Approaching Theoretical Performances of Electrocatalytic Hydrogen Peroxide Generation by Cobalt-Nitrogen Moieties

Runjia Lin; Liqun Kang; Karolina Lisowska; Weiying He; Siyu Zhao; Shusaku Hayama; Graham J Hutchings; Dan J L Brett; Furio Corà; Ivan P Parkin; Guanjie He

doi:10.1002/anie.202301433

Approaching Theoretical Performances of Electrocatalytic Hydrogen Peroxide Generation by Cobalt-Nitrogen Moieties

Angew Chem Int Ed Engl. 2023 May 15;62(21):e202301433. doi: 10.1002/anie.202301433. Epub 2023 Apr 18.

Authors

Runjia Lin^{1

2}, Liqun Kang^{3

4}, Karolina Lisowska¹, Weiying He^{3

5}, Siyu Zhao^{1

4}, Shusaku Hayama⁶, Graham J Hutchings², Dan J L Brett⁴, Furio Corà¹, Ivan P Parkin¹, Guanjie He^{1

4

7}

Affiliations

¹ Christopher Ingold Laboratory, Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK.
² Max Planck-Cardiff Centre on the Fundamentals of Heterogeneous Catalysis FUNCAT, Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff, UK.
³ Department of Inorganic Spectroscopy, Max-Planck-Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.
⁴ Department of Chemical Engineering, University College London (UCL), London, WC1E 7JE, UK.
⁵ University of Göttingen, Institute of Inorganic Chemistry, Tamannstrasse 4, 37077, Göttingen, Germany.
⁶ Diamond Light Source Ltd, Diamond House, Harwell Campus, Didcot, OX11 0DE, UK.
⁷ School of Chemistry, University of Lincoln, Brayford Pool, Lincoln, LN6 7TS, UK.

Abstract

Electrocatalytic oxygen reduction reaction (ORR) has been intensively studied for environmentally benign applications. However, insufficient understanding of ORR 2 e^- -pathway mechanism at the atomic level inhibits rational design of catalysts with both high activity and selectivity, causing concerns including catalyst degradation due to Fenton reaction or poor efficiency of H₂ O₂ electrosynthesis. Herein we show that the generally accepted ORR electrocatalyst design based on a Sabatier volcano plot argument optimises activity but is unable to account for the 2 e^- -pathway selectivity. Through electrochemical and operando spectroscopic studies on a series of CoN_x /carbon nanotube hybrids, a construction-driven approach based on an extended "dynamic active site saturation" model that aims to create the maximum number of 2 e^- ORR sites by directing the secondary ORR electron transfer towards the 2 e^- intermediate is proven to be attainable by manipulating O₂ hydrogenation kinetics.

Keywords: Cobalt-Nitrogen Moieties; Electrocatalyst; Hydrogen Peroxide; Oxygen Reduction Reaction.

Grants and funding

EP/V027433/1/Engineering and Physical Sciences Research Council