High-Density Cobalt Single-Atom Catalysts for Enhanced Oxygen Evolution Reaction

Pawan Kumar; Karthick Kannimuthu; Ali Shayesteh Zeraati; Soumyabrata Roy; Xiao Wang; Xiyang Wang; Subhajyoti Samanta; Kristen A Miller; Maria Molina; Dhwanil Trivedi; Jehad Abed; M Astrid Campos Mata; Hasan Al-Mahayni; Jonas Baltrusaitis; George Shimizu; Yimin A Wu; Ali Seifitokaldani; Edward H Sargent; Pulickel M Ajayan; Jinguang Hu; Md Golam Kibria

doi:10.1021/jacs.3c00537

High-Density Cobalt Single-Atom Catalysts for Enhanced Oxygen Evolution Reaction

J Am Chem Soc. 2023 Apr 12;145(14):8052-8063. doi: 10.1021/jacs.3c00537. Epub 2023 Mar 30.

Authors

Pawan Kumar¹, Karthick Kannimuthu¹, Ali Shayesteh Zeraati¹, Soumyabrata Roy², Xiao Wang³, Xiyang Wang⁴, Subhajyoti Samanta⁵, Kristen A Miller², Maria Molina^{1

6}, Dhwanil Trivedi¹, Jehad Abed⁷, M Astrid Campos Mata², Hasan Al-Mahayni³, Jonas Baltrusaitis⁵, George Shimizu⁶, Yimin A Wu⁴, Ali Seifitokaldani³, Edward H Sargent⁷, Pulickel M Ajayan², Jinguang Hu¹, Md Golam Kibria¹

Affiliations

¹ Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Drive, NW, Calgary, Alberta T2N 1N4, Canada.
² Department of Materials Science and NanoEngineering, Rice University, 6100 Main Street, Houston, Texas 77030, United States.
³ Department of Chemical Engineering, McGill University, Montreal, Quebec H3A 0C5, Canada.
⁴ Department of Mechanical and Mechatronics Engineering, Waterloo Institute for Nanotechnology, Materials Interface Foundry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
⁵ Department of Chemical and Biomolecular Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, Pennsylvania 18015, United States.
⁶ Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada.
⁷ Department of Electrical and Computer Engineering, University of Toronto, 10 King's College Road, Toronto, Ontario, M5S 3G4, Canada.

PMID: 36994816
DOI: 10.1021/jacs.3c00537

Abstract

Single atom catalysts (SACs) possess unique catalytic properties due to low-coordination and unsaturated active sites. However, the demonstrated performance of SACs is limited by low SAC loading, poor metal-support interactions, and nonstable performance. Herein, we report a macromolecule-assisted SAC synthesis approach that enabled us to demonstrate high-density Co single atoms (10.6 wt % Co SAC) in a pyridinic N-rich graphenic network. The highly porous carbon network (surface area of ∼186 m² g^-1) with increased conjugation and vicinal Co site decoration in Co SACs significantly enhanced the electrocatalytic oxygen evolution reaction (OER) in 1 M KOH (η₁₀ at 351 mV; mass activity of 2209 mA mg_Co^-1 at 1.65 V) with more than 300 h stability. Operando X-ray absorption near-edge structure demonstrates the formation of electron-deficient Co-O coordination intermediates, accelerating OER kinetics. Density functional theory (DFT) calculations reveal the facile electron transfer from cobalt to oxygen species-accelerated OER.