and increased active sites. As shown in Figure 4C, the Tafel plot decreases from 142.0 mV dec−1 for CC@Cu nanowires to 76.2 mV dec−1 for MCC@Cu nanowires. This manifested that both samples showed a Volmer‐Heyrovsky process, with the Volmer step as the rate‐determining step [39, 40]. The lower Tafel slope of the MCC@Cu nanowires indicated its facilitated water dissociation step [41]. The enhanced reaction kinetics of the MCC@Cu nanowires were also verified by the Nyquist plots and the corresponding fitting results (Figure 4D). The impedance analysis results (Table S2) demonstrated that MCC@Cu nanowires exhibited a smaller charge‐transfer (R ct) than CC@Cu, suggesting a faster electron transfer rate for the former one. Moreover, the double‐layer capacitance (C dl) of each sample was estimated to evaluate the electrochemically active surface area (ECSA) [42]. The C dl was calculated based on the cyclic voltammogram results (Figure S9). Figure 4E displayed that the C dl of MCC@Cu nanowires (283.3 mF cm−2) is higher than CC@Cu nanowires (236.9 mF cm−2). The high C dl leads to improved electrocatalytic activity, and this results from the molybdate modification. Furthermore, the ECSA normalized polarization curves were provided (Figure 4F). The MCC@Cu nanowires still possessed a larger current density (j ECSA) than CC@Cu nanowires at the same potential, illustrating its enhanced intrinsic activity. These results highlight the important role of molybdate modification for MCC@Cu nanowires.

FIGURE 4.

FIGURE 4

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(A) Polarization curves of MCC@Cu nanowires, CC@Cu nanowires, and Pt/C benchmark. (B) Comparison of the overpotential of documented HER electrocatalysts. (C) Tafel slopes, (D) Nyquist plots, (E) Difference in current density plotted against scan rate displaying the value of double‐layer capacitances, and (F) ECSA normalized polarization curves of MCC@Cu nanowires and CC@Cu nanowires. (G) Chronoamperometry results of MCC@Cu nanowires and CC@Cu nanowires. (H) Faradaic efficiency result of MCC@Cu nanowires.

Long‐term durability, another important parameter for HER, was measured using chronoamperometry measurements. As shown in Figure 4G, MCC@Cu nanowires can homogeneously sustain a current density of 65 mA cm−2 for 280 h, with a high current density retention rate of 91.2%. In sharp contrast, CC@Cu nanowires had a fast decline in output, and only about 53.1% of the initial current density was retained over 180 h. Furthermore, at a high current of 500 mA cm−2, MCC@Cu nanowires operated stably for 140 h, with a current retention rate of 96.3% (Figure S10). This result demonstrates the key role of molybdate modification for MCC@Cu nanowires towards alkaline HER durability. The Faraday efficiency was evaluated using a burette and determined to be about 99.2% (Figure 4H), suggesting the outstanding energy conversion efficiency for MCC@Cu nanowires. After durability measurement, the nanowires were well maintained, as revealed by the FESEM images (Figure S11). ICP‐OES analysis of the electrolyte delivered a Mo concentration of 81.26 mg L− 1 (Table S3), confirming the limited leaching of molybdate species. Moreover, the XPS analysis results exhibited that the oxidation states of Cu, Co, O, and Mo elements were analogous to the pristine ones (Figure S12). The abovementioned results highlight the robust structures of MCC@Cu nanowires, which are beneficial for their outstanding durability [43].

