Nitrate‐Stabilized Cuδ+ Sites Promote Selective CO2 Electroreduction to Ethanol for Tandem Acetamide Electrosynthesis

Chengying Guo; Rong Yang; Nannan Meng; Jiang Shao; Minghao Guo; Hongjiao Li; Ang Cao; Bin Zhang; Yifu Yu

doi:10.1002/anie.5526884

. 2026 May 23;65(30):e5526884. doi: 10.1002/anie.5526884

Nitrate‐Stabilized Cu^δ+ Sites Promote Selective CO₂ Electroreduction to Ethanol for Tandem Acetamide Electrosynthesis

Chengying Guo ^1,², Rong Yang ¹, Nannan Meng ¹, Jiang Shao ¹, Minghao Guo ¹, Hongjiao Li ³, Ang Cao ⁴, Bin Zhang ¹, Yifu Yu ^1,^2,^✉

PMCID: PMC13383254 PMID: 42175817

ABSTRACT

Electrosynthesis of acetamide, a multicarbon nitrogenous compound containing C─C─N bonds, from abundant CO₂ and nitrate is important for low‐carbon industry. However, the simultaneous electroreduction construction of C─C and C─N bonds is challenging. Herein, we propose a strategy to construct C─C and C─N bonds in tandem at the cathode and anode, respectively. At the cathode, a nitrate‐induced dynamic Cu^δ+ site is designed to promote C─C coupling activity from CO₂ reduction to ethanol, which is accompanied by the generation of ammonia from nitrate reduction, with a total Faradaic efficiency of 88.6%. The generated ethanol and ammonia serve as feedstocks for the tandem construction of C─N bonds at the anodic region via a possible nucleophilic attack pathway. We achieve the synthesis of acetamide with a Faradaic efficiency of 71.4% and a yield rate of 0.13 mmol h⁻¹ cm⁻². The carbon footprint analysis of this tandem strategy revealed net‐zero emissions at a carbon intensity of 0.23 kg_CO2e kWh⁻¹, indicating its sustainable nature from the viewpoint of carbon neutrality.

Keywords: cathode–anode tandem, C─C─N bond construction, dynamic Cu^δ+ , electrocatalysis, spontaneous redox reaction

A cathode‒anode tandem strategy is designed to synthesize acetamide with C─C─N bond from CO₂ and NO₃ ⁻, in which the simultaneous construction of C─C─N bond is transformed to the tandem construction. Based on this cathode−anode tandem system, the yield rate and Faradaic efficiency of acetamide are as high as 0.13 mmol h⁻¹ cm⁻² and 71.4%, respectively.

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1. Introduction

The electrosynthesis of organonitrogen compounds using abundant CO₂ and nitrogen‐containing small molecules (NO₃ ⁻/NO₂ ⁻/NO_x/N₂/NH₃) is alluring to reduce the current dependence on fossil energy as well as close the carbon and nitrogen cycles [1, 2, 3, 4, 5, 6]. At present, organonitrogen products are mainly concentrated in monocarbon nitrogenous compounds (containing C─N bonds), such as urea, methylamine, and formamide [7, 8, 9]. The electrosynthesis of acetamide, a multicarbon nitrogenous compound containing C─C─N bonds, is still challenging, as the simultaneous electroreduction construction of C─C and C─N bonds to form C─C─N bonds is unfavorable in both thermodynamics and kinetics. Simultaneously, the low‐value oxygen evolution reaction (OER) occurs at the anode (Scheme 1a). Our previous works found that alcohol and ammonia could undergo oxidative coupling to construct C─N bonds at the anode, which is preferable to the OER in terms of thermodynamics [10, 11]. In this way, we propose a cathode‒anode tandem strategy, which divides the preparation of acetamide with C─C─N bonds into C─C bond construction by the CO₂RR at the cathode and C─N bond construction by ethanol‒ammonia oxidation at the anode with the addition of ammonia (Scheme 1b).

SCHEME 1 — (a) Coreduction process to construct C─C─N bonds (C─C and C─N bonds are simultaneously constructed at the cathode). (b), Cathode‒anode tandem strategy to construct C─C─N bonds. At the cathode, CO₂ is reduced to ethanol to construct C─C bonds. At the anode, ethanol and ammonia undergo oxidative coupling to construct C─N bonds. (c) Schematic illustration of the CO₂RR on the surface of a Cu‐based catalyst. The blue, red, gray, and white spheres represent the Cu, O, C, and H atoms, respectively. (d) The modified cathode−anode tandem strategy to construct C─C─N bonds. At the cathode, nitrate‐induced dynamically stable Cu^δ+ sites selectively catalyze CO₂ to ethanol (C─C bonds), which is accompanied by the generation of ammonia. At the anode, ethanol and ammonia undergo oxidative coupling to construct C─N bonds.

For ethanol production from the CO₂ reduction reaction (CO₂RR), previous studies have shown that positively charged Cu^δ+ (+0.3 < δ < +1) sites are beneficial for C─C coupling, whereas metallic Cu⁰ and Cu²⁺ are conducive to C₁ products [12, 13, 14, 15]. Unfortunately, the desired Cu^δ+ sites are unstable and are easily reduced to Cu⁰ during the CO₂RR, leading to a decrease in C─C coupling activity (Scheme 1c) [16, 17, 18]. The construction of stable Cu^δ+ sites is crucial for the preparation of ethanol from the CO₂RR. Nitrate (NO₃ ⁻) ions with strong oxidation ability, have been reported to oxidize transition metals (TM: Fe, Co, Ni) under reduction potentials to form TM^δ+ sites [19]. Notably, Cu can also undergo spontaneous redox reactions with NO₃ ⁻ to produce Cu₂O and NO₂ ⁻, with a theoretical Gibbs free energy change of −66.95 kJ mol⁻¹ (2Cu + NO₃ ⁻ → Cu₂O + NO₂ ⁻). The produced Cu₂O is electrochemically reduced back to Cu under negative potentials (Cu₂O + 2H⁺ + 2e⁻ → 2Cu + H₂O). The simultaneous spontaneous redox and electroreduction reactions are expected to create many dynamically stable Cu^δ+ sites.

In this work, we design to introduce NO₃ ⁻ into the cathode region to achieve selective CO₂ electroreduction to ethanol over a commercial copper nanoparticle (Cu NP) catalyst, accompanied by the generation of ammonia from NO₃ ⁻ reduction. The generated ethanol and ammonia serve as feedstocks to construct C─N bonds at the anodic region in tandem to synthesize acetamides (Scheme 1d). After the introduction of 50 mM NO₃ ⁻, the selectivity of ethanol (Sel._C2H5OH) reaches 62.7% at −0.75 V (vs. RHE), obviously outperforming the performance without NO₃ ⁻ (7.9%). The total Faradaic efficiency of ethanol and ammonia reaches 88.6% (ethanol: 57.3%, ammonia: 31.3%). Electrochemical in situ spectroscopy and theoretical simulations unveil the function of NO₃ ⁻ in constructing dynamically stable Cu^δ+ species to promote C─C coupling. The reduction products of ethanol from CO₂ and ammonia from NO₃ ⁻ at the cathodic region can be tandemly upgraded to high‐value acetamide (CH₃CONH₂), with a Faradaic efficiency of 71.4% and a yield rate of 0.13 mmol h⁻¹ cm⁻². Two feasible reaction mechanisms of nucleophilic attack and co‐adsorption coupling are theoretically screened for alcohol‒ammonia oxidative coupling, in which the former is experimentally confirmed. In addition, the proposed cathode‒anode tandem strategy in an electrolyzer results in a net‐negative carbon emission footprint to generate acetamide directly from CO₂ and NO₃ ⁻ driven by renewable electricity, indicating promising application potential from the viewpoint of carbon neutrality.

2. Results and Discussion

2.1. Theoretical Simulation‐Directed Catalyst Design

A series of different Cu sites in Cu, Cu₂O, and defective Cu₂O with oxygen vacancies (named Cu₂O_1‐x) were studied via density functional theory (DFT) simulations (Figures S1−S7 and Tables S1−S9) [20]. On the basis of the scaling relations (Figure S8), the adsorption free energy of *CO, denoted by G _ad(*CO), can be selected as a descriptor [21]. After determining C─C coupling pathway [14, 22] (Figure S9), the two‐dimensional volcano relationships for C₂ activity were constructed using G _ad(*H) as the second descriptor [23]. Generally, the adsorption energy has a linear correlation with the adsorbed species, and this correlation restricts the intrinsic activity. As shown in Figure 1a and Figures S10−S12, the Cu₂O_1−x‐Vo exhibits weak adsorption for *H and appropriate adsorption for *CO; thus, it breaks the scaling relation and exhibits high intrinsic activity for C₂ products [13, 24]. However, the Cu₂O_1−x‐Vo site is unstable and can be easily reduced to Cu⁰ under CO₂RR conditions (Figure S13), leading to a decrease in C₂ activity (Challenge I). Inspired by our previous work [19], the oxidation ability of NO₃ ⁻ is conducive to stabilizing positively charged transition metals during the electroreduction reaction. Theoretically, Cu can also undergo a spontaneous redox reaction with NO₃ ⁻ to produce Cu₂O with a Gibbs free energy change of –66.95 kJ mol⁻¹ (2Cu + NO₃ ⁻ → Cu₂O + NO₂ ⁻). The as‐produced Cu₂O will be electrochemically reduced back to Cu under negative potentials (Cu₂O + 2H⁺ + 2e⁻ → 2Cu + H₂O). Simultaneous spontaneous redox and electroreduction reactions can create many dynamically stable Cu^δ+ sites with high intrinsic C₂ activity. Subsequently, the selectivity of C₂ products was investigated. As provided in Figures S14−S15, the former 9 steps of electron transfer are shared in ethylene and ethanol, leading to a low selectivity (Challenge II). For selectivity‐determining step, ethylene is formed via symmetric protonation (*CH₂−CHO + H⁺ + e⁻ → *O + C₂H₄, ∆G _C2H4), whereas ethanol is generated via asymmetric protonation (*CH₂−CHO + H⁺ + e⁻ → *CH₃−CHO, ∆G _C2H5OH). The difference between these two Gibbs free energy changes (∆G _C2H4 − ∆G _C2H5OH) can be directly used to indicate the selectivity, and the correlation between ∆G _C2H4 − ∆G _C2H5OH and G _ad(*CO) is displayed in Figure 1b and Figures S16−S17. After adsorbing NO₃ ⁻, the Cu₂O_1−x‐Vo site transformed from the ethylene region to the ethanol region, accompanied by a decrease in G _ad(*CO) (Figures S18−S19). The electronical analysis shows that the electronic structure of the Cu₂O_1−x‐Vo site becomes more localized after the adsorption of electron‐withdrawing NO₃ ⁻ (Figure 1c). As shown in Figure S19e, G _ad(*CO) decreases monotonically with increasing Bader charge when it is less than 0.4 |e⁻|. In this way, the NO₃ ⁻‐induced redistribution of charge can promote the adsorption of *CO, resulting in that Cu₂O_1−x‐Vo shifts toward the ethanol region. In addition, the activation energies are calculated to reveal the influence of NO₃ ⁻ from the perspective of the transition state, in which the kinetic barrier of the conversion from *CH₂−CHO to *O+C₂H₄ (1.17 eV) is more difficult than that to *CH₃−CHO (0.13 eV), further confirming the high selectivity of ethanol (Videos S1−S2). Thus, the introduction of NO₃ ⁻ into electrolyte is expected to construct dynamically stable Cu₂O_1−x species with NO₃ ⁻ adsorption (indicated as NO₃ ⁻‐Cu₂O_1−x), thereby solving the aforementioned two challenges (Figure 1d).

Theoretical simulation directing the design of catalysts for the selective reduction of CO₂ to ethanol. (a) Two‐dimensional volcano plot for C₂ activity with G _ad(*CO) and G _ad(*H) as the descriptors. (b) Selectivity map of ethanol and ethylene with G _ad(*CO) as the descriptor. (c) Charge density difference for the Cu₂O_1−x‐Vo site with *NO₃, corresponding to an isosurface of ρ = 0.005 e Bohr⁻³. The yellow and blue regions correspond to the accumulation and depletion of electrons, respectively. (d) Schematic illustration of the construction of NO₃ ⁻‐Cu₂O_1−x species for the CO₂RR toward ethanol.

2.2. Characterizations of Dynamically Stable Cu₂O_1−x Species With NO₃ ⁻ Adsorption

The Cu electrode was obtained via the prereduction of commercial Cu NP (Figure S20) at −0.8 V (vs. RHE) for 30 min in a 0.5 M KHCO₃ electrolyte. During the CO₂RR process in the presence of NO₃ ⁻, redox and electroreduction reactions occur simultaneously, which enables the cycling of Cu₂O and Cu, thereby creating dynamically stable NO₃ ⁻‐Cu₂O_1−x (Figure 2a). First, the spontaneous redox reaction between the Cu electrode and NO₃ ⁻ was characterized (Figure 2b,c). An ultraviolet−visible (UV−Vis) spectrophotometer proves the generation of NO₂ ⁻ after adding Cu electrode to KNO₃ solution (Figure 2b). In situ Raman spectra of the Cu electrode were immediately collected after soaking in 0.5 M KHCO₃ solution with different KNO₃ concentrations (left in Figure 2c). The characteristic Raman peaks of the Cu─O bonds in Cu₂O (148, 218, 419, 510, and 625 cm⁻¹) appear, and the peak intensity increases with increasing NO₃ ⁻ concentrations [1]. Moreover, in situ attenuated total reflection surface−enhanced infrared absorption spectroscopy (ATR−SEIRAS) data reveal the signal of adsorbed NO₃ ⁻ (NO₃ ⁻ _ad, 1390 cm⁻¹), indicating the adsorption of NO₃ ⁻ on the surface (right in Figure 2c and Figure S21). However, all the X‐ray diffraction (XRD) peaks of the Cu electrode after soaking in KNO₃ solution are indexed to metallic Cu, implying the maintenance of bulk‐phase Cu (Figure S22). These results demonstrate that the surface of the Cu electrode and NO₃ ⁻ undergo a quick redox reaction to produce NO₂ ⁻ and Cu₂O, which absorb NO₃ ⁻ on the surface. Next, a Cu₂O electrode was obtained by soaking the Cu electrode in a 0.5 M KHCO₃ + 50 mM KNO₃ solution for further characterization. Linear sweep voltammetry (LSV) measurements were performed in two modes. One was to directly obtain the LSV curves of the Cu₂O electrode in 0.5 M KHCO₃ electrolyte. As shown in the left image of Figure 2d, the reduction peak of Cu₂O only appears in the first scan, indicating the rapid reduction of the Cu₂O species under electroreduction conditions [25, 26]. The other mode involved alternatingly repeating the LSV test in a 0.5 M KHCO₃ solution and soaking in a KNO₃ solution. The processes were repeated 6 times, and the reduction peak of Cu₂O remained in LSV curves, indicating that the redox and electroreduction reactions occur simultaneously (right in Figure 2d). Moreover, the potential‐dependent electrochemical in situ Raman spectra also confirm the rapid conversion from Cu₂O to Cu in the 0.5 M KHCO₃ electrolyte (left in Figure 2e). When 0.5 M KHCO₃ + 50 mM KNO₃ is used as the electrolyte, the characteristic Raman peaks of Cu₂O always exist with increasing negative potentials (−0.25 to −1.35 V vs. RHE), implying that electrochemical reduction and spontaneous redox reactions achieve equilibrium to form stable Cu₂O species (right in Figure 2e and Figures S23−S24).

