Electrochemical Reduction of CO2 via Single-Atom Catalysts Supported on α-In2Se3

In this work, the electrochemical CO2 reductionreaction (CO2RR) over transition metal and & alpha;-In2Se3 monolayer catalysts was investigated by densityfunctional theory (DFT) and an effective screening medium method-referenceinteraction site model (ESM-RISM). On the basis of the scaling relationshipbetween the adsorption free energies of intermediates, we constructedthe relationships between oxygen-bound intermediates with *O and carbon-boundintermediates with *CHO. The calculation results indicate that *OCHOintermediates are more favorable for the first hydrogenation of CO2 on M@In2Se3 catalysts; thus, the adsorptionenergy of oxygen-bound species determines the catalytic performanceof M@In2Se3. The Co@In2Se3 & DARR;-C was predicted to be the most promising catalyst with alow limiting potential of -0.385 V as determined by the computationalhydrogen electrode method. Constant potential calculations also demonstratethat the M@In2Se3 catalysts hold great potentialfor highly efficient CO2RR. This work provides a fundamentalunderstanding for the rational design of ferroelectric single-atomcatalysts for the purpose of highly efficient electrocatalytic CO2 reduction.

Automated summary

The electrochemical CO2 reduction reaction (CO2RR) over transition metal and α-In2Se3 monolayer catalysts was investigated using density functional theory (DFT) and an effective screening medium method-reference interaction site model (ESM-RISM). Relationships between oxygen-bound intermediates with *O and carbon-bound intermediates with *CHO were constructed based on scaling relationships between the adsorption free energies of intermediates. The results indicate that *OCHO intermediates are more favorable for the first hydrogenation of CO2 on M@In2Se3 catalysts, and the adsorption energy of oxygen-bound species determines the catalytic performance of M@In2Se3. The Co@In2Se3 catalyst was predicted to be the most promising catalyst with a low limiting potential of -0.385 V, and the M@In2Se3 catalysts hold great potential for highly efficient CO2RR. This work provides a fundamental understanding for the rational design of ferroelectric single-atom catalysts for highly efficient electrocatalytic CO2 reduction.