Understanding the C−C coupling mechanism in electrochemical CO reduction at low CO coverage: Dynamic change in site preference matters

doi:10.1016/S1872-2067(24)60180-4

Abstract

Abstract:

A thoroughly mechanistic understanding of the electrochemical CO reduction reaction (eCORR) at the interface is significant for guiding the design of high-performance electrocatalysts. However, unintentionally ignored factors or unreasonable settings during mechanism simulations will result in false positive results between theory and experiment. Herein, we computationally identified the dynamic site preference change of CO adsorption with potentials on Cu(100), which was a previously unnoticed factor but significant to potential-dependent mechanistic studies. Combined with the different lateral interactions among adsorbates, we proposed a new C−C coupling mechanism on Cu(100), better explaining the product distribution at different potentials in experimental eCORR. At low potentials (from −0.4 to −0.6 V_RHE), the CO forms dominant adsorption on the bridge site, which couples with another attractively aggregated CO to form a C−C bond. At medium potentials (from −0.6 to −0.8 V_RHE), the hollow-bound CO becomes dominant but tends to isolate with another adsorbate due to the repulsion, thereby blocking the coupling process. At high potentials (above −0.8 V_RHE), the CHO intermediate is produced from the electroreduction of hollow-CO and favors the attraction with another bridge-CO to trigger C−C coupling, making CHO the major common intermediate for C−C bond formation and methane production. We anticipate that our computationally identified dynamic change in site preference of adsorbates with potentials will bring new opportunities for a better understanding of the potential-dependent electrochemical processes.

Key words: Electrochemical CO reduction reaction, Low CO coverage, Dynamic site-preference, Potential-dependent C-C coupling, Constant-potential density functional theory

Zhe Chen, Tao Wang. Understanding the C−C coupling mechanism in electrochemical CO reduction at low CO coverage: Dynamic change in site preference matters[J]. Chinese Journal of Catalysis, 2025, 69: 193-202.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60180-4

https://www.cjcatal.com/EN/Y2025/V69/I2/193

Figures/Tables 5

Fig. 1. Calculated potential-dependent free energy of three CO adsorption configurations (A) and the corresponding potential-dependent distributions (B). (C) Local density of states of a surface Cu atom at different potentials (vs. RHE) as well as the molecular orbital of isolated CO. (D) Planar-average charge-density for COb and COh as well as their difference charge density at different potentials (vs. RHE), where the isosurface value is set to be 0.005 e ??3. Yellow and cyan regions represent charge accumulation and depletion.

Scheme 1. (A) Experimental mass fragments of gaseous products of CO reduction on Cu(100) measured with online electrochemical mass spectrometry at pH = 7. The data are taken from Ref. [15]. (B) Schematic diagrams of lateral attraction and repulsion between adsorbates. (C) Schematic illustrations of aggregated 2CO and isolated 2CO at low surface coverage with bridge and hollow sites.

Fig. 2. Calculated adsorption free energy of two aggregated and isolated CO with potentials (A) and the corresponding potential-dependent distributions (B). (C) Calculated potential-dependent kinetic process for CO?CO coupling. Snapshots of the corresponding structures are also given, where the solvent water molecules are hidden for viewing convenience. (D) Calculated potential-dependent length and ICOHP of C?C bond. (E) Free energy pathway of *OCCO electroreduction to C2H4 at ?0.4 VRHE.

Fig. 3. (A) Calculated free energy pathway of CO electroreduction at ?0.8 VRHE. (B) Calculated potential-dependent adsorption free energy of CHO (COH) intermediates with adsorbed CO. (C) Calculated potential-dependent distributions of reduction intermediates with adsorbed CO, where M+COb is independent of M+COh. Calculated kinetic process for CHO-CO coupling (D) and CH2-CO coupling (E). Snapshots of the corresponding structures (top view) are also given, where the solvent water molecules are hidden for viewing convenience.

Fig. 4. Schematic diagram of potential-dependent eCORR mechanisms at low CO coverage.

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