“Beyond catalyst” factors influencing the performance of Cu-based CO₂ electroreduction were investigated based on rigorous microkinetic analysis under industrially relevant conditions. Our experimental results indicated that the activity and selectivity of Cu-based CO₂ electroreduction were not unaffected by electrolyte pH changes but were significantly influenced by operating conditions including pressure and temperature. Analyzing the kinetic data concerning CO₂ partial pressure (P_CO2) and operating temperature revealed that higher P_CO2 (≥25 kPa) or higher reaction temperature (≤333 K) favored CO formation, coinciding with a reduction of the C₂₊ and formate pathways. Product distribution control at 333 K was achieved by engineering the structure of the Cu gas-diffusion electrode (GDE), where CO was exclusively produced on bare Cu, and the faradic efficiency of C₂₊ was enhanced by introducing an optimized Nafion ionomer content in the catalyst layer, likely ascribable to the modulation of diffusion coefficients of reactants (e.g., CO₂ and H₂O) and key intermediates (e.g., CO).

基于工业相关条件下严格的微动力学分析，研究了影响铜基 CO ₂ 电还原性能的“催化剂之外”因素。我们的实验结果表明，铜基CO ₂ 电还原的活性和选择性并非不受电解质pH变化的影响，而是受到压力和温度等操作条件的显着影响。分析 CO ₂ 分压 (P _CO2 ) 和操作温度的动力学数据表明，较高的 P _CO2 (≥25 kPa) 或较高的反应温度 (≤ 333 K) 有利于 CO 的形成，与 C ₂₊ 和甲酸盐途径的减少同时发生。通过设计铜气体扩散电极（GDE）的结构实现了 333 K 的产物分布控制，其中 CO 完全在裸铜上产生，并且通过引入催化剂层中 Nafion 离聚物含量的优化，可能归因于反应物（例如 CO ₂ 和 H ₂ O）和关键中间体（例如 CO）扩散系数的调节。