Characterizations of dynamically stable Cu₂O_1‐x species with NO₃ ⁻ adsorption. (a) Schematic illustration of the surface species of the Cu electrode in the presence of NO₃ ⁻ at the reduction potential. The gray and blue spheres represent Cu and NO₃ ⁻‐Cu₂O_1‐x, respectively. (b) UV−Vis spectra of KNO₃ solution with a NO₂ ⁻ chromogenic agent before and after adding Cu electrode. The inset is the corresponding digital image. (c) In situ Raman (left) and ATR−SEIRAS (right) spectra of the Cu electrode after soaking in 0.5 M KHCO₃ solution with different KNO₃ concentrations. (d) LSV curves of the Cu₂O electrode in 0.5 M KHCO₃ electrolyte without (left) and with (right) NO₃ ⁻ solution soaking. (e) Potential‐dependent electrochemical in situ Raman spectra of the Cu₂O electrode in (left) 0.5 M KHCO₃ electrolyte and (right) 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte. (f) EPR spectra of the Cu₂O electrode, Cu electrode (−0.75 V), and Cu₂O_1‐x electrode (−0.75 V). (g) Potential‐dependent electrochemical in situ XANES spectra of the Cu electrode in 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte. (h) Line relationship between the Cu K‐edge absorption energy and the valence state of the surface Cu₂O_1‐x species obtained from (g). (i) Depth‐dependent Cu *LMM* Auger spectra of the Cu₂O_1‐x electrode (−0.75 V) with different etching times.

To further verify the structure of the in situ‐formed Cu₂O species, a series of characterizations were performed. For convenience, the Cu electrode after CO₂RR at −0.75 V (vs. RHE) in 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte for 1 h is named as the Cu₂O_1−x electrode (−0.75 V). As a control, the Cu electrode (−0.75 V) represents the Cu electrode after the CO₂RR at −0.75 V (vs. RHE) for 1 h in 0.5 M KHCO₃ electrolyte. As shown in Figure 2f, the Cu₂O_1−x electrode (−0.75 V) shows an electron paramagnetic resonance (EPR) signal of oxygen vacancies at g = 2.002, whereas the Cu₂O electrode and Cu electrode (−0.75 V) exhibit no EPR signal, confirming the dynamically formed Cu₂O_1−x species [27]. The presence of oxygen vacancies arises from NO₃ ⁻‐induced spontaneous redox and electrochemical reduction reactions, which proceed simultaneously and reach equilibrium. The electronic structure or coverage of the Cu₂O_1‐x species is affected by the NO₃ ⁻ concentration and the applied potential. The valence states of Cu^δ+ in the Cu₂O_1‐x electrode are revealed by potential‐dependent electrochemical in situ x ray absorption near edge structure (XANES) analysis in 0.5 M KHCO₃ + 50 mM NO₃ ⁻ electrolyte, and the corresponding x values in the Cu₂O_1‐x species are deduced (Figure 2g,h, Figures S23, S25, and Table S11) [19]. The valence states of Cu^δ+ in the dynamically stable Cu₂O_1‐x species are +0.69, +0.64, +0.55, +0.52, +0.44, and +0.32 at −0.25, −0.50, −0.75, −1.00, −1.20, and −1.35 V (vs. RHE), respectively. In addition, the depth‐dependent Cu LMM Auger spectra of the Cu₂O_1‐x electrode (−0.75 V) show that the intensity of the Cu₂O_1‐x peak (916.9 eV) [16, 28, 29] gradually decreases and that of the metallic Cu⁰ peak (918.8 eV) [25, 30] gradually increases with prolonged etching time (Figure 2i). To identify the origin of the Cu₂O_1‐x species, in situ XANES, isotope‐labeled secondary−ion mass spectrometry (SIMS), and Cu LMM were performed in 0.5 M KHCO₃ and 0.5 M KHCO₃ + 50 mM KNO₃ electrolytes, respectively. As shown in Figure S26, both Cu and Cu₂O_1−x are observed in the 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte, whereas only metallic Cu is detected in the 0.5 M KHCO₃ electrolyte, confirming that the formation of Cu₂O_1−x is attributed to the NO₃ ⁻‐induced redox reaction. Notably, the thickness of the oxidation layer obtained from transmission electron microscopy (TEM) and element mapping images is ∼30 nm (Figure S27). The aforementioned results clarify that we successfully construct a thin layer of dynamically stable NO₃ ⁻‐Cu₂O_1‐x species through the addition of NO₃ ⁻ into the electrolyte.

2.3. Electrocatalytic CO₂RR to Ethanol Over Dynamically Stable Cu₂O_1−x Species With NO₃ ⁻ Adsorption

A gas diffusion electrode‐based flow cell was adopted to investigate the electrocatalytic CO₂RR performance over a Cu electrode with and without NO₃ ⁻ (Figure 3a). The fresh electrolyte continuously flowed into the cell, and an inline gas chromatograph (GC) was used to detect the gaseous products (Figures S28−S30). The liquid carbon‐containing products were analyzed and quantified by ¹H‐nuclear magnetic resonance (¹H NMR) (Figures S31−S34). The product of ammonia (NH₃) was quantified via UV−Vis spectroscopy (Figure S35). At all tested potentials, the Faradaic efficiency of ethanol (FE_C2H5OH) significantly increases with the addition of 20 and 50 mM NO₃ ⁻ (Figure 3b). However, FE_C2H5OH decreases at a high NO₃ ⁻ concentration (100 mM) owing to the competing nitrate‐to‐ammonia reaction. The Faradaic efficiencies of ethanol and ammonia are 57.3% ± 4.6% and 31.3% ± 2.9%, respectively, at −0.75 V (vs. RHE) in the presence of 50 mM NO₃ ⁻ (Figures S36−S37). The maximum partial current density for ethanol (j _C2H5OH) is −69.6 mA cm⁻² in a 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte at −0.85 V (vs. RHE), which is 9.4 times higher than that in a 0.5 M KHCO₃ electrolyte (Figure 3c). In addition, the selectivity of ethanol (Sel._C2H5OH) increases from 7.9% ± 0.4% to 62.7% ± 5.7% after the addition of 50 mM NO₃ ⁻ (Figure 3d). The ethanol/ethylene ratio is as high as 96 at −0.75 V (vs. RHE) in a 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte. These results prove the ability of NO₃ ⁻ to increase ethanol activity and selectivity. The key performance parameters are summarized and compared with recently reported literature (Figure 3e and Table S12), from which the overall catalytic performance (including onset potential, potential, current density (j _tot), energy efficiency (EE), Faradaic efficiency (FE), and C₂H₅OH/C₂H₄ ratio) of the Cu electrode in the presence of 50 mM NO₃ ⁻ outperforms most of the state‐of‐the‐art Cu‐based catalysts for ethanol generation [31, 32, 33, 34, 35, 36, 37]. FE_C2H5OH and the C₂H₅OH/C₂H₄ ratio versus the Cu valence state are plotted in Figure 3f and Figure S38. They both show a volcano‐type tendency with an increasing Cu valence state, and the optimal FE_C2H5OH is obtained at a Cu valence of +0.55 (corresponding to −0.75 V in Figure 2h,i), which is basically consistent with the literature prediction that Cu^+0.5 possesses the highest C₂ activity [12]. To investigate the effect of NO₃ ⁻ on the stability of the Cu₂O_1‐x species, long‐term stability measurements were carried out in two modes at −0.75 V (vs. RHE). One mode involves the continuous supply of fresh 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte (Figure 3a,g). The other mode involves the recycled supply of 10 mL of electrolyte (0.5 M KHCO₃ + 50 mM KNO₃), in which NO₃ ⁻ is gradually consumed (Figure 3h and Figure S39a). In the former mode, FE_C2H5OH, FE_C2H4, FE_C1, FE_H2, and FE_NH4+ are well maintained for 100 h. Meanwhile, the characteristic Raman peaks of the Cu─O bonds in Cu₂O (148 cm⁻¹ and 218 cm⁻¹), the EPR signal of the oxygen vacancies (g = 2.002), and the morphology are well maintained after long‐term measurement, confirming the dynamic stability of the Cu₂O_1‐x species under electroreduction conditions with NO₃ ⁻ (Figures S39−S40) [27]. In the latter mode, NO₃ ⁻ is continuously consumed with increasing reaction time, which breaks the equilibrium between the electroreduction reaction and NO₃ ⁻‐induced spontaneous redox, resulting in a decrease in FE_C2+ and an increase in FE_C1 (Figure 3h and Figure S41). The aforementioned results confirm that CO₂ can be selectively reduced to ethanol via the introduction of NO₃ ⁻, accompanied by the generation of NH₃ from NO₃ ⁻ reduction.

Electrocatalytic CO₂RR performance over dynamically stable NO₃ ⁻‐Cu₂O_1‐x species. (a) Schematic illustration of the electrocatalytic CO₂RR test over a Cu electrode in a gas diffusion electrode‐based flow cell. (b−c) Potential‐dependent (b) FE_C2H5OH and (c) j _C2H5OH in 0.5 M KHCO₃ electrolyte with different NO₃ ⁻ concentrations. (d) Potential‐dependent Sel._C2H5OH in 0.5 M KHCO₃ and 0.5 M KHCO₃ + 50 mM KNO₃ electrolytes. (e) Comparison of the CO₂RR performance of the Cu electrode in 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte with that of other recently reported catalytic systems. (f) The correlation between FE_C2H5OH and the valence state of Cu in the Cu₂O_1‐x species. (g) Time‐dependent FE_C2H5OH, FE_C2H4, FE_C1 and j at −0.75 V (vs. RHE) for 100 h with a continuous supply of fresh electrolyte. (h) Time‐dependent FE_C2+ and FE_C1 at −0.75 V (vs. RHE) for 6 h with the recycled supply of 10 mL electrolyte.

2.4. Studies on the Mechanism of the Selective CO₂RR to Ethanol

Electrochemical in situ ATR−SEIRAS was employed on the same electrode to explore the enhancement mechanism induced by the addition of NO₃ ⁻. According to the potential‐dependent in situ ATR−SEIRAS spectra (Figure 4a,b, Figures S42−S43, and Table S13), the *HCOO signal (1390 cm⁻¹) of formic acid in the 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte is lower than that in the 0.5 M KHCO₃ electrolyte, implying a decrease of C₁ product caused by NO₃ ⁻. It has been proven that the stronger adsorption and greater coverage of *CO allow the triggering of CO₂ reduction toward ethanol [29, 31, 38, 39, 40]. Thus, the amplified *CO signal is provided in Figure 4c, from which the peak located at 2030–2080 cm⁻¹ indexed to the stretching band of linearly bonded CO (indicated as *CO) is clearly observed [41, 42]. The *CO peak has an obvious vibrational Stark effect, and the Stark tuning rates are different in the 0.5 M KHCO₃ electrolyte and 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte, implying a change in surface species from Cu to Cu₂O_1‐x in the presence of NO₃ ⁻ (Figure S44) [43]. Notably, *CO significantly redshifts after the addition of NO₃ ⁻, indicating a promotion in *CO adsorption (Figure 4d) [43, 44]. Moreover, the integrated area of the *CO peak in the 0.5 M KHCO₃ + 50 mM KNO₃ electrolyte is much greater than that in the 0.5 M KHCO₃ electrolyte, revealing increased coverage of *CO (Figure 4e) [45, 46].

Performance enhancement mechanism studies. (a−b) Potential‐dependent in situ ATR−SEIRAS spectra of the same Cu electrode in (a) 0.5 M KHCO₃ and (b) 0.5 M KHCO₃ + 50 mM KNO₃ electrolytes. (c) Locally amplified ATR−SEIRAS spectra to observe *CO. (d−e) Potential‐dependent (d) *CO peak frequency and (e) integrated *CO intensity. (f) Time‐dependent in situ ATR−SEIRAS spectra of the Cu electrode in 0.5 M KHCO₃ at −0.45 V (vs. RHE). (g) Time‐dependent in situ ATR−SEIRAS spectra and corresponding in situ Raman spectra of the Cu₂O_1‐x electrode (−0.75 V) in 0.5 M KHCO₃ at −0.45 V (vs. RHE). (h) Time‐dependent in situ ATR−SEIRAS spectra of the Cu₂O_1‐x electrode (−0.75 V) in 0.5 M KHCO₃ + 50 mM KNO₃ at −0.45 V (vs. RHE). (i) G _ad(*CO) in the Cu₂O_1−x model with and without NO₃ ⁻.

