Electrochemical Reduction of Carbon Dioxide to Methane at Transition Metal-Doped 1T′-MX2 Monolayers

Developing highly efficient catalysts for the electrochemicalCO(2) reduction reaction (CO2RR) to valuable chemicalsthrough a multi-electron reaction pathway remains a challenge, whichusually faces the drawbacks of high overpotential and low selectivity.Here, we designed 1T & PRIME;-MoSe2, -WS2, and-WSe2 (denoted as TM@MX2) catalysts doped with75 kinds of transition metal (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn,Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, and Au) andinvestigated their CO2RR activity via first-principlesscreening. In our screening strategy, the stability, CO2 adsorption, activity, and selectivity were adopted for the indicators.Among the considered candidates, Ru@WS2 was selected asthe optimal catalyst for deep CO2 reduction to methanewith the limiting potential of -0.47 V. Particularly, we foundthat the introductions of transition metals generate completely differentproducts from pristine VIB transition metal dichalcogenides duringCO(2)RR. In addition, most TM@MX2 catalysts favorto form HCOOH whereas Ru@WS2, Mn@WS2, Cr@WS2, and Au@WSe2 prefer to generate CH4 as the final product. The present work will promote the explorationsof VIB transition metal dichalcogenides in the area of reducing CO2 to CH4.

Automated summary

In this study, a MoSe2 catalyst doped with various transition metals was designed and screened. Ru@WS2 was found to be the best catalyst for the reduction of CO2 to methane. Additionally, the introduction of transition metals in VIB transition metal dichalcogenides was found to generate different products during CO(2) reduction. This study is of great significance for the exploration of reducing CO2 to methane.