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

Developing highly efficient catalysts for the electrochemical CO 2 reduction reaction (CO 2 RR) to valuable chemicals through a multi-electron reaction pathway remains a challenge, which usually faces the drawbacks of high overpotential and low selectivity. Here, we designed 1T′-MoSe 2, -WS 2, and -WSe 2 (denoted as TM@MX 2 ) catalysts doped with 75 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) and investigated their CO 2 RR activity via first-principles screening. In our screening strategy, the stability, CO 2 adsorption, activity, and selectivity were adopted for the indicators. Among the considered candidates, Ru@WS 2 was selected as the optimal catalyst for deep CO 2 reduction to methane with the limiting potential of −0.47 V. Particularly, we found that the introductions of transition metals generate completely different products from pristine VIB transition metal dichalcogenides during CO 2 RR. In addition, most TM@MX 2 catalysts favor to form HCOOH whereas Ru@WS 2, Mn@WS 2, Cr@WS 2, and Au@WSe 2 prefer to generate CH 4 as the final product. The present work will promote the explorations of VIB transition metal dichalcogenides in the area of reducing CO 2 to CH 4 .