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In single-atom catalysts (SACs), the single atoms are often exposed as protrusions above the substrate. The solvent molecules in the electrocatalytic environment can interact or even bind to these coordination-unsaturated single atoms and thus influence the reaction process, but this has not been studied in depth. In this work, we systematically investigate the thermodynamics of CO2 reduction reaction (CO2RR) to CO over MoS2-supported single metal atom catalysts (TM@MoS2, TM = transition metal) under vacuum and explicit solvent environments using density functional theory. In addition, the ab initio molecular dynamics results show that explicit H2O molecules can coordinate to the TM site and undergo competitive adsorption with the CO2RR intermediates, which significantly affects the energy and conformation of the CO2RR pathway. Electronic structure analysis reveals that the occupying H2O molecules change the electronic state of single atom and further influence the adsorption strength of different CO2RR intermediates. Our work shows that water molecules can not only act as ligands to influence the electronic state of TM, but also affect the energy and conformation of CO2RR intermediates, which highlights the important role of occupying H2O molecules at the single-atom sites in CO2RR and provides useful insights for the design of SACs for efficient CO2RR.
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