The water dissociation thermodynamic process is the key factor for alkaline HER activity [44]. To confirm the promoted water dissociation process of MCC@Cu nanowires, the in situ electrochemical Raman test was conducted. The Raman spectra of both MCC@Cu and CC@Cu nanowires exhibited similarly broad peaks in the range of 2800–3800 cm−1 (Figure 5A,D). These peaks are characteristic of the stretching modes of interface water molecules [45, 46]. The spectra were deconvoluted by Gaussian fitting into three components, including 4‐coordinated hydrogen‐bonded water (3225 cm− 1, 4‐HBW), 2‐coordinated hydrogen‐bonded water (3450 cm− 1, 2‐HBW), and free water (3615 cm− 1) (Figure 5B,E). A better description of the activation of water molecules on the catalyst surface can be described by comparing the proportion of the O–H stretching Raman band. The area ratio of free water for both samples gradually decreases with the negative potential increased (0 to −0.2 V vs. RHE). Notably, MCC@Cu nanowires have a more significant decrease than that for CC@Cu nanowires (Figure 5C,F), implying MCC@Cu nanowires more favorable water dissociation kinetics [47]. These results significantly demonstrate the critical role of molybdate modification on the HER activity promotion by water dissociation acceleration.

FIGURE 5.

FIGURE 5

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(A,D) In situ electrochemical Raman spectra of MCC@Cu nanowires and CC@Cu nanowires from 0 to −0.2 V versus RHE, (B,E) Gaussian fittings of three stretching modes of interfacial water at different applied potentials, and (C,F) Proportion of free water of interfacial water at different potentials for MCC@Cu nanowires and CC@Cu nanowires.

3. Conclusion

In summary, a highly active and durable electrocatalyst of molybdate modified Co(OH)2/Co@Cu nanowires for alkaline HER has been developed. The molybdate species was facially introduced through an impregnation procedure. The as‐modified molybdate was proven to be favorable for active site increase, reaction kinetic enhancement, water dissociation promotion, and long‐term durability improvement. As a result, the MCC@Cu nanowires need only 37 mV to drive a current density of 10 mA cm−2 and can stably perform for 280 h, with a current retention rate of 91.2%. We believe that the outstanding alkaline HER performance of MCC@Cu nanowires could make them promising electrocatalysts for HER.

Supporting Information

Additional figures and experimental details are given within the Supporting Information file [24, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61].

Conflicts of Interest

The authors declare no conflicts of interest.

Supporting information

Supporting File: asia70841‐sup‐0001‐SuppMat.docx

ASIA-21-e70841-s001.docx (2.4MB, docx)

Acknowledgments

This work was supported by the National Natural Science Foundation of China (52202193), Zhejiang Provincial Natural Science Foundation of China (LQN26E020012), Power Battery and Systems Research Center from State Key Laboratory of Catalysis, Strategic Priority Research Program of Chinese Academy of Sciences (XDB0600104), Dalian Revitalization Talents Program (2022RG01), Liaoning Binhai Laboratory (LBLB202304), National Undergraduate Training Program on Innovation and Entrepreneurship (202510345008), Zhejiang Provincial College Students' Science and Technology Innovation Activity Plan (Xinmiao Talent Program, 2025R404A001).

Contributor Information

Enlai Hu, Email: huenlai@zjnu.edu.cn.

Yating Wan, Email: ytwan@zju.edu.cn.

Zhongwei Chen, Email: zwchen@dicp.ac.cn.

Data Availability Statement

The data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions.