To study the functions of the Cu₂O_1‐x species with the adsorption of NO₃ ⁻, time‐dependent in situ ATR−SEIRAS was carried out over (i) a Cu electrode in 0.5 M KHCO₃, (ii) a Cu₂O_1‐x electrode (−0.75 V) in 0.5 M KHCO₃, and (iii) a Cu₂O_1‐x electrode (−0.75 V) in 0.5 M KHCO₃ + 50 mM KNO₃. For (i), the peak frequency of *CO (2067 cm⁻¹) remains well at −0.45 V (vs. RHE) (Figure 4f). For (ii), the initial peak frequency of *CO is located at 2060 cm⁻¹, which is lower than that of the Cu electrode (2067 cm⁻¹) (Figure 4g). The corresponding initial Raman spectrum proves its Cu₂O_1‐x structure. With prolonged reaction time, the peak frequency of *CO shifts to 2067 cm⁻¹ (similar to *CO adsorption on the Cu electrode), and the Raman peaks of Cu₂O_1‐x disappear, proving that *CO adsorption on Cu₂O_1‐x is stronger than that on Cu. For (iii) (Figure 4h), the peak frequency of *CO is well maintained at 2055 cm⁻¹, which is lower than that of (i) and (ii), indicating that the adsorption ability of *CO is improved owing to NO₃ ⁻‐induced dynamically stable Cu^δ+ with the adsorption of NO₃ ⁻ on the surface. Meanwhile, the surface coverage of *CO is in the same order as the adsorption ability of *CO: the Cu₂O_1−x electrode (−0.75 V) in 0.5 M KHCO₃ + 50 mM KNO₃ > the Cu₂O_1−x electrode (−0.75 V) in 0.5 M KHCO₃ > the Cu electrode in 0.5 M KHCO₃ (Figure S45). To study the function of only NO₃ ⁻ adsorption, DFT was employed over Cu₂O_1‐x with and without NO₃ ⁻ adsorption. The simulation results revealed that when NO₃ ⁻ adsorbs on the Cu₂O_1‐x‐cus site, the adjacent Cu₂O_1−x‐Vo site has a stronger adsorption of *CO (G _ad(*CO) = −1.63 eV), indicating that the adsorption ability of *CO can be further improved owing to NO₃ ⁻‐induced electron localization (Figure 4i and Figure S19). The aforementioned results demonstrate that the dynamically stable Cu₂O_1‐x species with NO₃ ⁻ adsorption can improve the adsorption ability and coverage of the *CO intermediate, resulting in asymmetric protonation pathways for the selective generation of ethanol (Figure 1c,d).

2.5. Electrosynthesis of Acetamide via Cathode−Anode Tandem System From CO₂ and NO₃ ⁻

First, 12 species of common metal anode catalysts, including Pt, IrO₂, RuO₂, Ni, Fe, Cu, Al, Co, Ti, Pb, Mo, and W, were screened using the galvanostatic method (+80 mA cm⁻²) in 0.5 M KHCO₃ + 2 M C₂H₅OH + 2 M NH₃·H₂O electrolyte. After 1 h electrolysis, the peak of acetamide located at ∼1.8 ppm is clearly observed in the ¹H NMR spectra, and Pt exhibits the highest activity for acetamide electrosynthesis (Figures S46−S47). Next, the ethanol‒ammonia electrooxidation coupling reaction was performed solely over a Pt‐covered Ti sheet (named as Pt electrode). After the potentiostatic test, the yield rate of acetamide is calculated to be 0.10 mmol h⁻¹ cm⁻² at +2.0 V (vs. Ag/AgCl) (Figure S48). Then, a cathode−anode tandem reaction was carried out in a membrane‐free single cell with 0.5 M KHCO₃ + 50 mM NO₃ ⁻ + 2 M C₂H₅OH + 2 M NH₃·H₂O as electrolyte, Cu electrode and Pt electrode as the cathode catalyst and anode catalyst, respectively (Figure S49). Specifically, the ethanol−ammonia coupling reaction can proceed directly in the electrolyte with ethanol and ammonia, and the consumed ethanol and ammonia were replenished via cathode reactions of CO₂RR and NO₃RR. In this way, the CO₂ and NO₃ ⁻ can be converted into acetamide via cathode‒anode tandem reaction with ethanol and ammonia as intermediate products. Based on this tandem system, the obtained yield rate and Faradaic efficiency of acetamide (FE_CH3CONH2) are as high as 0.13 ± 0.03 mmol h⁻¹ cm⁻² and 71.4% ± 4.2% at 80 mA cm⁻² (Figure 5b and Figure S50), which are both the highest reported values for multicarbon nitrogenous compounds from carbon‐ and nitrogen‐containing small molecules (Table S14). From the perspective of practical application, the separation of the acetamide product is crucial. The simulation of Aspen Plus V11 demonstrates that the acetamide produced in the tandem system can be obtained by a combination of extraction (acetone and ethyl acetate as extraction agents) and distillation (Figures S51−S52 and Tables S15−S17). Moreover, a cradle‐to‐gate life cycle assessment (LCA) of the carbon footprint for acetamide generation was performed by varying the carbon intensities (CI) of the electricity sources (Figure 5c and Figure S53) [47]. Notably, the carbon footprint of this acetamide synthesis process reaches net‐zero emissions at CI of 0.23 kg_CO2e kWh⁻¹. When renewable electricity is used, the cathode‒anode tandem strategy for acetamide preparation results in a net‐negative carbon emission footprint, indicating its sustainable nature from the viewpoint of carbon neutrality. In addition, a primary technoeconomic analysis (TEA) of this cathode‒anode tandem system was carried out (Figure S54). The total plant‐gate levelized cost of acetamide is as low as $4067 ton⁻¹, whereas the market price of acetamide is as high as $14,000 ton⁻¹, indicating the economic profit of this cathode‒anode tandem process. As shown in Figure S55, the break‐even point is marked as a white solid line in the TEA image, in which this cathode‒anode tandem craft could gain a profit at an electricity cost as high as $0.19 kWh⁻¹. As a result, the cathode‒anode tandem strategy achieves acetamide electrosynthesis with the highest performance, and both the LCA, TEA, and Aspen simulation confirm the high application potential of this strategy from the view of carbon footprint, economic profit, and practical application, respectively.

Electrosynthesis of acetamide via tandem cathodic C─C and anodic C─N coupling from CO₂ and NO₃ ⁻. (a) Schematic illustration of the cathode‒anode tandem system. (b) Yield rate and FE of acetamide at different current densities in the galvanostatic method with 0.5 M KHCO₃ +50 mM NO₃ ⁻ + 2 M C₂H₅OH + 2 M NH₃·H₂O as electrolyte. (c) Relationships between the CO₂ emission footprint of acetamide production and the CI of electricity from different sources. CO₂e represents the CO₂ equivalent.

2.6. Studies on the Electrooxidation Mechanism of Ethanol‒Ammonia Coupling

A series of control experiments was performed to study the mechanism of the anodic ethanol‒ammonia coupling. First, no acetamide can be detected in the absence of an applied current, ethanol, or ammonia, demonstrating that acetamide is produced by the electrooxidation of ethanol and ammonia (Entries 1−3 in Table S18 and Figure S56). Second, various possible oxidation derivatives of ammonia, such as NO₃ ⁻, NO₂ ⁻, and NH₂OH, are mixed with ethanol. After electrolysis, none of them produce acetamide (Entries 4−6 in Table S18 and Figure S56), indicating the key role of ammonia in the production of acetamide. When ethanol is replaced by acetaldehyde (CH₃CHO) or acetic acid (CH₃COOH), acetamide can be detected only in mixtures of CH₃CHO and ammonia (Entries 7−8 in Table S18 and Figure S56), which provides solid evidence that ethanol is first oxidized to acetaldehyde and then that acetaldehyde reacts with ammonia to form acetamide. To further explore the reaction mechanism of ethanol‒ammonia oxidative coupling, in situ ATR−SEIRAS and online differential electrochemical mass spectrometry (DEMS) were carried out. The infrared signals of the key intermediates tend to increase with increasing current density (Figure 6a). The characteristic peaks located at 1215, 1422, 1535, 1643, 1920, and 2140 cm⁻¹, corresponding to C─O/Si─O, C─N, NO, H₂O, C═O, and C≡N, can be identified (Table S13). Moreover, the DEMS signals at m/z 41, 43 and 44 are detected, and all the signals increase and decrease in conjunction with the on‐ and off‐switching circuits (Figure 6b), confirming the presence of CH₃C≡N, CH₃HC═NH and CH₃CHO intermediates. Furthermore, the in situ Raman spectra show that the characteristic peak of α−PtO₂ (589 cm⁻¹) appears and increases with increasing current density, suggesting that the α−PtO₂ on the surface is the veritable active species for the ethanol‒ammonia oxidation reaction (Figure 6c). As a result, a Pt model with surface‐oxidized α−PtO₂ was constructed to study the reaction mechanism, denoted as Pt/α−PtO₂ ¹⁰. The reaction network involved in ethanol and ammonia oxidation was fully considered, as shown in Figure 6d [48, 49]. Fifty elementary steps were considered, resulting in dozens of reaction pathways (Table S19). In this way, ethanol is first oxidized to acetaldehyde (*CH₃CHO), and then, two feasible mechanisms stand out: path A and path B (Figure S57). For path A, the positively charged C atom in *CH₃CHO (Figure 6e,f) is nucleophilically attacked by the electronegative N atom in ammonia, and then the hemiaminal‐like intermediate is immediately formed after molecular rearrangement. Subsequently, the ethanimine (CH₃CH═NH) formed by dehydration of the hemiaminal‐like intermediate is further oxidized to acetonitrile, which can be directly converted to acetamide by a thermodynamically spontaneous hydrolysis reaction. Notably, the calculation results show that the potential‐determining step (PDS) of path A is the conversion of *CH₃CH═NH to *CH₃CH≡N (1.14 eV). For path B, *CH₃CO and *NH₂ are directly coupled to form acetamide (Figure 6g), whereas the positively charged C in *CH₃CO is favorable for coupling with *NH₂ (Figure 6h). The chemical coupling process and the kinetic barrier for this step were also calculated. The results show that a low barrier (0.1 eV) is involved; thus, this process can be easily performed at room temperature (Video S3). Notably, the PDS of path B is the conversion of *NH₃ to *NH₂ (0.72 eV). At the optimal current density (80 mA cm⁻²), the potential is greater than +1.5 V, which can easily overcome the thermodynamic limitations of both path A (1.14 eV) and path B (0.72 eV). In summary, owing to the similar reaction energies of PDS in the above two pathways, we propose that these two pathways are both important, and path A is experimentally confirmed (Figure S58). Path A is sensitive to the electronic structure of the catalyst (the electrophilicity of C in *CH₃CHO), whereas path B is more sensitive to the reaction microenvironment (the local concentrations of *CH₃CO and *NH₂ on the catalyst surface), which provides guidance for catalyst design in the future.

Mechanistic studies of the electrocatalytic transformation from ethanol and ammonia to acetamide. (a) Current density‐dependent in situ ATR−SEIRAS spectra over Pt using C₂H₅OH and NH₃ as feedstocks. (b) The online DEMS over Pt at +80 mA cm⁻². (c) Current density‐dependent in situ Raman spectra of Pt. (d) Visualization of chemical reaction spaces as graphs with molecules as nodes and reactions as edges for ethanol and ammonia reactions to acetamide. Nodes are colored according to the number of incident edges/reactions (degree) from low (blue) to medium (white) to high (red). (e) Free energy diagram of path A in Figure S57 for the generation of acetamide. (f) Differential charge density and Bader charge for *CH₃CHO over Pt/α−PtO₂, corresponding to an isosurface of ρ = 0.0005 e Bohr⁻³. Notably, 0.93 is the Bader charge of aldehyde‐C in *CH₃COH. (g) Free energy diagram of path B in Figure S57 for the generation of acetamide. (h) Differential charge density and Bader charge for *CH₃CO over Pt/α−PtO₂, corresponding to an isosurface of ρ = 0.005 e Bohr⁻³. 0.92 is the Bader charge of carbonyl‐C in *CH₃CO.

3. Conclusion

In summary, we report a cathode‒anode tandem strategy to synthesize acetamide with C─C─N bonds from CO₂ and NO₃ ⁻, in which C─C bonds and C─N bonds are constructed at the cathode and anode, respectively. At the cathode, NO₃ ⁻‐induced dynamically stable Cu^δ+ sites obviously increase the selectivity of ethanol from the CO₂RR (7.9% to 62.7%), accompanied by the generation of ammonia from NO₃ ⁻ reduction. The combined results of electrochemical in situ ATR−SEIRAS, XANES, Raman, and theoretical simulations reveal that simultaneous spontaneous redox (2Cu + NO₃ ⁻ → Cu₂O + NO₂ ⁻) and electroreduction (Cu₂O + 2e⁻ + 2H⁺ → 2Cu + H₂O) reactions create a larger number of dynamically stable Cu^δ+ sites, which are highly active for C─C coupling during the CO₂RR. Moreover, the adsorption of electron‐withdrawing NO₃ ⁻ on Cu^δ+ sites results in a localized electron distribution and thus improves the adsorption capacity and surface coverage of the *CO intermediate, leading to the enhancement of the asymmetric protonation pathways toward ethanol. Furthermore, the generated ethanol and ammonia (FE_C2H5OH: 57.3%, FE_NH3: 31.3%) at the cathode served as feedstocks to construct C─N bonds in tandem at the anode through the ethanol‒ammonia oxidative coupling reaction, which is preferable in thermodynamics to the OER. Based on this cathode−anode tandem system, the yield rate and Faradaic efficiency of acetamide are as high as 0.13 mmol h⁻¹ cm⁻² and 71.4%, respectively, outperforming the reported values for multicarbon nitrogenous compounds. This work provide a simple way to the preparation of multicarbon nitrogenous compounds from CO₂ and NO₃ ⁻ via tandem cathodic‒anodic reactions.

Author Contributions

Chengying Guo: conceptualization, writing – original draft, investigation. Rong Yang: investigation, writing – original draft. Nannan Meng: investigation. Jiang Shao: investigation. Minghao Guo: investigation. Hongjiao Li: investigation. Ang Cao: investigation, formal analysis. Bin Zhang: investigation, formal analysis. Yifu Yu: conceptualization, writing – review and editing, supervision, formal analysis.

Conflicts of Interest

The authors declare no conflicts of interest.

Supporting information

The authors have cited additional references within the Supporting Information [8, 10, 29, 35, 36, 37, 47, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126].

Supporting File 1: anie72755‐sup‐0001‐SuppMat.docx.

