Neighboring Ni-Cu dual single-atom sites regulate the local environment of interfacial water for promoting CO2 electroreduction kinetics in CO2-to-CO conversion

doi:10.1016/S1872-2067(26)65092-9

Abstract

Abstract:

We develop a Ni-Cu dual single-atom catalyst (DSAC) as a model catalyst to investigate the neighboring synergy in dual single-atom sites for promoting the electrocatalytic carbon dioxide reduction reaction (ECO₂RR) kinetics. Through detailed electrochemical tests, in situ spectroscopic observations and theoretical calculations, we found that during ECO₂RR, the neighboring Ni-Cu dual single-atom sites synergistically weaken the rigidity of the hydrogen-bond networks of interfacial water and optimize the spatial configuration of water molecules surrounding the Ni-Cu dual single-atom sites, which increases the proportion of easily dissociated water species in the interfacial water, thus accelerating the CO₂ protonation kinetics during the conversion of CO₂ to CO. As a result, Ni-Cu DSAC exhibits a 1.5-fold increase and a 15-fold increase in ECO₂RR activity compared to Ni SAC and Cu SAC, respectively. In flow cell electrolyzer, Ni-Cu DSAC achieves almost 100% Faradaic efficiency for CO production (FE_CO) from applied current density of 50 to 400 mA cm⁻², with the optimal full-cell energy efficiency of 61.1% for CO production, reflecting the excellent catalytic performance of neighboring Ni-Cu dual single-atom sites for selective conversion of CO₂ to CO. Benefiting from the efficient suppression of carbonates formation in acidic media, Ni-Cu DSAC achieves an outstanding single-pass carbon efficiency of 67.3% for CO₂-to-CO conversion at 200 mA cm⁻². Additionally, Ni-Cu DSAC also exhibits excellent long-term stability, with less than 10% decay of FE_CO throughout a 170-h continuous electrolysis in strong acid (pH = 1, j = 200 mA cm⁻²).

Key words: CO₂ electroreduction, Neighboring synergistic effect, Microenvironment regulation, Optimized CO₂ protonation kinetics, Industrial-level current densities

Qi Hao, Qi Tang, Junxiu Wu, Kai Liu, Jun Lu, Tianpin Wu. Neighboring Ni-Cu dual single-atom sites regulate the local environment of interfacial water for promoting CO₂ electroreduction kinetics in CO₂-to-CO conversion[J]. Chinese Journal of Catalysis, 2026, 87: 47-58.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65092-9

https://www.cjcatal.com/EN/Y2026/V87/I8/47

Figures/Tables 5

Fig. 1. (a) XRD patterns of Cl-Ni1-C, Cl-Cu1-C, and Cl-Ni1Cu1-C. (b) EPR spectra of Cl-Ni1-C, Cl-Cu1-C, and Cl-Ni1Cu1-C. (c) Raman spectra of Cl-Ni1-C, Cl-Cu1-C, and Cl-Ni1Cu1-C. (d) Low-resolution HAADF-STEM image of Cl-Ni1Cu1-C. (e,f) High-resolution HAADF-STEM images of Cl-Ni1Cu1-C. (g) The 3D fitting maps of dual single-atom sites in Cl-Ni1Cu1-C based on Area 1 and Area 2. (h) Atomic distance statistics based on Figs. 1(e) and Figs. 1(f). Low-resolution HAADF-STEM image (i) and the corresponding EDS mapping (j) of Cl-Ni1Cu1-C.

Fig. 2. (a) Ni K-edge XANES spectra of standard references (Ni foil, NiO and NiPc), Cl-Ni1-C and Cl-Ni1Cu1-C. (b) Ni K-edge FT-EXAFS spectra of standard references (Ni foil, NiO and NiPc), Cl-Ni1-C and Cl-Ni1Cu1-C. (c) Ni K-edge experimental and fiited FT-EXAFS spectra of standard references (Ni foil, NiO and NiPc), Cl-Ni1-C and Cl-Ni1Cu1-C. (d) Cu K-edge XANES spectra of standard references (Cu foil, CuO and CuPc,), Cl-Cu1-C and Cl-Ni1Cu1-C. (e) Cu K-edge FT-EXAFS spectra of standard references (Cu foil, CuO and CuPc,), Cl-Cu1-C and Cl-Ni1Cu1-C. (f) Cu K-edge experimental and fiited FT-EXAFS spectra of standard references (Cu foil, CuO and CuPc,), Cl-Cu1-C and Cl-Ni1Cu1-C. (g,h) Ni K-edge wavelet transform spectra of Cl-Ni1-C (g) and Cl-Ni1Cu1-C (h). (i,j) Cu K-edge wavelet transform spectra of Cl-Cu1-C (i) and Cl-Ni1Cu1-C (j).

Fig. 3. (a) LSV curves of Cl-Cu1-C, Cl-Ni1-C, and Cl-Ni1Cu1-C under CO2 atmosphere. Scan rate, 10 mV s−1. (b) FECOs of Cl-Cu1-C, Cl-Ni1-C, and Cl-Ni1Cu1-C under different potentials. (c) jCOs of Cl-Cu1-C, Cl-Ni1-C, and Cl-Ni1Cu1-C under different potentials. (d) The recorded Ecells for ECO2RR with using Cl-Ni1Cu1-C as the electrocatalyst in flow cell electrolyzers. (e) FECOs at different current densities (f) SPCE comparisons of Cl-Ni1Cu1-C with other recently reported electrocatalysts [8,38-46]. (g) Long-term stability test of Cl-Ni1Cu1-C in strong acid (j = 200 mA cm−2).

Fig. 4. The potential-dependent IR spectra on Cl-Ni1Cu1-C (a), Cl-Ni1-C (b), and Cl-Cu1-C (c) during ECO2RR. The fitted bands of potential-dependent O-H stretching vibrations on Cl-Ni1Cu1-C (d), Cl-Ni1-C (e), and Cl-Cu1-C (f) during ECO2RR. The normalized peak area of 4-HB water and 2-HB water on Cl-Ni1Cu1-C (g), Cl-Ni1-C (h), and Cl-Cu1-C (i) during ECO2RR under different potentials.

Fig. 5. AIMD simulations of the interactions between the interfacial water and single-atom Ni site (a), single-atom Cu site (b), and Ni-Cu dual single-atom sites (c). (d) The adsorption energy of water molecule on various atomic sites. (e) The calculated free energies for CO2-to-CO conversion on various atomic sites. (f) The calculated free energies for HER-Volmer step on various atomic sites. The gray, yellow, blue, cyan, white, and red spheres represent C, Ni, Cu, Cl, H and O atoms, respectively.

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Neighboring Ni-Cu dual single-atom sites regulate the local environment of interfacial water for promoting CO₂ electroreduction kinetics in CO₂-to-CO conversion

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