References

  • 1. Odenweller A., Ueckerdt F., Nemet G. F., Jensterle M., and Luderer G., “Probabilistic Feasibility Space of Scaling up Green Hydrogen Supply,” Nature Energy 7 (2022): 854–865, 10.1038/s41560-022-01097-4. [DOI] [Google Scholar]
  • 2. Oliveira A. M., Beswick R. R., and Yan Y., “A Green Hydrogen Economy for a Renewable Energy Society,” Current Opinion in Chemical Engineering 33 (2021): 100701, 10.1016/j.coche.2021.100701. [DOI] [Google Scholar]
  • 3. Dinh C.‐T., Jain A., de Arquer F. P. G., et al., “Multi‐Site Electrocatalysts for Hydrogen Evolution in Neutral media by Destabilization of Water Molecules,” Nature Energy 4 (2019): 107–114, 10.1038/s41560-018-0296-8. [DOI] [Google Scholar]
  • 4. Tüysüz H., “Alkaline Water Electrolysis for Green Hydrogen Production,” Accounts of Chemical Research 57 (2024): 558–567, 10.1021/acs.accounts.3c00709. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 5. You H., Geng T., Liu Y., et al., “Surface Hydroxylation‐engineered Ni3S2/Ni‐OH Heterostructure for Durable Alkaline Hydrogen Evolution via Facile pH‐Induced Electrodeposition,” Advanced Functional Materials 36 (2025): 23386, 10.1002/adfm.202523386. [DOI] [Google Scholar]
  • 6. Zhang T., Hang L., Liu Q., Tao S., Bao H., and Fan H. J., “Positively Charged Hollow Co Nanoshells by Kirkendall Effect Stabilized by Electron Sink for Alkaline Water Dissociation,” Advanced Materials 36 (2024): 2405386, 10.1002/adma.202405386. [DOI] [PubMed] [Google Scholar]
  • 7. Duan Y., Xin X., Gao S., Zhou L., Tang H., and Ce C., “Facet‐Defined Crystalline Ruthenium Enables Ampere‐Level Alkaline Hydrogen Evolution via Lattice Reconstruction,” Applied Surface Science 720 (2026): 165130, 10.1016/j.apsusc.2025.165130. [DOI] [Google Scholar]
  • 8. Wang X., Xu C., Jaroniec M., Zheng Y., and Qiao S.‐Z., “Anomalous Hydrogen Evolution Behavior in High‐pH Environment Induced by Locally Generated Hydronium Ions,” Nature Communications 10 (2019): 4876, 10.1038/s41467-019-12773-7. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 9. Liang X., Zhang Z., Wang Z., et al., “Breaking the H2O Dissociation‐OH Desorption Scaling Relationship in Alkaline Hydrogen Evolution by Oxophilic Single Atom M1–Run Electrocatalysts,” Energy & Environmental Science 18 (2025): 4302–4311, 10.1039/D5EE00152H. [DOI] [Google Scholar]
  • 10. Wu W., Yang S., Qian H., et al., “Interface Engineering of Advanced Electrocatalysts Toward Alkaline Hydrogen Evolution Reactions,” Chinese Journal of Catalysis 66 (2024): 1–19. [Google Scholar]
  • 11. Zhang J., Ma C., Jia S., et al., “Electrocatalysts Design Guided by Active Intermediates of Hydrogen Evolution Reaction,” Advanced Energy Materials 13 (2023): 2302436. [Google Scholar]
  • 12. Sun J., Ren G., Qin S., et al., “Reconstruction Co‐O‐Mo in Amorphous‐crystalline MoOx/Co(OH)2 Interface for Industry‐level Active and Stable Electrocatalytic Seawater Hydrogen Evolution,” Nano Energy 121 (2024): 109246, 10.1016/j.nanoen.2023.109246. [DOI] [Google Scholar]
  • 13. Yu X., Chen Y., Wu Y., et al., “Self‐reconstructed ZIF‐L/Co(OH)2 Heterointerface Modulates Electronic Structure of Ru and Boosts Electrocatalytic Hydrogen Evolution,” Chemical Engineering Journal 490 (2024): 151926, 10.1016/j.cej.2024.151926. [DOI] [Google Scholar]