ANIE-65-e5526884-s002.docx^{(48.8MB, docx)}

Supporting File 2: anie72755‐sup‐0002‐VideoS1.mp4.

Download video file^{(282.1KB, mp4)}

Supporting File 3: anie72755‐sup‐0003‐VideoS2.mp4.

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Supporting File 4: anie72755‐sup‐0004‐VideoS3.mp4.

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Acknowledgments

We acknowledge the National Natural Science Foundation of China (224B2306 to Rong Yang 22509147 to Chengying Guo, and 22109115 to Yifu Yu) and the Tianjin Science and Technology Program (22ZYJDSS00060 to Yifu Yu).

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. Li J., Zhang Y., Kuruvinashetti K., and Kornienko N., “Construction of C─N Bonds From Small‐Molecule Precursors Through Heterogeneous Electrocatalysis,” Nature Reviews Chemistry 6 (2022): 303–319. [DOI] [PubMed] [Google Scholar]
2. Jouny M., Lv J., Cheng T., et al., “Formation of Carbon–Nitrogen Bonds in Carbon Monoxide Electrolysis,” Nature Chemistry 11 (2019): 846–851. [DOI] [PubMed] [Google Scholar]
3. Liu C., Gao Y., and Zhang B., “Organonitrogen Electrosynthesis From CO₂ and Nitrogenous Sources in Water,” Nature Synthesis 3 (2024): 794–796. [Google Scholar]
4. Lv C., Zhong L., Liu, et al., “Selective Electrocatalytic Synthesis of Urea With Nitrate and Carbon Dioxide,” Nature Sustainability 4 (2021): 868–876. [Google Scholar]
5. Huang Y., Yang R., Wang C., et al., “Direct Electrosynthesis of Urea From Carbon Dioxide and Nitric Oxide,” ACS Energy Letters 7 (2022): 284–291. [Google Scholar]
6. Xiong H., Yu P., Chen K., et al., “Urea Synthesis via Electrocatalytic Oxidative Coupling of CO With NH₃ on Pt,” Nature Catalysis 7 (2024): 785–795. [Google Scholar]
7. Wu Y., Jiang Z., Lin Z., Liang Y., and Wang H., “Direct Electrosynthesis of Methylamine From Carbon Dioxide and Nitrate,” Nature Sustainability 4 (2021): 725–730. [Google Scholar]
8. Lan J., Wei Z., Lu Y., et al., “Efficient Electrosynthesis of Formamide From Carbon Monoxide and Nitrite on a Ru‐Dispersed Cu Nanocluster Catalyst,” Nature Communications 14 (2023): 2870. [DOI] [PMC free article] [PubMed] [Google Scholar]
9. Luo Y., Xie K., Ou P., et al., “Selective Electrochemical Synthesis of Urea From Nitrate and CO₂ via Relay Catalysis on Hybrid Catalysts,” Nature Catalysis 6 (2023): 939–948. [Google Scholar]
10. Meng N., Shao J., Li H., et al., “Electrosynthesis of Formamide From Methanol and Ammonia Under Ambient Conditions,” Nature Communications 13 (2022): 5452. [DOI] [PMC free article] [PubMed] [Google Scholar]
11. Shao J., Meng N., Wang Y., et al., “Scalable Electrosynthesis of Formamide Through C─N Coupling at the Industrially Relevant Current Density of 120 mA cm⁻² ,” Angewandte Chemie International Edition 61 (2022): e202213009. [DOI] [PubMed] [Google Scholar]
12. Li H., Jiang Y., Li X., et al., “C₂₊ Selectivity for CO₂ Electroreduction on Oxidized Cu‐Based Catalysts,” Journal of the American Chemical Society 145 (2023): 14335–14344. [DOI] [PubMed] [Google Scholar]
13. De Luna P., Quintero‐Bermudez R., Dinh C., et al., “Catalyst Electro‐Redeposition Controls Morphology and Oxidation State for Selective Carbon Dioxide Reduction,” Nature Catalysis 1 (2018): 103–110. [Google Scholar]
14. Ma W., Xie S., Liu T., et al., “Electrocatalytic Reduction of CO₂ to Ethylene and Ethanol Through Hydrogen‐Assisted C–C Coupling Over Fluorine‐Modified Copper,” Nature Catalysis 3 (2020): 478–487. [Google Scholar]
15. Zang Y., Liu T., Wei P., et al., “Selective CO₂ Electroreduction to Ethanol Over a Carbon–Coated CuO_x Catalyst,” Angewandte Chemie International Edition 61 (2022): e202209629. [DOI] [PubMed] [Google Scholar]
16. Liang Z., Zhuang T., Seifitokaldani A., et al., “Copper‐on‐Nitride Enhances the Stable Electrosynthesis of Multi‐Carbon Products From CO₂ ,” Nature Communications 9 (2018): 3828. [DOI] [PMC free article] [PubMed] [Google Scholar]
17. Lei Q., Zhu H., Song K., et al., “Investigating the Origin of Enhanced C₂₊ Selectivity in Oxide‐/Hydroxide‐Derived Copper Electrodes During CO₂ Electroreduction,” Journal of the American Chemical Society 142 (2020): 4213–4222. [DOI] [PubMed] [Google Scholar]
18. Kuang S., Su Y., Li M., et al., “Asymmetrical Electrohydrogenation of CO₂ to Ethanol With Copper‐Gold Heterojunctions,” Proceedings of the National Academy of Sciences 120 (2023): 2214175120. [DOI] [PMC free article] [PubMed] [Google Scholar]
19. Han S., Li H., Li T., et al., “Ultralow Overpotential Nitrate Reduction to Ammonia via a Three‐Step Relay Mechanism,” Nature Catalysis 6 (2023): 402–414. [Google Scholar]
20. Xiao H., Goddard W. A., Cheng T., and Liu Y., “Cu Metal Embedded in Oxidized Matrix Catalyst to Promote CO₂ Activation and CO Dimerization for Electrochemical Reduction of CO₂ ,” Proceedings of the National Academy of Sciences 114 (2017): 6685–6688. [DOI] [PMC free article] [PubMed] [Google Scholar]
21. Calle‐Vallejo F., Loffreda D., Koper M. T. M., and Sautet P., “Introducing Structural Sensitivity Into Adsorption‐Energy Scaling Relations by Means of Coordination Numbers,” Nature Chemistry 7 (2015): 403–410. [DOI] [PubMed] [Google Scholar]
22. Cai Z., Cao N., Zhang F., et al., “Hierarchical Ag‐Cu Interfaces Promote C─C Coupling in Tandem CO₂ Electroreduction,” Applied Catalysis B: Environmental 325 (2023): 122310. [Google Scholar]
23. Zhong M., Tran K., Min Y., et al., “Accelerated Discovery of CO₂ Electrocatalysts Using Active Machine Learning,” Nature 581 (2020): 178–183. [DOI] [PubMed] [Google Scholar]
24. Jiang K., Sandberg R. B., Akey A. J., et al., “Metal Ion Cycling of Cu Foil for Selective C─C Coupling in Electrochemical CO₂ Reduction,” Nature Catalysis 1 (2018): 111–119. [Google Scholar]
25. Zhou Y., Yao Y., Zhao R., et al., “Stabilization of Cu⁺ via Strong Electronic Interaction for Selective and Stable CO₂ Electroreduction,” Angewandte Chemie International Edition 61 (2022): 202205832. [DOI] [PubMed] [Google Scholar]
26. Lum Y. and Ager J. W., “Stability of Residual Oxides in Oxide−Derived Copper Catalysts for Electrochemical CO₂ Reduction Investigated With ¹⁸O Labeling,” Angewandte Chemie International Edition 57 (2017): 551–554. [DOI] [PubMed] [Google Scholar]
27. Ye F., Zhang S., Cheng Q., et al., “The Role of Oxygen‐Vacancy in Bifunctional Indium Oxyhydroxide Catalysts for Electrochemical Coupling of Biomass Valorization With CO₂ Conversion,” Nature Communications 14 (2023): 2040. [DOI] [PMC free article] [PubMed] [Google Scholar]
28. Wang P., Yang H., Tang C., et al., “Boosting Electrocatalytic CO₂‐to‐Ethanol Production via Asymmetric C─C Coupling,” Nature Communications 13 (2022): 3754. [DOI] [PMC free article] [PubMed] [Google Scholar]
29. Lin Y., Wang T., Zhang L., et al., “Tunable CO₂ Electroreduction to Ethanol and Ethylene With Controllable Interfacial Wettability,” Nature Communications 14 (2023): 3575. [DOI] [PMC free article] [PubMed] [Google Scholar]
30. Chang X., Wang T., Zhao Z., et al., “Tuning Cu/Cu₂O Interfaces for the Reduction of Carbon Dioxide to Methanol in Aqueous Solutions,” Angewandte Chemie International Edition 57 (2018): 15415–15419. [DOI] [PubMed] [Google Scholar]
31. Gu Z., Shen H., Chen Z., et al., “Efficient Electrocatalytic CO₂ Reduction to C₂₊ Alcohols at Defect‐Site‐Rich Cu Surface,” Joule 5 (2021): 429–440. [Google Scholar]
32. Zhou Y., Che F., Liu M., et al., “Dopant‐induced Electron Localization Drives CO₂ Reduction to C₂ Hydrocarbons,” Nature Chemistry 10 (2018): 974–980. [DOI] [PubMed] [Google Scholar]
33. Ren D., Deng Y., Handoko A. D., Chen C. S., Malkhandi S., and Yeo B. S., “Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts,” ACS Catalysis 5 (2015): 2814–2821. [Google Scholar]
34. Chen C., Sun X., Lu L., et al., “Efficient Electroreduction of CO₂ to C₂ Products Over B‐Doped Oxide‐Derived Copper,” Green Chemistry 20 (2018): 4579–4583. [Google Scholar]
35. Karapinar D., Huan N. T., Ranjbar Sahraie N., et al., “Electroreduction of CO₂ on Single‐Site Copper‐Nitrogen‐Doped Carbon Material: Selective Formation of Ethanol and Reversible Restructuration of the Metal Sites,” Angewandte Chemie International Edition 58 (2019): 15098–15103. [DOI] [PubMed] [Google Scholar]
36. Dutta A., Montiel I. Z., Erni R., et al., “Activation of Bimetallic AgCu Foam Electrocatalysts for Ethanol Formation From CO₂ by Selective Cu Oxidation/Reduction,” Nano Energy 68 (2020): 104331. [Google Scholar]
37. Ma G., Syzgantseva O. A., Huang Y., et al., “A Hydrophobic Cu/Cu₂O Sheet Catalyst for Selective Electroreduction of CO to Ethanol,” Nature Communications 14 (2023): 501. [DOI] [PMC free article] [PubMed] [Google Scholar]
38. Wang X., Wang Z., García de Arquer F. P., et al., “Efficient Electrically Powered CO₂‐to‐Ethanol via Suppression of Deoxygenation,” Nature Energy 5 (2020): 478–486. [Google Scholar]
39. Li Z., Wang L., Wang T., Sun L., and Yang W., “Steering the Dynamics of Reaction Intermediates and Catalyst Surface During Electrochemical Pulsed CO₂ Reduction for Enhanced C₂₊ Selectivity,” Journal of the American Chemical Society 145 (2023): 20655–20664. [DOI] [PubMed] [Google Scholar]
40. Xie Y., Ou P., Wang X., et al., “High Carbon Utilization in CO₂ Reduction to Multi‐Carbon Products in Acidic Media,” Nature Catalysis 5 (2022): 564–570. [Google Scholar]
41. Chou T., Chang C., Yu H., et al., “Controlling the Oxidation State of the Cu Electrode and Reaction Intermediates for Electrochemical CO₂ Reduction to Ethylene,” Journal of the American Chemical Society 142 (2020): 2857–2867. [DOI] [PubMed] [Google Scholar]
42. Zhu S., Wang Q., Qin X., et al., “Tuning Structural and Compositional Effects in Pd‐Au Nanowires for Highly Selective and Active CO₂ Electrochemical Reduction Reaction,” Advanced Energy Materials 8 (2018): 201802238. [Google Scholar]
43. Chang X., Vijay S., Zhao Y., Oliveira N. J., Chan K., and Xu B., “Understanding the Complementarities of Surface‐Enhanced Infrared and Raman Spectroscopies in CO Adsorption and Electrochemical Reduction,” Nature Communications 13 (2022): 2625. [DOI] [PMC free article] [PubMed] [Google Scholar]
44. Yang Y., He A., Li H., et al., “Operando Constructing Cu/Cu₂O Electrocatalysts for Efficient CO₂ Electroreduction to Ethanol: CO₂‐Assisted Structural Evolution of Octahedral Cu₂O by Operando CV Activation,” ACS Catalysis 12 (2022): 12942–12953. [Google Scholar]
45. Liu K., Yang C., Wei R., et al., “Unraveling and Tuning the Linear Correlation Between CH₄ and C₂ Production Rates in CO₂ Electroreduction,” Science Bulletin 67 (2022): 1042–1048. [DOI] [PubMed] [Google Scholar]
46. Zhuansun M., Liu Y., Lu R., et al., “Promoting CO₂ Electroreduction to Multi−Carbon Products by Hydrophobicity‐Induced Electro‐Kinetic Retardation,” Angewandte Chemie International Edition 62 (2023): e202309875. [DOI] [PubMed] [Google Scholar]
47. Luna D., Hahn C., Higgins D., Jaffer S. A., Jaramillo T. F., and Sargent E. H., “What Would It Take for Renewably Powered Electrosynthesis to Displace Petrochemical Processes?” Science 364 (2019): 350. [DOI] [PubMed] [Google Scholar]
48. Stocker S., Csányi G., Reuter K., and Margraf J. T., “Machine Learning in Chemical Reaction Space,” Nature Communications 11 (2020): 5505. [DOI] [PMC free article] [PubMed] [Google Scholar]
49. Margraf J. T., Jung H., Scheurer C., and Reuter K., “Exploring Catalytic Reaction Networks With Machine Learning,” Nature Catalysis 6 (2023): 112–121. [Google Scholar]
50. Hafner J., “Ab−Initio Simulations of Materials Using VASP: Density−Functional Theory and Beyond,” Journal of Computational Chemistry 29 (2008): 2044–2078. [DOI] [PubMed] [Google Scholar]
51. Kresse G. and Joubert D., “From Ultrasoft Pseudopotentials to the Projector Augmented‐Wave Method,” Physical Review B 59 (1999): 1758–1775. [Google Scholar]
52. Mathew K., Kolluru V. S. C., Mula S., Steinmann S. N., and Hennig R. G., “Implicit Self‐Consistent Electrolyte Model in Plane‐Wave Density‐Functional Theory,” Journal of Chemical Physics 151 (2019): 234101. [DOI] [PubMed] [Google Scholar]
53. Nørskov J. K., Rossmeisl J., Logadottir A., and Lindqvist L., “Origin of the Overpotential for Oxygen Reduction at a Fuel‐Cell Cathode,” Journal of Physical Chemistry B 108 (2004): 17886. [DOI] [PubMed] [Google Scholar]
54. Henkelman G., Uberuaga B. P., and Jónsson H., “A Climbing Image Nudged Elastic Band Method for Finding Saddle Points and Minimum Energy Paths,” Journal of Chemical Physics 113 (2000): 9901–9904. [Google Scholar]
55. Perdew J. P., Burke K., and Ernzerhof M., “Generalized Gradient Approximation Made Simple,” Physical Review Letter 77 (1996): 3865–3868. [DOI] [PubMed] [Google Scholar]
56. Ricardo U.‐O., Builes S., and Calle‐Vallejo F., “Fast Correction of Errors in the DFT‐Calculated Energies of Gaseous Nitrogen‐Containing Species,” ChemCatChem 13 (2021): 2508. [Google Scholar]
57. Granda‐Marulanda L. P., Rendón‐Calle A., Builes S., Illas F., Koper M. T. M., and Calle‐Vallejo F., “A Semiempirical Method to Detect and Correct DFT‐Based Gas‐Phase Errors and Its Application in Electrocatalysis,” ACS Catalysis 10 (2020): 6900–6907. [Google Scholar]
58. Wang V., Xu N., Liu J., Tang G., and Geng W.‐T., “VASPKIT: A User‐Friendly Interface Facilitating High‐Throughput Computing and Analysis Using VASP Code,” Computer Physics Communications 267 (2021): 108033. [Google Scholar]
59. Vojtěch Š., Chun S., Pokorný V., Fulem M., and Růẑiĉka K., “Thermodynamic Study of Acetamides,” Journal of Molecular Liquids 319 (2020): 114019. [Google Scholar]
60. Wang W., Dai S., Li X., Yang J., Srolovitz D. J., and Zheng Q., “Measurement of the Cleavage Energy of Graphite,” Nature Communications 6 (2015): 7853. [DOI] [PMC free article] [PubMed] [Google Scholar]
61. Ricardo U. O., Builes S., Illas F., and Calle‐Vallejo F., “Gas‐Phase Errors in Computational Electrocatalysis: A Review,” EES Catalysis 2 (2024): 157. [Google Scholar]
62. Peterson A. A., Abild‐Pedersen F., Studt F., Rossmeisl J., and Nørskov J. K., “How Copper Catalyzes the Electroreduction of Carbon Dioxide Into Hydrocarbon Fuels,” Energy & Environmental Science 3 (2010): 1311. [Google Scholar]
