Ndlangamandla Simphiwe L, Radhakrishnan Shankara G
Department of Chemistry, University of Pretoria, Pretoria, 0002, South Africa.
ChemistryOpen. 2025 Aug;14(8):e202400488. doi: 10.1002/open.202400488. Epub 2025 Jun 16.
Electrochemical reduction of CO (ECR) on transition metal-containing porphyrin systems often leads to carbon monoxide. Herein, a modified zero-gap polymer electrolyte membrane water electrolyzer is used with 5,10,15,20-tetraphenyl-21H,23H-porphine copper (II) as a cathodic electrocatalyst for ECR in 0.1 M NaOH as an aqueous catholyte. The setup yields CO, CH, and CH along with hydrogen evolution, with selectivity toward CH formation as indicated by gas chromatographic analysis. Although hydrogen formation is predominant, the system yields a high average current density of 146.94 mA cm and a Tafel slope of ≈226 mV dec in concurrence. The cyclic voltammetric experiments show the stepwise formation of Cu (II) → Cu (I) → Cu (0) based on the potentials referenced against the reversible hydrogen electrode, which could have been the driving factor for the ECR.
在含过渡金属的卟啉体系上进行的一氧化碳电化学还原（ECR）通常会生成一氧化碳。在此，使用了一种改进的零间隙聚合物电解质膜水电解槽，以5,10,15,20-四苯基-21H,23H-卟吩铜（II）作为阴极电催化剂，在0.1 M NaOH作为水性阴极电解液的条件下进行ECR。该装置除了析氢外，还生成了CO、CH和CH，气相色谱分析表明对CH形成具有选择性。尽管析氢占主导，但该系统同时产生了146.94 mA cm的高平均电流密度和约226 mV dec的塔菲尔斜率。循环伏安实验表明，基于相对于可逆氢电极的电位，Cu（II）→Cu（I）→Cu（0）逐步形成，这可能是ECR的驱动因素。
