通过局部环境优化实现铜纳米团簇高效二氧化碳电还原制甲烷OA

In electrocatalytic CO2 reduction reaction(CO2 RR),modulating the catalyst layer structure is an effective strategy for optimizing the local CO2 concentration and enhancing catalytic performance.This study synthesized an atomically precise Cu4 nanocluster([Cu4(PPh3)4(4-EBA)3]PF6)featuring a tetrahedral copper core and investigated the influence of catalyst layer fabrication methods on CO2 RR performance.By optimizing the drop-casting,hand-painting,and spray-coating techniques,it was found that the catalyst layer prepared by drop-casting was thin and dense,exhibiting the largest double-layer capacitance(Cdl=0.951 mF/cm2),which indicates a higher electrochemical active area conducive to CH4 generation at high current densities.After optimizing the feed concentration and flow rate,the system achieved a Faradaic efficiency of 61%for CH4 at a current density of 400 mA/cm2.The high activity of the drop-cast catalyst electrode may be attributed to two factors:the thin catalyst layer shortens the transport pathways for electrons and protons,while the dense structure confers high hydrophobicity,effectively suppressing the hydrogen evolution reaction.This work provides new insights into the design of efficient copper nanocluster catalysts and the optimization of catalyst layers.