63. Urrego‐Ortiz R., Builes S., and Calle‐Vallejo F., “Impact of Intrinsic Density Functional Theory Errors on the Predictive Power of Nitrogen Cycle Electrocatalysis Models,” ACS Catalysis 12 (2022): 4784–4791. [DOI] [PMC free article] [PubMed] [Google Scholar]
64. Lide D. R., CRC Handbook of Chemistry and Physics, 85th ed. (CRC Press, 2004). [Google Scholar]
65. Chase M. W., Davies C. A., Downey J. R., Frurip D. J., MacDonald R. A., and Syverud A. N., “NIST−JANAF Thermochemical Tables,” Journal of Physical and Chemical Reference Data 14 (1985): 1856, NIST Chemistry WebBook, accessed October 18, https://webbook.nist.gov/chemistry/. [Google Scholar]
66. Lide D. R., CRC Handbook of Chemistry and Physics, 90th ed. (CRC Press, 2010). [Google Scholar]
67. Nitopi S., Bertheussen E., and Scott S. B., “Progress and Perspectives of Electrochemical CO₂ Reduction on Copper in Aqueous Electrolyte,” Chemical Reviews 119 (2019): 7610–7672. [DOI] [PubMed] [Google Scholar]
68. Mathew K., Sundararaman R., Letchworth‐Weaver K., Arias T. A., and Hennig R. G., “Implicit Solvation Model for Density‐Functional Study of Nanocrystal Surfaces and Reaction Pathways,” Journal of Chemical Physics 140 (2014): 084106. [DOI] [PubMed] [Google Scholar]
69. Calle‐Vallejo F., Martínez J. I., García‐Lastra J. M., Rossmeisl J., and Koper M. T. M., “Physical and Chemical Nature of the Scaling Relations Between Adsorption Energies of Atoms on Metal Surfaces,” Physical Review Letter 108 (2012): 116103. [DOI] [PubMed] [Google Scholar]
70. Abild‐Pedersen F., Greeley J., Studt F., et al., “Scaling Properties of Adsorption Energies for Hydrogen‐Containing Molecules on Transition‐Metal Surfaces,” Physical Review Letter 99 (2007): 016105. [DOI] [PubMed] [Google Scholar]
71. Zhao Z., Liu S., Zha S., et al., “Theory‐Guided Design of Catalytic Materials Using Scaling Relationships and Reactivity Descriptors,” Nature Reviews Materials 4 (2019): 792–804. [Google Scholar]
72. Calle‐Vallejo F., Huang M., Henry J. B., Koper M. T. M., and Bandarenka A. S., “Theoretical Design and Experimental Implementation of Ag/Au Electrodes for the Electrochemical Reduction of Nitrate,” Physical Chemistry Chemical Physics 15 (2013): 3196. [DOI] [PubMed] [Google Scholar]
73. Hao W., Alexander B., and Jan R., “Electrochemical Nitric Oxide Reduction on Metal Surfaces,” Angewandte Chemie International Edition 60 (2021): 21966. [DOI] [PubMed] [Google Scholar]
74. Guo C., Fu X., Long J., et al., “Toward Computational Design of Chemical Reactions With Reaction Phase Diagram,” WIREs Computational Molecular Science 11 (2021): e1514. [Google Scholar]
75. Beverskog B. and Puigdomenech I., “Revised Pourbaix Diagrams for Copper at 25 to 300°C,” Journal of the Electrochemical Society 144 (1997): 3476–3483. [Google Scholar]
76. Stenlid J. H., Dos Santos E. C., Bagger A., Johansson A. J., Rossmeisl J., and Pettersson L. G. M., “Electrochemical Interface During Corrosion of Copper in Anoxic Sulfide‐Containing Groundwater–A Computational Study,” Journal of Physical Chemistry C 124 (2019): 469–481. [Google Scholar]
77. Chang X., Wang T., Zhao Z., et al., “Tuning Cu/Cu₂O Interfaces for the Reduction of Carbon Dioxide to Methanol in Aqueous Solutions,” Angewandte Chemie International Edition 57 (2018): 15415–15419. [DOI] [PubMed] [Google Scholar]
78. Liang Z., Zhuang T., Seifitokaldani A., et al., “Copper‐on‐Nitride Enhances the Stable Electrosynthesis of Multicarbon Products From CO₂ ,” Nature Communications 9 (2018): 3828. [DOI] [PMC free article] [PubMed] [Google Scholar]
79. Zhou Y., Yao Y., Zhao R., et al., “Stabilization of Cu⁺ via Strong Electronic Interaction for Selective and Stable CO₂ Electroreduction,” Angewandte Chemie International Edition 61 (2022): e202205832. [DOI] [PubMed] [Google Scholar]
80. Kuang S., Xiao T., Chi H., et al., “Acetamide Electrosynthesis From CO₂ and Nitrite in Water,” Angewandte Chemie International Edition 63 (2024): e202316772. [DOI] [PubMed] [Google Scholar]
81. Zhou Y., Che F., Liu M., et al., “Dopant‐induced Electron Localization Drives CO₂ Reduction to C₂ Hydrocarbons,” Nature Chemistry 10 (2018): 974–980. [DOI] [PubMed] [Google Scholar]
82. Jiang K., Sandberg R. B., Akey A. J., et al., “Metal Ion Cycling of Cu Foil for Selective C–C Coupling in Electrochemical CO₂ Reduction,” Nature Catalysis 1 (2018): 111–119. [Google Scholar]
83. Zhu Q., Sun X., Yang D., et al., “Carbon Dioxide Electroreduction to C₂ Products Over Copper‐Cuprous Oxide Derived From Electrosynthesized Copper Complex,” Nature Communications 10 (2019): 3851. [DOI] [PMC free article] [PubMed] [Google Scholar]
84. Ren D., Deng Y., Handoko A. D., Chen C. S., Malkhandi S., and Yeo B. S., “Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts,” ACS Catalysis 5 (2015): 2814–2821. [Google Scholar]
85. Chen C., Sun X., Lu L., et al., “Efficient Electroreduction of CO₂ to C₂ Products Over B‐Doped Oxide‐Derived Copper,” Green Chemistry 20 (2018): 4579–4583. [Google Scholar]
86. Handoko A. D., Chan K. W., and Yeo B. S., “–CH₃ Mediated Pathway for the Electroreduction of CO₂ to Ethane and Ethanol on Thick Oxide‐Derived Copper Catalysts at Low Overpotentials,” ACS Energy Letters 2 (2017): 2103–2109. [Google Scholar]
87. Lee S., Park G., and Lee J., “Importance of Ag‐Cu Biphasic Boundaries for Selective Electrochemical Reduction of CO₂ to Ethanol,” ACS Catalysis 7 (2017): 8594–8604. [Google Scholar]
88. Wang P., Yang H., Tang C., et al., “Boosting Electrocatalytic CO₂‐to‐Ethanol Production via Asymmetric C–C Coupling,” Nature Communications 13 (2022): 3754. [DOI] [PMC free article] [PubMed] [Google Scholar]
89. Li Y. C., Wang Z., Yuan T., et al., “Binding Site Diversity Promotes CO₂ Electroreduction to Ethanol,” Journal of the American Chemical Society 141 (2019): 8584–8591. [DOI] [PubMed] [Google Scholar]
90. Ren D., Ang B. S., and Yeo B. S., “Tuning the Selectivity of Carbon Dioxide Electroreduction Toward Ethanol on Oxide‐derived Cu_xZn Catalysts,” ACS Catalysis 6 (2016): 8239–8247. [Google Scholar]
91. Song Y., Peng R., Hensley D. K., et al., “High–Selectivity Electrochemical Conversion of CO₂ to Ethanol Using a Copper Nanoparticle/N–Doped Graphene Electrode,” ChemistrySelect 1 (2016): 6055–6061. [Google Scholar]
92. Han Z., Kortlever R., Chen H., Peters J. C., and Agapie T., “CO₂ Reduction Selective for C_≥2 Products on Polycrystalline Copper With N‐Substituted Pyridinium Additives,” ACS Central Science 3 (2017): 853–859. [DOI] [PMC free article] [PubMed] [Google Scholar]
93. Ren D., Gao J., Pan L., et al., “Atomic Layer Deposition of ZnO on CuO Enables Selective and Efficient Electroreduction of Carbon Dioxide to Liquid Fuels,” Angewandte Chemie International Edition 58 (2019): 15036–15040. [DOI] [PubMed] [Google Scholar]
94. Wang X., Wang Z., García de Arquer F. P., et al., “Efficient Electrically Powered CO₂‐to‐Ethanol via Suppression of Deoxygenation,” Nature Energy 5 (2020): 478–486. [Google Scholar]
95. Gu Z., Shen H., Chen Z., et al., “Efficient Electrocatalytic CO₂ Reduction to C₂₊ Alcohols at Defect‐Site‐Rich Cu Surface,” Joule 5 (2021): 429–440. [Google Scholar]
96. Xu H., Rebollar D., He H., et al., “Highly Selective Electrocatalytic CO₂ Reduction to Ethanol by Metallic Clusters Dynamically Formed From Atomically Dispersed Copper,” Nature Energy 5 (2020): 623–632. [Google Scholar]
97. Zhao Z., Huang J., Liao P., and Chen X., “Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal‐Organic Framework With Heterodimetal Dual Sites,” Journal of the American Chemical Society 145 (2023): 26783–26790. [DOI] [PubMed] [Google Scholar]
98. Kuang S., Su Y., and Li M., “Asymmetrical Electrohydrogenation of CO₂ to Ethanol With Copper‐Gold Heterojunctions,”Proceedings of the National Academy of Sciences 120 (2023): e2214175120. [DOI] [PMC free article] [PubMed] [Google Scholar]
99. Zhang T., Yuan B., Wang W., He J., and Xiang X., “Tailoring *H Intermediate Coverage on the CuAl₂O₄/CuO Catalyst for Enhanced Electrocatalytic CO₂ Reduction to Ethanol,” Angewandte Chemie International Edition 62 (2023): e202302096. [DOI] [PubMed] [Google Scholar]
100. Kim C., Cho K. M., Park K., et al., “Cu/Cu₂O Interconnected Porous Aerogel Catalyst for Highly Productive Electrosynthesis of Ethanol From CO₂ ,” Advanced Functional Materials 31 (2021): 2102142. [Google Scholar]
101. Zhuang T., Liang Z., Seifitokaldani A., et al., “Steering Post‐C–C Coupling Selectivity Enables High Efficiency Electroreduction of Carbon Dioxide to Multi‐Carbon Alcohols,” Nature Catalysis 1 (2018): 421–428. [Google Scholar]
102. Lv C., Zhong L., Liu H., et al., “Selective Electrocatalytic Synthesis of Urea With Nitrate and Carbon Dioxide,” Nature Sustainability 4 (2021): 868–876. [Google Scholar]
103. Ye L., Liu J., Gao Y., et al., “Highly Oriented MOF Thin Film‐Based Electrocatalytic Device for the Reduction of CO₂ to CO Exhibiting High Faradaic Efficiency,” Journal of Materials Chemistry A 4 (2016): 15320–15326. [Google Scholar]
104. Han S., Li H., Li T., et al., “Ultralow Overpotential Nitrate Reduction to Ammonia via a Three‐Step Relay Mechanism,” Nature Catalysis 6 (2023): 402–414. [Google Scholar]
105. Zhong W., Chen Y., Chen P., et al., “Balancing Hydrogen Evolution and Hydrogenation Reaction via Facet Engineering for Efficient Conversion of Nitrate to Ammonia in Actual Wastewater,” Angewandte Chemie International Edition 64 (2025): e202503117. [DOI] [PubMed] [Google Scholar]
106. Zhao H., Liu P., Cheng X., et al., “A Cu‐Cu₂O/Ni₂P Heterostructure for Efficient Tandem Catalysis of Electrosynthesis of Ammonia From Nitrate Reduction Reaction in Neutral Medium,” Advanced Functional Materials 35 (2025): 2425459. [Google Scholar]
107. Dai Y., Li S., Li X., et al., “Tandem Active Sites in Cu/Mo‐WO₃ Electrocatalysts for Efficient Electrocatalytic Nitrate Reduction to Ammonia,” Advanced Functional Materials 35 (2025): 2420282. [Google Scholar]
108. Li X., Wang S., Li L., Sun Y., and Xie Y., “Progress and Perspective for In Situ Studies of CO₂ Reduction,” Journal of the American Chemical Society 142 (2020): 9567. [DOI] [PubMed] [Google Scholar]
109. Chou T., Chang C., Yu H., et al., “Controlling the Oxidation State of the Cu Electrode and Reaction Intermediates for Electrochemical CO₂ Reduction to Ethylene,” Journal of the American Chemical Society 142 (2020): 2857–2867. [DOI] [PubMed] [Google Scholar]
110. Shi Y., Ji Y., Long J., et al., “Unveiling Hydrocerussite as an Electrochemically Stable Active Phase for Efficient Carbon Dioxide Electroreduction to Formate,” Nature Communications 11 (2020): 3415. [DOI] [PMC free article] [PubMed] [Google Scholar]
111. Sun W., Wang P., Jiang Y., et al., “V‐Doped Cu₂Se Hierarchical Nanotubes Enabling Flow‐cell CO₂ Electroreduction to Ethanol With High Efficiency and Selectivity,” Advanced Materials 34 (2022): 2207691. [DOI] [PubMed] [Google Scholar]
112. Tao Z., Wu Y., Wu Z., Shang B., Rooney C., and Wang H., “Cascade Electrocatalytic Reduction of Carbon Dioxide and Nitrate to Ethylamine,” Journal of Energy Chemistry 65 (2022): 367–370. [Google Scholar]
113. Wu Y., Jiang Z., Lin Z., Liang Y., and Wang H., “Direct Electrosynthesis of Methylamine From Carbon Dioxide and Nitrate,” Nature Sustainability 4 (2021): 725–730. [Google Scholar]
114. Chen C., Zhu X., Wen X., et al., “Coupling N₂ and CO₂ in H₂O to Synthesize Urea Under Ambient Conditions,” Nature Chemistry 12 (2020): 717–724. [DOI] [PubMed] [Google Scholar]
115. Li J. and Kornienko N., “Electrochemically Driven C–N Bond Formation From CO₂ and Ammonia at the Triple‐Phase Boundary,” Chemical Science 13 (2022): 3957–3964. [DOI] [PMC free article] [PubMed] [Google Scholar]
116. Jouny M., Lv J., Cheng T., et al., “Formation of Carbon–Nitrogen Bonds in Carbon Monoxide Electrolysis,” Nature Chemistry 11 (2019): 846–851. [DOI] [PubMed] [Google Scholar]
117. Huang Y., Yang R., Wang C., et al., “Direct Electrosynthesis of Urea From Carbon Dioxide and Nitric Oxide,” ACS Energy Letters 7 (2022): 284–291. [Google Scholar]
118. Tong Y., Wang Z., Yang E., et al., “Determination and Correlation of Solubility and Solution Thermodynamics of Ethenzamide in Different Pure Solvents,” Fluid Phase Equilibria 427 (2016): 549–556. [Google Scholar]
119. Xu D., Tan B., Shi H., Hao M., Guan Y., and Liu J., “Measurement and Correlation of Liquid‐Liquid Equilibrium Data for the Extraction of Glycerol Carbonate From Glycerol Using Ethyl Acetate and 2‐Butanone + Benzene Mixture,” Journal of Chemical & Engineering Data 69 (2024): 1939–1947. [Google Scholar]
120. Zhang X., Hao X., Jian C., et al., “Experimental Isobaric Vapour‐Liquid Equilibrium Data for Binary Systems of {Sec‐Butyl Acetate (SBAC)+Acetamide} and {Sec‐butyl Alcohol (SBA)+Acetamide} and the Ternary System of (SBAC+SBA+Acetamide) at 101.3 kPa,” Journal of Chemical Thermodynamics 144 (2020): 106087. [Google Scholar]
121. Mo W., Tan X., and Ong W., “Prospective Life Cycle Assessment Bridging Biochemical, Thermochemical, and Electrochemical CO₂ Reduction Toward Sustainable Ethanol Synthesis,” ACS Sustainable Chemistry & Engineering 11 (2023): 5782–5799. [Google Scholar]
122. Zhao B., Chen F., Wang M., et al., “Economically Viable Electrocatalytic Ethylene Production With High Yield and Selectivity,” Nature Sustainability 6 (2023): 827–837. [Google Scholar]
123. Jouny M., Luc W., and Jiao F., “General Techno‐Economic Analysis of CO₂ Electrolysis Systems,” Industrial & Engineering Chemistry Research 57 (2018): 2165–2177. [Google Scholar]
124. Lum Y., Huang J. E., Wang Z., et al., “Tuning OH Binding Energy Enables Selective Electrochemical Oxidation of Ethylene to Ethylene Glycol,” Nature Catalysis 3 (2020): 14–22. [Google Scholar]
125. Shin H., Hansen K. U., and Jiao F., “Techno‐Economic Assessment of Low‐Temperature Carbon Dioxide Electrolysis,” Nature Sustainability 4 (2021): 911–919. [Google Scholar]
126. Guo C., Guo Y., Shi Y., et al., “Electrocatalytic Reduction of CO₂ to Ethanol at Close to Theoretical Potential via Engineering Abundant Electron‐Donating Cu^δ+ Species,” Angewandte Chemie International Edition 61 (2022): e2022059. [DOI] [PubMed] [Google Scholar]