  • 14. Munawar T., Bashir A., El‐Marghany A., et al., “Scalable Synthesis of Co2C‐Covered NiTe (Co2C‐NiTe) Nanosheets as an Efficient Electrocatalyst for HER & OER in an Alkaline Medium,” Fuel 375 (2024): 132445, 10.1016/j.fuel.2024.132445. [DOI] [Google Scholar]
  • 15. Frederiksen M. L., Kragh‐Schwarz M. V., Bentien A., Nielsen L. P., and Lu P., “Performance of Co–Co(OH)2 coated nickel foam as catalysts for the hydrogen evolution reaction Under industrially relevant conditions,” International Journal of Hydrogen Energy 49 (2024): 668–675, 10.1016/j.ijhydene.2023.08.367. [DOI] [Google Scholar]
  • 16. Shi Y., Wang R., Liu S., Zhu X., and Jiao S., “Co (1 1 1) Loaded on Amorphous Co(OH)2‐Derived Porous Ni With Maximized Co (1 1 1) Utilization for Hydrogen Evolution Reaction,” Fuel 398 (2025): 135426, 10.1016/j.fuel.2025.135426. [DOI] [Google Scholar]
  • 17. Liu Y., You H., Bai C., et al., “Facile Exposure of P‐Co/Co(OH)2 Heterointerfaces for Enhanced Activity and Stability in Alkaline Hydrogen Evolution Reaction,” Advanced Energy Materials 15 (2025): e03695, 10.1002/aenm.202503695. [DOI] [Google Scholar]
  • 18. Shi H., Zhou Y.‐T., Yao R.‐Q., et al., “Spontaneously Separated Intermetallic Co3Mo From Nanoporous Copper as Versatile Electrocatalysts for Highly Efficient Water Splitting,” Nature Communication 11 (2020): 2940, 10.1038/s41467-020-16769-6. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 19. Zhang J., Wang T., Liu P., et al., “Efficient Hydrogen Production on MoNi4 Electrocatalysts With Fast Water Dissociation Kinetics,” Nature Communication 8 (2017): 15437, 10.1038/ncomms15437. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 20. Zhang J., Zhang Q., and Feng X., “Support and Interface Effects in Water‐Splitting Electrocatalysts,” Advanced Materials 31 (2019): 1808167, 10.1002/adma.201808167. [DOI] [PubMed] [Google Scholar]
  • 21. Liu Z., Zhang G., Bu J., et al., “Single‐Crystalline Mo‐Nanowire‐Mediated Directional Growth of High‐Index‐Faceted MoNi Electrocatalyst for Ultralong‐Term Alkaline Hydrogen Evolution,” ACS Applied Materials & Interfaces 12 (2020): 36259–36267, 10.1021/acsami.0c11716. [DOI] [PubMed] [Google Scholar]
  • 22. Li Z., Gan M., Wang Y., et al., “Superior Activity and Durability of Co3Mo Correlated With Interfacial Microenvironment for Hydrogen Evolution,” Applied Catalysis B: Environment and Energy 358 (2024): 124395, 10.1016/j.apcatb.2024.124395. [DOI] [Google Scholar]
  • 23. Jiang L.‐W., Huang Y., Zou Y., et al., “Boosting the Stability of Oxygen Vacancies in α‐Co(OH)2 Nanosheets With Coordination Polyhedrons as Rivets for High‐Performance Alkaline Hydrogen Evolution Electrocatalyst,” Advanced Energy Materials 12 (2022): 2202351, 10.1002/aenm.202202351. [DOI] [Google Scholar]
  • 24. Yu L., Zhou H., Sun J., et al., “Cu Nanowires Shelled With NiFe Layered Double Hydroxide Nanosheets as Bifunctional Electrocatalysts for Overall Water Splitting,” Energy & Environmental Science 10 (2017): 1820–1827, 10.1039/C7EE01571B. [DOI] [Google Scholar]
  • 25. Zhang J., Li X., Zang Z., et al., “Ir Loaded Co(OH)2 Nanosheets With Vacancy Defects for Boosting Oxygen Evolution Reaction and Stability,” Journal of Catalysis 430 (2024): 115352, 10.1016/j.jcat.2024.115352. [DOI] [Google Scholar]
