Modulating local environment for electrocatalytic CO2reduction to alcohol

The fundamental drivers for the selective CO2electroreduction reaction (CO2RR) to alcohol (e.g. C2H5OH) or alkene (e.g. C2H4) still remain unexplored. Previous studies mainly focus on catalyst engineering to enhance electrocatalytic performance, while the selectivity to alcohol has reached a bottleneck. Here, we modulate local environment to reveal the contribution of *CO and *H reaction intermediates in the selectivity of CO2to alcohol/alkene on Cu electrocatalyst. Through modifications on local CO2concentration, varied *CO/*H coverage ratios can be achieved. Based on the reaction kinetics analysis, we find that there is a direct connection between local CO2concentration and interfacial *CO and *H coverage, which finally affects the selectivity of CO2to alcohol or alkene. To verify this principle, polyvinylidene fluoride (PVDF), a hydrophobic binder, were selected and introduced into the catalyst surface for further enhancement of interfacial *CO/*H coverage. With PVDF decoration, alcohol/alkene ratio increased from 0.69 to 1.35. The Faradic Efficiency of alcohol is up to 37.5 % under a high current density of 800 mA cm–2(a partial current density of 300 mA cm–2), surpassing most reported Cu-based materials. Our findings provide a fundamental guidance for CO2RR to alcohol under an industrial-level current density.