Associated Data

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

Supplementary Materials

Supporting File 1: anie72755‐sup‐0001‐SuppMat.docx.

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Supporting File 2: anie72755‐sup‐0002‐VideoS1.mp4.

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Supporting File 3: anie72755‐sup‐0003‐VideoS2.mp4.

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Supporting File 4: anie72755‐sup‐0004‐VideoS3.mp4.

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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.

[anie72755-bib-0001] 1. Li J., Zhang Y., Kuruvinashetti K., and Kornienko N., “Construction of C─N Bonds From Small‐Molecule Precursors Through Heterogeneous Electrocatalysis,” Nature Reviews Chemistry 6 (2022): 303–319. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0002] 2. Jouny M., Lv J., Cheng T., et al., “Formation of Carbon–Nitrogen Bonds in Carbon Monoxide Electrolysis,” Nature Chemistry 11 (2019): 846–851. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0003] 3. Liu C., Gao Y., and Zhang B., “Organonitrogen Electrosynthesis From CO₂ and Nitrogenous Sources in Water,” Nature Synthesis 3 (2024): 794–796. [Google Scholar]

[anie72755-bib-0004] 4. Lv C., Zhong L., Liu, et al., “Selective Electrocatalytic Synthesis of Urea With Nitrate and Carbon Dioxide,” Nature Sustainability 4 (2021): 868–876. [Google Scholar]

[anie72755-bib-0005] 5. Huang Y., Yang R., Wang C., et al., “Direct Electrosynthesis of Urea From Carbon Dioxide and Nitric Oxide,” ACS Energy Letters 7 (2022): 284–291. [Google Scholar]

[anie72755-bib-0006] 6. Xiong H., Yu P., Chen K., et al., “Urea Synthesis via Electrocatalytic Oxidative Coupling of CO With NH₃ on Pt,” Nature Catalysis 7 (2024): 785–795. [Google Scholar]

[anie72755-bib-0007] 7. Wu Y., Jiang Z., Lin Z., Liang Y., and Wang H., “Direct Electrosynthesis of Methylamine From Carbon Dioxide and Nitrate,” Nature Sustainability 4 (2021): 725–730. [Google Scholar]

[anie72755-bib-0008] 8. Lan J., Wei Z., Lu Y., et al., “Efficient Electrosynthesis of Formamide From Carbon Monoxide and Nitrite on a Ru‐Dispersed Cu Nanocluster Catalyst,” Nature Communications 14 (2023): 2870. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0009] 9. Luo Y., Xie K., Ou P., et al., “Selective Electrochemical Synthesis of Urea From Nitrate and CO₂ via Relay Catalysis on Hybrid Catalysts,” Nature Catalysis 6 (2023): 939–948. [Google Scholar]

[anie72755-bib-0010] 10. Meng N., Shao J., Li H., et al., “Electrosynthesis of Formamide From Methanol and Ammonia Under Ambient Conditions,” Nature Communications 13 (2022): 5452. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0011] 11. Shao J., Meng N., Wang Y., et al., “Scalable Electrosynthesis of Formamide Through C─N Coupling at the Industrially Relevant Current Density of 120 mA cm⁻² ,” Angewandte Chemie International Edition 61 (2022): e202213009. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0012] 12. Li H., Jiang Y., Li X., et al., “C₂₊ Selectivity for CO₂ Electroreduction on Oxidized Cu‐Based Catalysts,” Journal of the American Chemical Society 145 (2023): 14335–14344. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0013] 13. De Luna P., Quintero‐Bermudez R., Dinh C., et al., “Catalyst Electro‐Redeposition Controls Morphology and Oxidation State for Selective Carbon Dioxide Reduction,” Nature Catalysis 1 (2018): 103–110. [Google Scholar]

[anie72755-bib-0014] 14. Ma W., Xie S., Liu T., et al., “Electrocatalytic Reduction of CO₂ to Ethylene and Ethanol Through Hydrogen‐Assisted C–C Coupling Over Fluorine‐Modified Copper,” Nature Catalysis 3 (2020): 478–487. [Google Scholar]

[anie72755-bib-0015] 15. Zang Y., Liu T., Wei P., et al., “Selective CO₂ Electroreduction to Ethanol Over a Carbon–Coated CuO_x Catalyst,” Angewandte Chemie International Edition 61 (2022): e202209629. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0016] 16. Liang Z., Zhuang T., Seifitokaldani A., et al., “Copper‐on‐Nitride Enhances the Stable Electrosynthesis of Multi‐Carbon Products From CO₂ ,” Nature Communications 9 (2018): 3828. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0017] 17. Lei Q., Zhu H., Song K., et al., “Investigating the Origin of Enhanced C₂₊ Selectivity in Oxide‐/Hydroxide‐Derived Copper Electrodes During CO₂ Electroreduction,” Journal of the American Chemical Society 142 (2020): 4213–4222. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0018] 18. Kuang S., Su Y., Li M., et al., “Asymmetrical Electrohydrogenation of CO₂ to Ethanol With Copper‐Gold Heterojunctions,” Proceedings of the National Academy of Sciences 120 (2023): 2214175120. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0019] 19. Han S., Li H., Li T., et al., “Ultralow Overpotential Nitrate Reduction to Ammonia via a Three‐Step Relay Mechanism,” Nature Catalysis 6 (2023): 402–414. [Google Scholar]

[anie72755-bib-0020] 20. Xiao H., Goddard W. A., Cheng T., and Liu Y., “Cu Metal Embedded in Oxidized Matrix Catalyst to Promote CO₂ Activation and CO Dimerization for Electrochemical Reduction of CO₂ ,” Proceedings of the National Academy of Sciences 114 (2017): 6685–6688. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0021] 21. Calle‐Vallejo F., Loffreda D., Koper M. T. M., and Sautet P., “Introducing Structural Sensitivity Into Adsorption‐Energy Scaling Relations by Means of Coordination Numbers,” Nature Chemistry 7 (2015): 403–410. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0022] 22. Cai Z., Cao N., Zhang F., et al., “Hierarchical Ag‐Cu Interfaces Promote C─C Coupling in Tandem CO₂ Electroreduction,” Applied Catalysis B: Environmental 325 (2023): 122310. [Google Scholar]

[anie72755-bib-0023] 23. Zhong M., Tran K., Min Y., et al., “Accelerated Discovery of CO₂ Electrocatalysts Using Active Machine Learning,” Nature 581 (2020): 178–183. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0024] 24. Jiang K., Sandberg R. B., Akey A. J., et al., “Metal Ion Cycling of Cu Foil for Selective C─C Coupling in Electrochemical CO₂ Reduction,” Nature Catalysis 1 (2018): 111–119. [Google Scholar]

[anie72755-bib-0025] 25. Zhou Y., Yao Y., Zhao R., et al., “Stabilization of Cu⁺ via Strong Electronic Interaction for Selective and Stable CO₂ Electroreduction,” Angewandte Chemie International Edition 61 (2022): 202205832. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0026] 26. Lum Y. and Ager J. W., “Stability of Residual Oxides in Oxide−Derived Copper Catalysts for Electrochemical CO₂ Reduction Investigated With ¹⁸O Labeling,” Angewandte Chemie International Edition 57 (2017): 551–554. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0027] 27. Ye F., Zhang S., Cheng Q., et al., “The Role of Oxygen‐Vacancy in Bifunctional Indium Oxyhydroxide Catalysts for Electrochemical Coupling of Biomass Valorization With CO₂ Conversion,” Nature Communications 14 (2023): 2040. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0028] 28. Wang P., Yang H., Tang C., et al., “Boosting Electrocatalytic CO₂‐to‐Ethanol Production via Asymmetric C─C Coupling,” Nature Communications 13 (2022): 3754. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0029] 29. Lin Y., Wang T., Zhang L., et al., “Tunable CO₂ Electroreduction to Ethanol and Ethylene With Controllable Interfacial Wettability,” Nature Communications 14 (2023): 3575. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0030] 30. Chang X., Wang T., Zhao Z., et al., “Tuning Cu/Cu₂O Interfaces for the Reduction of Carbon Dioxide to Methanol in Aqueous Solutions,” Angewandte Chemie International Edition 57 (2018): 15415–15419. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0031] 31. Gu Z., Shen H., Chen Z., et al., “Efficient Electrocatalytic CO₂ Reduction to C₂₊ Alcohols at Defect‐Site‐Rich Cu Surface,” Joule 5 (2021): 429–440. [Google Scholar]