  • 26. Fan J., Qu H., Li Y., Zhang J., Savilov S. V., and Chen M., “Simultaneously Introducing N Dopants and O Vacancies in CoMoO4 for High‐Performance Hybrid Capacitors,” Journal of Energy Storage 103 (2024): 114349, 10.1016/j.est.2024.114349. [DOI] [Google Scholar]
  • 27. Meng T., Jia H., Ye H., et al., “Facile Preparation of CoMoO4 Nanorods at Macroporous Carbon Hybrid Electrocatalyst for Non‐Enzymatic Glucose Detection,” Journal of Colloid and Interface Science 560 (2020): 1–10, 10.1016/j.jcis.2019.10.054. [DOI] [PubMed] [Google Scholar]
  • 28. Nam K. M., Shim J. H., Ki H., et al., “Single‐Crystalline Hollow Face‐Centered‐Cubic Cobalt Nanoparticles From Solid Face‐Centered‐Cubic Cobalt Oxide Nanoparticles,” Angewandte Chemie International Edition 47 (2008): 9504–9508, 10.1002/anie.200803048. [DOI] [PubMed] [Google Scholar]
  • 29. Ghodselahi T., Vesaghi M. A., Shafiekhani A., Baghizadeh A., and Lameii M., “XPS Study of the Cu@Cu2O Core‐Shell Nanoparticles,” Applied Surface Science 255 (2008): 2730–2734, 10.1016/j.apsusc.2008.08.110. [DOI] [Google Scholar]
  • 30. Espinós J. P., Morales J., Barranco A., Caballero A., Holgado J. P., and González‐Elipe A. R., “Interface Effects for Cu, CuO, and Cu2O Deposited on SiO2 and ZrO2. XPS Determination of the Valence State of Copper in Cu/SiO2 and Cu/ZrO2 Catalysts,” Journal of Physical Chemistry B 106 (2002): 6921–6929, 10.1021/jp014618m. [DOI] [Google Scholar]
  • 31. Hu E., Yao Y., Chen Y., Cui Y., Wang Z., and Qian G., “Boosting Hydrogen Generation by Anodic Oxidation of Iodide Over Ni–Co(OH)2 Nanosheet Arrays,” Nanoscale Advances 3 (2021): 604–610, 10.1039/D0NA00847H. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 32. Liu X., Wei X., Zhang Z., et al., “Design of Defect‐Rich MgCo‐Layered Double Hydroxide Microspheres as Highly Effective Sulfur Reduction Reaction Electrocatalyst for High‐Performance Li‐S Batteries,” Renewables 2 (2024): 162–170, 10.31635/rnwb.024.202400051. [DOI] [Google Scholar]
  • 33. Li Z., Ning S., Xu J., et al., “In Situ Electrochemical Activation of Co(OH)2@Ni(OH)2 Heterostructures for Efficient Ethanol Electrooxidation Reforming and Innovative Zinc–Ethanol–Air Batteries,” Energy & Environmental Science 15 (2022): 5300–5312, 10.1039/D2EE01816K. [DOI] [Google Scholar]
  • 34. Bai J., Mei J., Liao T., Sun Q., Chen Z.‐G., and Sun Z., “Molybdenum‐Promoted Surface Reconstruction in Polymorphic Cobalt for Initiating Rapid Oxygen Evolution,” Advanced Energy Materials 12 (2022): 2103247, 10.1002/aenm.202103247. [DOI] [Google Scholar]
  • 35. Li B., Cui Z., Tao Y., et al., “A Mo‐Doped amorphous Ni(OH)2 Modified Fe3O4 Heterostructure Catalyst for Enhancing Hydrogen Evolution Reaction,” Applied Surface Science 720 (2026): 165283, 10.1016/j.apsusc.2025.165283. [DOI] [Google Scholar]
  • 36. Tang Y., Chen H., Chen X., et al., “Molybdenum‐Doping to Enhance the Deprotonation Ability of Nickel‐Based Hydroxide Electrocatalysts for Ethanol Oxidation,” Journal of Colloid and Interface Science 680 (2025): 441–452, 10.1016/j.jcis.2024.10.197. [DOI] [PubMed] [Google Scholar]
