Unlocking asymmetric C-C coupling pathways on commercial Cu catalysts via Cu (100) grain boundaries for efficient and durable CO electroreduction

doi:10.1016/S1872-2067(25)64753-X

Abstract

Abstract:

Copper (Cu)-based catalysts show significant potential for producing high value-added C₂₊ products in electrocatalytic CO₂/CO reduction reactions (CO₍₂₎RR). However, the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site, especially under similar mass transport conditions. Herein, three typical and commercial Cu-based catalysts (Cu, CuO, and Cu₂O) are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer. Notably, only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction, thus achieving the highest FE of 86.7% for C₂₊ products at a current density of 500 mA cm^-2 and maintaining a stable electrolysis over 110 h at a current of 200 mA cm^-2. The influence of chemical valence state of Cu, electrochemical surface area, and local pH were firstly investigated and ruled out for the significant FE differences. Finally, based on the structure analysis from high resolution transmission electron microscope, OH^- adsorption, in situ infrared spectroscopy and density functional theory calculations, it is suggested that the asymmetric C-C coupling (via *CHO and *CO) is the most probable reaction pathway for forming C₂₊ products, with Cu (100)-dominant grain boundaries (GBs) being the most favorable active sites. These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.

Key words: CO electroreduction, Asymmetric C-C coupling, Grain boundaries, Cu-based catalyst, C₂₊ product

Xianlong Lu, Lili Wang, Xueyang Zhao, Binbin Pan, Zhendong Li, Xiangfei Du, Shihan Zhang, Fan Dong, Bangwei Deng. Unlocking asymmetric C-C coupling pathways on commercial Cu catalysts via Cu (100) grain boundaries for efficient and durable CO electroreduction[J]. Chinese Journal of Catalysis, 2025, 76: 198-209.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64753-X

https://www.cjcatal.com/EN/Y2025/V76/I9/198

Figures/Tables 4

Fig. 1. CORR performance in alkaline MEA electrolyzers. FE and current density curves of Cu (a), CuO (b), and Cu2O (c) in 1 mol L-1 KOH electrolyte. (d) Corresponding FE(C2+/H2) ratio at various current densities. (e) Partial current density of C2+ products as a function of current density for Cu, CuO, and Cu2O. (f) Full cell voltage at various current densities. (g) Comparative analysis of C2+ partial current density and FE (C2+) on Cu and the reported advanced catalysts. (h) FE and full cell voltage during stability assessment of Cu at a current density of 200 mA cm-2.

Fig. 2. XRD physicochemical characterizations of catalysts. XRD patterns (a) and Cu LMM spectra (b) of Cu, CuO, and Cu2O catalysts after reaction. (c) The corresponding fitting results of Cu LMM, representing the proportions of Cu0, Cu+, and Cu2+ in the three catalysts. In situ Raman spectroscopy obtained during chronopotentiometry in a current range from OCP to -50 mA for Cu (d), CuO (e) and Cu2O (f), under CORR conditions. (g) Cdl of Cu, Cu2O, and CuO calculated from CV with various scan rates. (h) Evaluation of local pH via CV measurements in Ar-saturated 1 mol L-1 KOH solution. The onset oxidation potential of Cu, CuO, and Cu2O is 0.47, 0.47, and 0.46 V, respectively. (i) The corresponding calculated local pH change (ΔpH) based on the pH of bulk electrolyte.

Fig. 3. Structural and chemical characterizations of the catalyst. HRTEM images (a-c) and corresponding SAED patterns (d-f) of Cu, CuO, and Cu2O after constant electrolysis at 200 mA cm-2 for 1 h, respectively. The inset images are the fitting results of SEAD based on the CrysTBox. (g) CV curves of OH- adsorption experiments for Cu, CuO and Cu2O. Corresponding fitted OH- adsorption peaks (h) and proportions of exposed surface facets (i) on Cu, CuO, and Cu2O. The CV curves were measured in Ar-saturated 1 mol L-1 KOH solution with a scanning rate of 100 mV s-1. The CV curves represent from four consecutive measurements.

Fig. 4. In-situ ATR SEIRAS characterizations and DFT calculations. In-situ ATR-SEIRAS spectra obtained during chronopotentiometry in a potential window from OCP to -1.5 V vs. RHE for Cu (a), CuO (b) and Cu2O (c) under CORR conditions. (d) Potential dependence of the ratio of *CObridge/*COatop obtained for Cu, CuO and Cu2O catalysts. Adsorption geometries of *CObridge and *COatop (e), free energy of *CObridge and *COatop adsorption (f), and geometries of *CO and *CHO adsorption (g) on Cu (100)/Cu (100), Cu (100)/Cu (111), and Cu (111)/Cu (111) interfaces. (h) Free energy diagram for the energetics of *CO and *CHO forming *OCCHO on three interfaces. Orange, red, gray, and white spheres represent Cu, O, C, and H, respectively.

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