[anie72755-bib-0032] 32. Zhou Y., Che F., Liu M., et al., “Dopant‐induced Electron Localization Drives CO₂ Reduction to C₂ Hydrocarbons,” Nature Chemistry 10 (2018): 974–980. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0033] 33. Ren D., Deng Y., Handoko A. D., Chen C. S., Malkhandi S., and Yeo B. S., “Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts,” ACS Catalysis 5 (2015): 2814–2821. [Google Scholar]

[anie72755-bib-0034] 34. Chen C., Sun X., Lu L., et al., “Efficient Electroreduction of CO₂ to C₂ Products Over B‐Doped Oxide‐Derived Copper,” Green Chemistry 20 (2018): 4579–4583. [Google Scholar]

[anie72755-bib-0035] 35. Karapinar D., Huan N. T., Ranjbar Sahraie N., et al., “Electroreduction of CO₂ on Single‐Site Copper‐Nitrogen‐Doped Carbon Material: Selective Formation of Ethanol and Reversible Restructuration of the Metal Sites,” Angewandte Chemie International Edition 58 (2019): 15098–15103. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0036] 36. Dutta A., Montiel I. Z., Erni R., et al., “Activation of Bimetallic AgCu Foam Electrocatalysts for Ethanol Formation From CO₂ by Selective Cu Oxidation/Reduction,” Nano Energy 68 (2020): 104331. [Google Scholar]

[anie72755-bib-0037] 37. Ma G., Syzgantseva O. A., Huang Y., et al., “A Hydrophobic Cu/Cu₂O Sheet Catalyst for Selective Electroreduction of CO to Ethanol,” Nature Communications 14 (2023): 501. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0038] 38. Wang X., Wang Z., García de Arquer F. P., et al., “Efficient Electrically Powered CO₂‐to‐Ethanol via Suppression of Deoxygenation,” Nature Energy 5 (2020): 478–486. [Google Scholar]

[anie72755-bib-0039] 39. Li Z., Wang L., Wang T., Sun L., and Yang W., “Steering the Dynamics of Reaction Intermediates and Catalyst Surface During Electrochemical Pulsed CO₂ Reduction for Enhanced C₂₊ Selectivity,” Journal of the American Chemical Society 145 (2023): 20655–20664. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0040] 40. Xie Y., Ou P., Wang X., et al., “High Carbon Utilization in CO₂ Reduction to Multi‐Carbon Products in Acidic Media,” Nature Catalysis 5 (2022): 564–570. [Google Scholar]

[anie72755-bib-0041] 41. Chou T., Chang C., Yu H., et al., “Controlling the Oxidation State of the Cu Electrode and Reaction Intermediates for Electrochemical CO₂ Reduction to Ethylene,” Journal of the American Chemical Society 142 (2020): 2857–2867. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0042] 42. Zhu S., Wang Q., Qin X., et al., “Tuning Structural and Compositional Effects in Pd‐Au Nanowires for Highly Selective and Active CO₂ Electrochemical Reduction Reaction,” Advanced Energy Materials 8 (2018): 201802238. [Google Scholar]

[anie72755-bib-0043] 43. Chang X., Vijay S., Zhao Y., Oliveira N. J., Chan K., and Xu B., “Understanding the Complementarities of Surface‐Enhanced Infrared and Raman Spectroscopies in CO Adsorption and Electrochemical Reduction,” Nature Communications 13 (2022): 2625. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0044] 44. Yang Y., He A., Li H., et al., “Operando Constructing Cu/Cu₂O Electrocatalysts for Efficient CO₂ Electroreduction to Ethanol: CO₂‐Assisted Structural Evolution of Octahedral Cu₂O by Operando CV Activation,” ACS Catalysis 12 (2022): 12942–12953. [Google Scholar]

[anie72755-bib-0045] 45. Liu K., Yang C., Wei R., et al., “Unraveling and Tuning the Linear Correlation Between CH₄ and C₂ Production Rates in CO₂ Electroreduction,” Science Bulletin 67 (2022): 1042–1048. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0046] 46. Zhuansun M., Liu Y., Lu R., et al., “Promoting CO₂ Electroreduction to Multi−Carbon Products by Hydrophobicity‐Induced Electro‐Kinetic Retardation,” Angewandte Chemie International Edition 62 (2023): e202309875. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0047] 47. Luna D., Hahn C., Higgins D., Jaffer S. A., Jaramillo T. F., and Sargent E. H., “What Would It Take for Renewably Powered Electrosynthesis to Displace Petrochemical Processes?” Science 364 (2019): 350. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0048] 48. Stocker S., Csányi G., Reuter K., and Margraf J. T., “Machine Learning in Chemical Reaction Space,” Nature Communications 11 (2020): 5505. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0049] 49. Margraf J. T., Jung H., Scheurer C., and Reuter K., “Exploring Catalytic Reaction Networks With Machine Learning,” Nature Catalysis 6 (2023): 112–121. [Google Scholar]

[anie72755-bib-0050] 50. Hafner J., “Ab−Initio Simulations of Materials Using VASP: Density−Functional Theory and Beyond,” Journal of Computational Chemistry 29 (2008): 2044–2078. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0051] 51. Kresse G. and Joubert D., “From Ultrasoft Pseudopotentials to the Projector Augmented‐Wave Method,” Physical Review B 59 (1999): 1758–1775. [Google Scholar]

[anie72755-bib-0052] 52. Mathew K., Kolluru V. S. C., Mula S., Steinmann S. N., and Hennig R. G., “Implicit Self‐Consistent Electrolyte Model in Plane‐Wave Density‐Functional Theory,” Journal of Chemical Physics 151 (2019): 234101. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0053] 53. Nørskov J. K., Rossmeisl J., Logadottir A., and Lindqvist L., “Origin of the Overpotential for Oxygen Reduction at a Fuel‐Cell Cathode,” Journal of Physical Chemistry B 108 (2004): 17886. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0054] 54. Henkelman G., Uberuaga B. P., and Jónsson H., “A Climbing Image Nudged Elastic Band Method for Finding Saddle Points and Minimum Energy Paths,” Journal of Chemical Physics 113 (2000): 9901–9904. [Google Scholar]

[anie72755-bib-0055] 55. Perdew J. P., Burke K., and Ernzerhof M., “Generalized Gradient Approximation Made Simple,” Physical Review Letter 77 (1996): 3865–3868. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0056] 56. Ricardo U.‐O., Builes S., and Calle‐Vallejo F., “Fast Correction of Errors in the DFT‐Calculated Energies of Gaseous Nitrogen‐Containing Species,” ChemCatChem 13 (2021): 2508. [Google Scholar]

[anie72755-bib-0057] 57. Granda‐Marulanda L. P., Rendón‐Calle A., Builes S., Illas F., Koper M. T. M., and Calle‐Vallejo F., “A Semiempirical Method to Detect and Correct DFT‐Based Gas‐Phase Errors and Its Application in Electrocatalysis,” ACS Catalysis 10 (2020): 6900–6907. [Google Scholar]

[anie72755-bib-0058] 58. Wang V., Xu N., Liu J., Tang G., and Geng W.‐T., “VASPKIT: A User‐Friendly Interface Facilitating High‐Throughput Computing and Analysis Using VASP Code,” Computer Physics Communications 267 (2021): 108033. [Google Scholar]

[anie72755-bib-0059] 59. Vojtěch Š., Chun S., Pokorný V., Fulem M., and Růẑiĉka K., “Thermodynamic Study of Acetamides,” Journal of Molecular Liquids 319 (2020): 114019. [Google Scholar]

[anie72755-bib-0060] 60. Wang W., Dai S., Li X., Yang J., Srolovitz D. J., and Zheng Q., “Measurement of the Cleavage Energy of Graphite,” Nature Communications 6 (2015): 7853. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0061] 61. Ricardo U. O., Builes S., Illas F., and Calle‐Vallejo F., “Gas‐Phase Errors in Computational Electrocatalysis: A Review,” EES Catalysis 2 (2024): 157. [Google Scholar]

[anie72755-bib-0062] 62. Peterson A. A., Abild‐Pedersen F., Studt F., Rossmeisl J., and Nørskov J. K., “How Copper Catalyzes the Electroreduction of Carbon Dioxide Into Hydrocarbon Fuels,” Energy & Environmental Science 3 (2010): 1311. [Google Scholar]

[anie72755-bib-0063] 63. Urrego‐Ortiz R., Builes S., and Calle‐Vallejo F., “Impact of Intrinsic Density Functional Theory Errors on the Predictive Power of Nitrogen Cycle Electrocatalysis Models,” ACS Catalysis 12 (2022): 4784–4791. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0064] 64. Lide D. R., CRC Handbook of Chemistry and Physics, 85th ed. (CRC Press, 2004). [Google Scholar]

[anie72755-bib-0065] 65. Chase M. W., Davies C. A., Downey J. R., Frurip D. J., MacDonald R. A., and Syverud A. N., “NIST−JANAF Thermochemical Tables,” Journal of Physical and Chemical Reference Data 14 (1985): 1856, NIST Chemistry WebBook, accessed October 18, https://webbook.nist.gov/chemistry/. [Google Scholar]

[anie72755-bib-0066] 66. Lide D. R., CRC Handbook of Chemistry and Physics, 90th ed. (CRC Press, 2010). [Google Scholar]

[anie72755-bib-0067] 67. Nitopi S., Bertheussen E., and Scott S. B., “Progress and Perspectives of Electrochemical CO₂ Reduction on Copper in Aqueous Electrolyte,” Chemical Reviews 119 (2019): 7610–7672. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0068] 68. Mathew K., Sundararaman R., Letchworth‐Weaver K., Arias T. A., and Hennig R. G., “Implicit Solvation Model for Density‐Functional Study of Nanocrystal Surfaces and Reaction Pathways,” Journal of Chemical Physics 140 (2014): 084106. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0069] 69. Calle‐Vallejo F., Martínez J. I., García‐Lastra J. M., Rossmeisl J., and Koper M. T. M., “Physical and Chemical Nature of the Scaling Relations Between Adsorption Energies of Atoms on Metal Surfaces,” Physical Review Letter 108 (2012): 116103. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0070] 70. Abild‐Pedersen F., Greeley J., Studt F., et al., “Scaling Properties of Adsorption Energies for Hydrogen‐Containing Molecules on Transition‐Metal Surfaces,” Physical Review Letter 99 (2007): 016105. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0071] 71. Zhao Z., Liu S., Zha S., et al., “Theory‐Guided Design of Catalytic Materials Using Scaling Relationships and Reactivity Descriptors,” Nature Reviews Materials 4 (2019): 792–804. [Google Scholar]

[anie72755-bib-0072] 72. Calle‐Vallejo F., Huang M., Henry J. B., Koper M. T. M., and Bandarenka A. S., “Theoretical Design and Experimental Implementation of Ag/Au Electrodes for the Electrochemical Reduction of Nitrate,” Physical Chemistry Chemical Physics 15 (2013): 3196. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0073] 73. Hao W., Alexander B., and Jan R., “Electrochemical Nitric Oxide Reduction on Metal Surfaces,” Angewandte Chemie International Edition 60 (2021): 21966. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0074] 74. Guo C., Fu X., Long J., et al., “Toward Computational Design of Chemical Reactions With Reaction Phase Diagram,” WIREs Computational Molecular Science 11 (2021): e1514. [Google Scholar]

[anie72755-bib-0075] 75. Beverskog B. and Puigdomenech I., “Revised Pourbaix Diagrams for Copper at 25 to 300°C,” Journal of the Electrochemical Society 144 (1997): 3476–3483. [Google Scholar]

[anie72755-bib-0076] 76. Stenlid J. H., Dos Santos E. C., Bagger A., Johansson A. J., Rossmeisl J., and Pettersson L. G. M., “Electrochemical Interface During Corrosion of Copper in Anoxic Sulfide‐Containing Groundwater–A Computational Study,” Journal of Physical Chemistry C 124 (2019): 469–481. [Google Scholar]

[anie72755-bib-0077] 77. Chang X., Wang T., Zhao Z., et al., “Tuning Cu/Cu₂O Interfaces for the Reduction of Carbon Dioxide to Methanol in Aqueous Solutions,” Angewandte Chemie International Edition 57 (2018): 15415–15419. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0078] 78. Liang Z., Zhuang T., Seifitokaldani A., et al., “Copper‐on‐Nitride Enhances the Stable Electrosynthesis of Multicarbon Products From CO₂ ,” Nature Communications 9 (2018): 3828. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0079] 79. Zhou Y., Yao Y., Zhao R., et al., “Stabilization of Cu⁺ via Strong Electronic Interaction for Selective and Stable CO₂ Electroreduction,” Angewandte Chemie International Edition 61 (2022): e202205832. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0080] 80. Kuang S., Xiao T., Chi H., et al., “Acetamide Electrosynthesis From CO₂ and Nitrite in Water,” Angewandte Chemie International Edition 63 (2024): e202316772. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0081] 81. Zhou Y., Che F., Liu M., et al., “Dopant‐induced Electron Localization Drives CO₂ Reduction to C₂ Hydrocarbons,” Nature Chemistry 10 (2018): 974–980. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0082] 82. Jiang K., Sandberg R. B., Akey A. J., et al., “Metal Ion Cycling of Cu Foil for Selective C–C Coupling in Electrochemical CO₂ Reduction,” Nature Catalysis 1 (2018): 111–119. [Google Scholar]

[anie72755-bib-0083] 83. Zhu Q., Sun X., Yang D., et al., “Carbon Dioxide Electroreduction to C₂ Products Over Copper‐Cuprous Oxide Derived From Electrosynthesized Copper Complex,” Nature Communications 10 (2019): 3851. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0084] 84. Ren D., Deng Y., Handoko A. D., Chen C. S., Malkhandi S., and Yeo B. S., “Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts,” ACS Catalysis 5 (2015): 2814–2821. [Google Scholar]

