Catalytic Potential of Post‐Transition Metal Doped Graphene‐Based Single‐Atom Catalysts for the CO2 Electroreduction Reaction

• Published in: Chemphyschem Vol. 23; no. 8; pp. e202200024 - n/a
• Main Authors: Lambie, Stephanie, Low, Jian Liang, Gaston, Nicola, Paulus, Beate
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 20.04.2022; John Wiley and Sons Inc
• Subjects: Carbon dioxide; carbon dioxide reduction; Chemical reduction; density functional calculations; Density functional theory; electrocatalysis; Graphene; Lead; Noble metals; p-block elements; Single atom catalysts; single-atom catalysis; Tin; Transition metals
• ISSN: 1439-4235; 1439-7641; 1439-7641
• DOI: 10.1002/cphc.202200024

Catalysts are required to ensure electrochemical reduction of CO2 to fuels proceeds at industrially acceptable rates and yields. As such, highly active and selective catalysts must be developed. Herein, a density functional theory study of p‐block element and noble metal doped graphene‐based single‐atom catalysts in two defect sites for the electrochemical reduction of CO2 to CO and HCOOH is systematically undertaken. It is found that on all of the systems considered, the thermodynamic product is HCOOH. Pb/C3, Pb/N4 and Sn/C3 are identified as having the lowest overpotential for HCOOH production while Al/C3, Al/N4, Au/C3 and Ga/C3 are identified as having the potential to form higher order products due to the strength of binding of adsorbed HCOOH. HCOOH is the preferred thermodynamic product resulting from the two electron transfer process in CO2 electroreduction for Al, Au, Bi, Ga, In, Pb and Sn doped C3‐ and N4‐defect sites in graphene based single‐atom catalysts. This results from the considerable stability of the *OCHO intermediate compared to the *COOH intermediate on the catalysts considered in this study. Furthermore, available descriptors are unable to describe trends in behaviour of p‐block doped single‐atom catalysts.