Molecular Nickel Thiolate Complexes for Electrochemical Reduction of CO2 to C1-3 Hydrocarbons

Jiehao Du; Banggui Cheng; Huiqing Yuan; Yuan Tao; Ya Chen; Mei Ming; Zhiji Han; Richard Eisenberg

doi:10.1002/anie.202211804

Molecular Nickel Thiolate Complexes for Electrochemical Reduction of CO₂ to C_1-3 Hydrocarbons

Angew Chem Int Ed Engl. 2023 Feb 20;62(9):e202211804. doi: 10.1002/anie.202211804. Epub 2023 Jan 24.

Authors

Jiehao Du¹, Banggui Cheng¹, Huiqing Yuan¹, Yuan Tao¹, Ya Chen¹, Mei Ming¹, Zhiji Han¹, Richard Eisenberg²

Affiliations

¹ MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University, 510275, Guangzhou, China.
² Department of Chemistry, University of Rochester, 14627, Rochester, NY, USA.

PMID: 36599806
DOI: 10.1002/anie.202211804

Abstract

We report the unprecedented electrocatalytic activity of a series of molecular nickel thiolate complexes (1-5) in reducing CO₂ to C_1-3 hydrocarbons on carbon paper in pH-neutral aqueous solutions. Ni(mpo)₂ (3, mpo=2-mercaptopyridyl-N-oxide), Ni(pyS)₃ ^- (4, pyS=2-mercaptopyridine), and Ni(mp)₂ ^- (5, mp=2-mercaptophenolate) were found to generate C₃ products from CO₂ for the first time in molecular complex. Compound 5 exhibits Faradaic efficiencies (FEs) of 10.6 %, 7.2 %, 8.2 % for C₁ , C₂ , C₃ hydrocarbons respectively at -1.0 V versus the reversible hydrogen electrode. Addition of CO to the system significantly promotes the FE_C1-C3 to 41.1 %, suggesting that a key Ni-CO intermediate is associated with catalysis. A variety of spectroscopies have been performed to show that the structures of nickel complexes remain intact during CO₂ reduction.

Keywords: CO2 Reduction; Electrocatalysis; Hydrocarbons; Nickel-Thiolate.

Grants and funding

Sun Yat-sen University