  • 37. Luo Y., Tang L., Khan U., et al., “Morphology and Surface Chemistry Engineering Toward pH‐Universal Catalysts for Hydrogen Evolution at High Current Density,” Nature Communications 10 (2019): 269, 10.1038/s41467-018-07792-9. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 38. Kang X., Yang F., Zhang Z., et al., “A Corrosion‐resistant RuMoNi Catalyst for Efficient and Long‐lasting Seawater Oxidation and Anion Exchange Membrane Electrolyzer,” Nature Communications 14 (2023): 3607, 10.1038/s41467-023-39386-5. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 39. Men Y., Li P., Zhou J., Cheng G., Chen S., and Luo W., “Tailoring the Electronic Structure of Co2P by N Doping for Boosting Hydrogen Evolution Reaction at all pH Values,” ACS Catalysis 9 (2019): 3744–3752, 10.1021/acscatal.9b00407. [DOI] [Google Scholar]
  • 40. Yan Y., Zheng Q., Yan Y., Yan S., and Zou Z., “Highly Durable Volmer‐Heyrovsky Hydrogen Evolution Reaction in Alkaline media,” Journal of Energy Chemistry 113 (2026): 177–185, 10.1016/j.jechem.2025.09.037. [DOI] [Google Scholar]
  • 41. Yan Y., Lin J., Xu T., et al., “Atomic‐Level Platinum Filling Into Ni‐Vacancies of Dual‐Deficient NiO for Boosting Electrocatalytic Hydrogen Evolution,” Advanced Energy Materials 12 (2022): 2200434, 10.1002/aenm.202200434. [DOI] [Google Scholar]
  • 42. Tian J., Liu Q., Asiri A. M., and Sun X., “Self‐Supported Nanoporous Cobalt Phosphide Nanowire Arrays: An Efficient 3D Hydrogen‐Evolving Cathode Over the Wide Range of pH 0–14,” Journal of the American Chemical Society 136 (2014): 7587–7590, 10.1021/ja503372r. [DOI] [PubMed] [Google Scholar]
  • 43. He L., Wang N., Sun L., et al., “Heterostructure WC/Ni/Cu Nanorod Array Towards Ultra‐Long Hydrogen Evolution Durability at Room Temperature and Industrial Conditions,” Chemical Engineering Journal 500 (2024): 157271, 10.1016/j.cej.2024.157271. [DOI] [Google Scholar]
  • 44. Li Q., Chen C., Luo W., et al., “In Situ Active Site Refreshing of Electro‐Catalytic Materials for Ultra‐Durable Hydrogen Evolution at Elevated Current Density,” Advanced Energy Materials 14 (2024): 2304099, 10.1002/aenm.202304099. [DOI] [Google Scholar]
  • 45. Wang Y.‐H., Zheng S., Yang W.‐M., et al., “In Situ Raman Spectroscopy Reveals the Structure and Dissociation of Interfacial Water,” Nature 600 (2021): 81–85, 10.1038/s41586-021-04068-z. [DOI] [PubMed] [Google Scholar]
  • 46. Gong L., Xia F., Zhu J., et al., “Hydrogen Evolution Reactivity of Pentagonal Carbon Rings and p‐d Orbital Hybridization Effect With Ru,” Angewandte Chemie International Edition 63 (2024): e202411125, 10.1002/anie.202411125. [DOI] [PubMed] [Google Scholar]
  • 47. Dai Q., Wang L., Wang K., et al., “Accelerated Water Dissociation Kinetics By Electron‐Enriched Cobalt Sites for Efficient Alkaline Hydrogen Evolution,” Advanced Functional Materials 32 (2022): 2109556, 10.1002/adfm.202109556. [DOI] [Google Scholar]
  • 48. Li C., Wang N., Wang S., et al., “Vertically Arrayed Co4N/MoN Nanosheets for Robust Alkaline Electrocatalytic Hydrogen Evolution at Ampere‐Level Current Density,” Advanced Functional Materials 35 (2025): 2423856, 10.1002/adfm.202423856. [DOI] [Google Scholar]
  • 49. Qian G., Wang Y., Li L., et al., “Strategies for Tuning Tensile Strain and Localized Electrons in a Mo‐Doped NiCoCu Alloy for Enhancing Ampere‐Level Current Density HER Performance,” Advanced Functional Materials 34 (2024): 2404055, 10.1002/adfm.202404055. [DOI] [Google Scholar]
  • 50. Wang J., Xiao Y., Feng J., et al., “Phosphorus Incorporation in Cobalt Molybdate: Controlling Mo Leaching for Surface Reconstruction to Improve Hydrogen Evolution,” Chemical Engineering Journal 525 (2025): 170812, 10.1016/j.cej.2025.170812. [DOI] [Google Scholar]
