Efficient screening and influencing effect of superior catalysts among TM@Janus WSSe for CO2RR to various C1 products

Abstract

The electrochemical reduction of carbon dioxide (CO₂RR) can efficiently convert CO₂ into high-value products and develop renewable energy resources, in which the catalysts play vital role to enhance the efficiency. A variety of SACs by anchoring 28 transition metal (TM) atoms on Se-monovacant Janus WSSe monolayer (TM@J-WSSe) are designed. An efficient "four-step" screening scheme is proposed to select potential CO₂RR catalysts. The optimal reaction pathways toward CO, HCOOH, CH₃OH and CH₄ are picked out from all possible pathways, and the most potential catalysts are (Os, Cu, Mn, Cr)@J-WSSe with limiting potentials of -0.34 V, -0.39 V, -0.54 V and -0.41 V, respectively, under implicit solvation model. The Faraday efficiency values of four catalytic products are 99.91%, 95.75 %, 100 % and 99.07 %, respectively. The Cr@J-WSSe exhibits a dynamic cyclic behavior compared with (Os, Cu, Mn)@J-WSSe by holding the initial and final TM active site. Moreover, different constant electrode potentials do not change the potential determining step (PDS) of Cr@J-WSSe, although slightly alter the U_L values. The catalytic mechanism is expounded by electronic properties of Cr@J-WSSe. The electron transfers along the route of moiety 1→2→3, where moiety 2 acts as an intermediary transmitter when the electrons are transferred from electron reservoir to receiver.

This work facilitates the systematic understanding of the catalyst design and activity regulation, moreover, it paves an efficient way for experimental preparations.