Role of Pyridinic Nitrogen in the Mechanism of the Oxygen Reduction Reaction on Carbon Electrocatalysts
Authors:
- 10 November 2020
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 60 (10) , 5121-5124
Abstract
The introduction of pyridinic nitrogen (pyri‐N) into carbon‐based electrocatalysts for the oxygen reduction reaction is considered to create new active sites. Herein, the role of pyri‐N in such catalysts was investigated from a mechanistic viewpoint using carbon black (CB)‐supported pyri‐N‐containing molecules as model catalysts; the highest activity was observed for 1,10‐phenanthroline/CB. X‐ray photoemission spectroscopy showed that in acidic electrolytes, both pyri‐N atoms of 1,10‐phenanthroline could be protonated to form pyridinium ions (pyri‐NH+). In O2‐saturated electrolytes, one of the pyri‐NH+ species was reduced to pyri‐NH upon the application of a potential; no such reduction was observed in N2‐saturated electrolytes. This behavior was ascribed to electrochemical reduction of pyri‐NH+ occurring simultaneously with the thermal adsorption of O2, as supported by DFT calculations. According to these calculations, the coupled reduction was promoted by hydrophobic environments.Keywords
Funding Information
- Japan Society for the Promotion of Science (17F17345, 17H01342, 19K15356)
This publication has 18 references indexed in Scilit:
- Identification of active sites for acidic oxygen reduction on carbon catalysts with and without nitrogen dopingNature Catalysis, 2019
- Identifying the Active Site of N-Doped Graphene for Oxygen Reduction by Selective Chemical ModificationACS Energy Letters, 2018
- High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materialsNature Catalysis, 2018
- Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalystsScience, 2016
- Electrocatalytic Oxygen Activation by Carbanion Intermediates of Nitrogen-Doped Graphitic CarbonJournal of the American Chemical Society, 2014
- Atomic-scale characterization of nitrogen-doped graphite: Effects of dopant nitrogen on the local electronic structure of the surrounding carbon atomsPhysical Review B, 2012
- Effect of Microstructure of Nitrogen-Doped Graphene on Oxygen Reduction Activity in Fuel CellsLangmuir, 2012
- On the mechanism of enhanced oxygen reduction reaction in nitrogen-doped graphene nanoribbonsPhysical Chemistry Chemical Physics, 2011
- Oxygen reduction reaction mechanism on nitrogen-doped graphene: A density functional theory studyJournal of Catalysis, 2011
- Hydrogen Peroxide Production in the Oxygen Reduction Reaction at Different Electrocatalysts as Quantified by Scanning Electrochemical MicroscopyAnalytical Chemistry, 2009