  • 51. Ou Y., Liu L., Peng X., et al., “Structure Transformation Induced Bi‐Component Co–Mo/A‐Co(OH)2 as Highly Efficient Hydrogen Evolution Catalyst in Alkaline media,” Nano Materials Science 6 (2024): 565–575, 10.1016/j.nanoms.2023.11.006. [DOI] [Google Scholar]
  • 52. Alemayehu D. D., Tsai M.‐C., Tsai M.‐H., et al., “Heterogeneous Interfaces of Ni3Se4 Nanoclusters Decorated on a Ni3N Surface Enhance Efficient and Durable Hydrogen Evolution Reactions in Alkaline Electrolyte,” Journal of the American Chemical Society 147 (2025): 16047–16059, 10.1021/jacs.4c17747. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 53. Lu H., Liu M., and Baiyin M., “Electrooxidation of Glycerol to Formic Acid Coupled With Energy‐Saving Hydrogen Production Over Ruthenium Doped Cobalt‐Based Nanosheet Arrays,” Chemical Engineering Journal 499 (2024): 155923, 10.1016/j.cej.2024.155923. [DOI] [Google Scholar]
  • 54. Li B., Sun Y., Zhang Y., et al., “Copper‐cobalt‐sulfide and Cu‐MOF Nanoflower Composite on Copper Foam: Highly Efficient Bifunctional Catalysis for Low‐barrier Overall Water Splitting,” Small 21 (2025): e10545, 10.1002/smll.202510545. [DOI] [PubMed] [Google Scholar]
  • 55. Eom H., Kim S.‐I., Jeong N., et al., “Ru‐Modified CoMoOx Catalyst on Carbon Cloth for Efficient HER in Alkaline Seawater Electrolysis at High Current Densities,” Applied Surface Science 707 (2025): 163534, 10.1016/j.apsusc.2025.163534. [DOI] [Google Scholar]
  • 56. Li M., Wang X., Liu K., et al., “Ce‐Induced Differentiated Regulation of Co Sites via Gradient Orbital Coupling for Bifunctional Water‐Splitting Reactions,” Advanced Energy Materials 13 (2023): 2301162, 10.1002/aenm.202301162. [DOI] [Google Scholar]
  • 57. Wang P., Zhu J., Pu Z., et al., “Interfacial Engineering of Co Nanoparticles/Co2C Nanowires Boosts Overall Water Splitting Kinetics,” Applied Catalysis B: Environmental 296 (2021): 120334, 10.1016/j.apcatb.2021.120334. [DOI] [Google Scholar]
  • 58. Yuan S., Xia M., Liu Z., et al., “Dual Synergistic Effects Between Co and Mo2C in Co/Mo2C Heterostructure for Electrocatalytic Overall Water Splitting,” Chemical Engineering Journal 430 (2022): 132697, 10.1016/j.cej.2021.132697. [DOI] [Google Scholar]
  • 59. Yao M., Wang B., Sun B., et al., “Rational Design of Self‐Supported Cu@WC Core‐Shell Mesoporous Nanowires for pH‐Universal Hydrogen Evolution Reaction,” Applied Catalysis B: Environmental 280 (2021): 119451, 10.1016/j.apcatb.2020.119451. [DOI] [Google Scholar]
  • 60. Wang J., Feng J., Li Y., et al., “Multilayered Molybdate Microflowers Fabricated by One‐Pot Reaction for Efficient Water Splitting,” Advanced Science 10 (2023): 2206952, 10.1002/advs.202206952. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 61. Liu S.‐Q., Gao M.‐R., Liu S., and Luo J.‐L., “Hierarchically Assembling Cobalt/Nickel Carbonate Hydroxide on Copper Nitride Nanowires for Highly Efficient Water Splitting,” Applied Catalysis B: Environmental 292 (2021): 120148, 10.1016/j.apcatb.2021.120148. [DOI] [Google Scholar]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Supporting File: asia70841‐sup‐0001‐SuppMat.docx

ASIA-21-e70841-s001.docx (2.4MB, docx)

Data Availability Statement

The data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions.

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