[anie72755-bib-0085] 85. Chen C., Sun X., Lu L., et al., “Efficient Electroreduction of CO₂ to C₂ Products Over B‐Doped Oxide‐Derived Copper,” Green Chemistry 20 (2018): 4579–4583. [Google Scholar]

[anie72755-bib-0086] 86. Handoko A. D., Chan K. W., and Yeo B. S., “–CH₃ Mediated Pathway for the Electroreduction of CO₂ to Ethane and Ethanol on Thick Oxide‐Derived Copper Catalysts at Low Overpotentials,” ACS Energy Letters 2 (2017): 2103–2109. [Google Scholar]

[anie72755-bib-0087] 87. Lee S., Park G., and Lee J., “Importance of Ag‐Cu Biphasic Boundaries for Selective Electrochemical Reduction of CO₂ to Ethanol,” ACS Catalysis 7 (2017): 8594–8604. [Google Scholar]

[anie72755-bib-0088] 88. Wang P., Yang H., Tang C., et al., “Boosting Electrocatalytic CO₂‐to‐Ethanol Production via Asymmetric C–C Coupling,” Nature Communications 13 (2022): 3754. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0089] 89. Li Y. C., Wang Z., Yuan T., et al., “Binding Site Diversity Promotes CO₂ Electroreduction to Ethanol,” Journal of the American Chemical Society 141 (2019): 8584–8591. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0090] 90. Ren D., Ang B. S., and Yeo B. S., “Tuning the Selectivity of Carbon Dioxide Electroreduction Toward Ethanol on Oxide‐derived Cu_xZn Catalysts,” ACS Catalysis 6 (2016): 8239–8247. [Google Scholar]

[anie72755-bib-0091] 91. Song Y., Peng R., Hensley D. K., et al., “High–Selectivity Electrochemical Conversion of CO₂ to Ethanol Using a Copper Nanoparticle/N–Doped Graphene Electrode,” ChemistrySelect 1 (2016): 6055–6061. [Google Scholar]

[anie72755-bib-0092] 92. Han Z., Kortlever R., Chen H., Peters J. C., and Agapie T., “CO₂ Reduction Selective for C_≥2 Products on Polycrystalline Copper With N‐Substituted Pyridinium Additives,” ACS Central Science 3 (2017): 853–859. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0093] 93. Ren D., Gao J., Pan L., et al., “Atomic Layer Deposition of ZnO on CuO Enables Selective and Efficient Electroreduction of Carbon Dioxide to Liquid Fuels,” Angewandte Chemie International Edition 58 (2019): 15036–15040. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0094] 94. Wang X., Wang Z., García de Arquer F. P., et al., “Efficient Electrically Powered CO₂‐to‐Ethanol via Suppression of Deoxygenation,” Nature Energy 5 (2020): 478–486. [Google Scholar]

[anie72755-bib-0095] 95. Gu Z., Shen H., Chen Z., et al., “Efficient Electrocatalytic CO₂ Reduction to C₂₊ Alcohols at Defect‐Site‐Rich Cu Surface,” Joule 5 (2021): 429–440. [Google Scholar]

[anie72755-bib-0096] 96. Xu H., Rebollar D., He H., et al., “Highly Selective Electrocatalytic CO₂ Reduction to Ethanol by Metallic Clusters Dynamically Formed From Atomically Dispersed Copper,” Nature Energy 5 (2020): 623–632. [Google Scholar]

[anie72755-bib-0097] 97. Zhao Z., Huang J., Liao P., and Chen X., “Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal‐Organic Framework With Heterodimetal Dual Sites,” Journal of the American Chemical Society 145 (2023): 26783–26790. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0098] 98. Kuang S., Su Y., and Li M., “Asymmetrical Electrohydrogenation of CO₂ to Ethanol With Copper‐Gold Heterojunctions,”Proceedings of the National Academy of Sciences 120 (2023): e2214175120. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0099] 99. Zhang T., Yuan B., Wang W., He J., and Xiang X., “Tailoring *H Intermediate Coverage on the CuAl₂O₄/CuO Catalyst for Enhanced Electrocatalytic CO₂ Reduction to Ethanol,” Angewandte Chemie International Edition 62 (2023): e202302096. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0100] 100. Kim C., Cho K. M., Park K., et al., “Cu/Cu₂O Interconnected Porous Aerogel Catalyst for Highly Productive Electrosynthesis of Ethanol From CO₂ ,” Advanced Functional Materials 31 (2021): 2102142. [Google Scholar]

[anie72755-bib-0101] 101. Zhuang T., Liang Z., Seifitokaldani A., et al., “Steering Post‐C–C Coupling Selectivity Enables High Efficiency Electroreduction of Carbon Dioxide to Multi‐Carbon Alcohols,” Nature Catalysis 1 (2018): 421–428. [Google Scholar]

[anie72755-bib-0102] 102. Lv C., Zhong L., Liu H., et al., “Selective Electrocatalytic Synthesis of Urea With Nitrate and Carbon Dioxide,” Nature Sustainability 4 (2021): 868–876. [Google Scholar]

[anie72755-bib-0103] 103. Ye L., Liu J., Gao Y., et al., “Highly Oriented MOF Thin Film‐Based Electrocatalytic Device for the Reduction of CO₂ to CO Exhibiting High Faradaic Efficiency,” Journal of Materials Chemistry A 4 (2016): 15320–15326. [Google Scholar]

[anie72755-bib-0104] 104. Han S., Li H., Li T., et al., “Ultralow Overpotential Nitrate Reduction to Ammonia via a Three‐Step Relay Mechanism,” Nature Catalysis 6 (2023): 402–414. [Google Scholar]

[anie72755-bib-0105] 105. Zhong W., Chen Y., Chen P., et al., “Balancing Hydrogen Evolution and Hydrogenation Reaction via Facet Engineering for Efficient Conversion of Nitrate to Ammonia in Actual Wastewater,” Angewandte Chemie International Edition 64 (2025): e202503117. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0106] 106. Zhao H., Liu P., Cheng X., et al., “A Cu‐Cu₂O/Ni₂P Heterostructure for Efficient Tandem Catalysis of Electrosynthesis of Ammonia From Nitrate Reduction Reaction in Neutral Medium,” Advanced Functional Materials 35 (2025): 2425459. [Google Scholar]

[anie72755-bib-0107] 107. Dai Y., Li S., Li X., et al., “Tandem Active Sites in Cu/Mo‐WO₃ Electrocatalysts for Efficient Electrocatalytic Nitrate Reduction to Ammonia,” Advanced Functional Materials 35 (2025): 2420282. [Google Scholar]

[anie72755-bib-0108] 108. Li X., Wang S., Li L., Sun Y., and Xie Y., “Progress and Perspective for In Situ Studies of CO₂ Reduction,” Journal of the American Chemical Society 142 (2020): 9567. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0109] 109. Chou T., Chang C., Yu H., et al., “Controlling the Oxidation State of the Cu Electrode and Reaction Intermediates for Electrochemical CO₂ Reduction to Ethylene,” Journal of the American Chemical Society 142 (2020): 2857–2867. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0110] 110. Shi Y., Ji Y., Long J., et al., “Unveiling Hydrocerussite as an Electrochemically Stable Active Phase for Efficient Carbon Dioxide Electroreduction to Formate,” Nature Communications 11 (2020): 3415. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0111] 111. Sun W., Wang P., Jiang Y., et al., “V‐Doped Cu₂Se Hierarchical Nanotubes Enabling Flow‐cell CO₂ Electroreduction to Ethanol With High Efficiency and Selectivity,” Advanced Materials 34 (2022): 2207691. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0112] 112. Tao Z., Wu Y., Wu Z., Shang B., Rooney C., and Wang H., “Cascade Electrocatalytic Reduction of Carbon Dioxide and Nitrate to Ethylamine,” Journal of Energy Chemistry 65 (2022): 367–370. [Google Scholar]

[anie72755-bib-0113] 113. Wu Y., Jiang Z., Lin Z., Liang Y., and Wang H., “Direct Electrosynthesis of Methylamine From Carbon Dioxide and Nitrate,” Nature Sustainability 4 (2021): 725–730. [Google Scholar]

[anie72755-bib-0114] 114. Chen C., Zhu X., Wen X., et al., “Coupling N₂ and CO₂ in H₂O to Synthesize Urea Under Ambient Conditions,” Nature Chemistry 12 (2020): 717–724. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0115] 115. Li J. and Kornienko N., “Electrochemically Driven C–N Bond Formation From CO₂ and Ammonia at the Triple‐Phase Boundary,” Chemical Science 13 (2022): 3957–3964. [DOI] [PMC free article] [PubMed] [Google Scholar]

[anie72755-bib-0116] 116. Jouny M., Lv J., Cheng T., et al., “Formation of Carbon–Nitrogen Bonds in Carbon Monoxide Electrolysis,” Nature Chemistry 11 (2019): 846–851. [DOI] [PubMed] [Google Scholar]

[anie72755-bib-0117] 117. Huang Y., Yang R., Wang C., et al., “Direct Electrosynthesis of Urea From Carbon Dioxide and Nitric Oxide,” ACS Energy Letters 7 (2022): 284–291. [Google Scholar]

[anie72755-bib-0118] 118. Tong Y., Wang Z., Yang E., et al., “Determination and Correlation of Solubility and Solution Thermodynamics of Ethenzamide in Different Pure Solvents,” Fluid Phase Equilibria 427 (2016): 549–556. [Google Scholar]

[anie72755-bib-0119] 119. Xu D., Tan B., Shi H., Hao M., Guan Y., and Liu J., “Measurement and Correlation of Liquid‐Liquid Equilibrium Data for the Extraction of Glycerol Carbonate From Glycerol Using Ethyl Acetate and 2‐Butanone + Benzene Mixture,” Journal of Chemical & Engineering Data 69 (2024): 1939–1947. [Google Scholar]

[anie72755-bib-0120] 120. Zhang X., Hao X., Jian C., et al., “Experimental Isobaric Vapour‐Liquid Equilibrium Data for Binary Systems of {Sec‐Butyl Acetate (SBAC)+Acetamide} and {Sec‐butyl Alcohol (SBA)+Acetamide} and the Ternary System of (SBAC+SBA+Acetamide) at 101.3 kPa,” Journal of Chemical Thermodynamics 144 (2020): 106087. [Google Scholar]

[anie72755-bib-0121] 121. Mo W., Tan X., and Ong W., “Prospective Life Cycle Assessment Bridging Biochemical, Thermochemical, and Electrochemical CO₂ Reduction Toward Sustainable Ethanol Synthesis,” ACS Sustainable Chemistry & Engineering 11 (2023): 5782–5799. [Google Scholar]

[anie72755-bib-0122] 122. Zhao B., Chen F., Wang M., et al., “Economically Viable Electrocatalytic Ethylene Production With High Yield and Selectivity,” Nature Sustainability 6 (2023): 827–837. [Google Scholar]

[anie72755-bib-0123] 123. Jouny M., Luc W., and Jiao F., “General Techno‐Economic Analysis of CO₂ Electrolysis Systems,” Industrial & Engineering Chemistry Research 57 (2018): 2165–2177. [Google Scholar]

[anie72755-bib-0124] 124. Lum Y., Huang J. E., Wang Z., et al., “Tuning OH Binding Energy Enables Selective Electrochemical Oxidation of Ethylene to Ethylene Glycol,” Nature Catalysis 3 (2020): 14–22. [Google Scholar]

[anie72755-bib-0125] 125. Shin H., Hansen K. U., and Jiao F., “Techno‐Economic Assessment of Low‐Temperature Carbon Dioxide Electrolysis,” Nature Sustainability 4 (2021): 911–919. [Google Scholar]

[anie72755-bib-0126] 126. Guo C., Guo Y., Shi Y., et al., “Electrocatalytic Reduction of CO₂ to Ethanol at Close to Theoretical Potential via Engineering Abundant Electron‐Donating Cu^δ+ Species,” Angewandte Chemie International Edition 61 (2022): e2022059. [DOI] [PubMed] [Google Scholar]

PERMALINK

Nitrate‐Stabilized Cuδ+ Sites Promote Selective CO2 Electroreduction to Ethanol for Tandem Acetamide Electrosynthesis

Chengying Guo

Rong Yang

Nannan Meng

Jiang Shao

Minghao Guo

Hongjiao Li

Ang Cao

Bin Zhang

Yifu Yu

ABSTRACT

1. Introduction

SCHEME 1.

2. Results and Discussion

2.1. Theoretical Simulation‐Directed Catalyst Design

FIGURE 1.

2.2. Characterizations of Dynamically Stable Cu2O1−x Species With NO3 − Adsorption

FIGURE 2.

2.3. Electrocatalytic CO2RR to Ethanol Over Dynamically Stable Cu2O1−x Species With NO3 − Adsorption

FIGURE 3.

2.4. Studies on the Mechanism of the Selective CO2RR to Ethanol

FIGURE 4.

2.5. Electrosynthesis of Acetamide via Cathode−Anode Tandem System From CO2 and NO3 −

FIGURE 5.

2.6. Studies on the Electrooxidation Mechanism of Ethanol‒Ammonia Coupling

FIGURE 6.

3. Conclusion

Author Contributions

Conflicts of Interest

Supporting information

Acknowledgments

Data Availability Statement

References

Associated Data

Supplementary Materials

Data Availability Statement

ACTIONS

PERMALINK

RESOURCES

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Nitrate‐Stabilized Cu^δ+ Sites Promote Selective CO₂ Electroreduction to Ethanol for Tandem Acetamide Electrosynthesis

2.2. Characterizations of Dynamically Stable Cu₂O_1−x Species With NO₃ ⁻ Adsorption

2.3. Electrocatalytic CO₂RR to Ethanol Over Dynamically Stable Cu₂O_1−x Species With NO₃ ⁻ Adsorption

2.4. Studies on the Mechanism of the Selective CO₂RR to Ethanol

2.5. Electrosynthesis of Acetamide via Cathode−Anode Tandem System From CO₂ and NO₃ ⁻