Exfoliated 2D Layered and Nonlayered Metal Phosphorous Trichalcogenides Nanosheets as Promising Electrocatalysts for CO2 Reduction.

Two‐dimensional (2D) materials catalysts provide an atomic‐scale view on a fascinating arena for understanding the mechanism of electrocatalytic carbon dioxide reduction (CO2 ECR). Here, we successfully exfoliated both layered and nonlayered ultra‐thin metal phosphorous trichalcogenides (MPCh3) nanosheets via wet grinding exfoliation (WGE), and systematically investigated the mechanism of MPCh3 as catalysts for CO2 ECR. Unlike the layered CoPS3 and NiPS3 nanosheets, the active Sn atoms tend to be exposed on the surfaces of nonlayered SnPS3 nanosheets. Correspondingly, the nonlayered SnPS3 nanosheets exhibit clearly improved catalytic activity, showing formic acid selectivity up to 31.6 % with −7.51 mA cm−2 at −0.65 V vs. RHE. The enhanced catalytic performance can be attributed to the formation of HCOO* via the first proton‐electron pair addition on the SnPS3 surface. These results provide a new avenue to understand the novel CO2 ECR mechanism of Sn‐based and MPCh3‐based catalysts. [ABSTRACT FROM AUTHOR]