Computational Exploration of the Direct Reduction of CO2 to CO Mediated by Alkali Metal and Alkaline Earth Metal Chloride Anions

Joakim S Jestilä,Einar Uggerud

doi:10.1021/acs.organomet.1c00213

Abstract

Computational Exploration of the Direct Reduction of CO<sub>2</sub> to CO Mediated by Alkali Metal and Alkaline Earth Metal Chloride Anions

Highlights

From a circular economy perspective, the use of CO2 as feedstock for synthetic fuels or commodity chemicals is an attractive prospect
CO2 to form complexes in gas phase reactions, formally metal carbonites (MCO2). Their preferred structures are shown in Scheme 1, which in the case of alkali and alkaline earth metals is the bidentate coordination of the metal to both oxygen atoms (κ2-O2C),[4−12] while for transition metals, the metal ftaysphicioanlly(ηb2i-nCdOs 2t)o.1t3h−e19cEarabrolyntraatnosmitio(ηn1-mCeOta2l)s, or M
Decarbonylation is energetically favored for the reaction between CO2 and carbonites over the reaction proceeding via the oxalates

Summary

Introduction

From a circular economy perspective, the use of CO2 as feedstock for synthetic fuels or commodity chemicals is an attractive prospect. Once formed, CO may serve as a reactant, for example, in the Fischer−Tropsch synthesis of hydrocarbons[1] and the Cativa/Monsanto processes for production of acetic acid.[2,3] Obviously, direct reduction of CO2 to CO is an endothermic reaction: CO2(g) → CO(g) + 1 2O2(g) ΔH°rxn = 283 kJ/mol (i). It is well established that metal atoms and anions may add CO2 to form complexes in gas phase reactions, formally metal carbonites (MCO2). Their preferred structures are shown in Scheme 1, which in the case of alkali and alkaline earth metals is the bidentate coordination of the metal to both oxygen atoms (κ2-O2C),[4−12] while for transition metals, the metal ftaysphicioanlly(ηb2i-nCdOs 2t)o.1t3h−e19cEarabrolyntraatnosmitio(ηn1-mCeOta2l)s, or M in =

Methods

Results

Conclusion