Theoretical Investigation of Graphene Supported Sn–M (M = Fe, Co, Ni, Cu, Zn) Dual-Atom Catalysts for CO₂ Hydrogenation to HCOOH

Abstract

This work selects a series of transition metals (Fe, Co, Ni, Cu, and Zn) and Sn metal to construct a series of Sn−M dual-atom catalysts (SnMN 6 /G). Formation energy calculations are conducted to evaluate the stability of the studied catalyst. The calculated results demonstrate that SnMN 6 /G (M = Fe, Co, Ni, Cu, Zn) dual-atom catalysts exhibit high structural stability. From the calculated electrostatic potential and Fukui(−) index, it is determined that the Sn atom is the main reaction site for CO 2 hydrogenation. Based on the analysis, the optimal path of HCOOH synthesis is CO 2 * → HCOO* → HCOOH* on SnMN 6 /G. In addition, the rate-determining step of the reaction CO 2 → HCOOH is CO 2 * → HCOO* on all SnMN 6 /G. Furthermore, the catalytic activity of SnMN 6 /G is ranked in the following order: SnZnN 6 /G > SnNiN 6 /G > SnCoN 6 /G > SnCuN 6 /G > SnFeN 6 /G. Moreover, the activity origin of the catalyst is explored through Mulliken charge analysis, which SnZnN 6 /G exhibits stronger charge fluctuation during the reaction process, which may be the source of its high activity. This work clarifies that SnZnN 6 /G is a highly active dual-atom catalyst for HCOOH synthesis.

A synergic investigation of experimental and computational dual atom electrocatalysis for CO2 conversion to C1 and C2+ products

“…125 Ma and Chen theoretically studied a series of Sn–M DACs. 126 DFT study was used to set up models for five systems of Sn–M (M = Fe, Co, Ni, Cu, Zn) on N-doped graphene. SnMN 6 /G configuration was found stable for all five systems as demonstrated by formation energy analysis.…”

Reaction Mechanism of Rapid CO Electroreduction to Propylene and Cyclopropane (C3+) over Triple Atom Catalysts

“…Single- and dual-atom catalysts (SACs and DACs) are emerging heterogeneous catalysts and have attracted widespread attention because of their high atom utilization, tunable coordination environments, and superior catalytic performance. − Several experimental and theoretical studies reported that SACs and DACs embedded in nitrogen-doped graphene and other 2D supports provide excellent electrocatalytic performance for a diverse set of electrochemical reactions. ,− Recently, theoretical studies have been reported exploring the electrochemical performance of DACs for CORR and CO 2 RR to C 2+ products. , For example, a series of phthalocyanine-based DACs were investigated for the rapid CO electroreduction toward ethylene (C 2 H 4 ) enabled by high CO adsorption energy and low CO dimerization energy . Several DACs such as FeFe, RuRu, CoCo, IrIr, and IrCo were disclosed as the best candidates for converting CO to C 2 H 4 .…”