Efficient water dissociation on confined ultrafine Pt via pyridinic N-enhanced heavy d−π interaction

Dong, Y., Chen, J.-B., Ying, J., Xiao, Y.-X., Tian, G., Symes, M. D. and Yang, X.-Y. (2022) Efficient water dissociation on confined ultrafine Pt via pyridinic N-enhanced heavy d−π interaction. Chemistry of Materials, 34(18), pp. 8271-8279. (doi: 10.1021/acs.chemmater.2c01738)

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Sluggish water dissociation on Pt electrocatalysts results in poor performance for the alkaline hydrogen evolution reaction (HER) and thus greatly limits their practical application in industrial water electrolysis. Herein, ultrafine Pt nanoparticles have been confined into N-doped carbon by an in situ galvanic replacement reaction, and the pyridinic N-enhanced heavy d−π interaction is found to significantly enhance the water dissociation catalytic activity of Pt. The electron-deficient Pt generated by this enhanced heavy d−π effect exhibits an ultralow overpotential for hydrogen evolution of 10 mV at a current density of 10 mA cm–2 and an ultrahigh mass current density of 7.74 mA μgPt–1 at an overpotential of 70 mV (7.9-fold higher than that of commercial Pt/C). Theoretical calculations reveal that the pyridinic N-enhanced heavy d−π effect can largely reduce the water dissociation energy barrier on Pt, thus greatly enhancing Pt’s performance for the alkaline HER.

Item Type:Articles
Additional Information:This work was supported by National Natural Science Foundation of China (51861135313), Sino-German Centre’s COVID-19 Related Bilateral Collaborative project (C-0046), FRFCU (2021qntd13), National 111 project (B20002), Program for Changjiang Scholars and Innovative Research Team in University (IRT_15R52), Guangdong Basic and Applied Basic Research Foundation (2019A1515110436, 2021A1515111131, 2022A1515011905, 2022A1515010137, and 2022A1515010504), Guangzhou Science and Technology Project (202102020463), Guangdong Province International Scientific and Technological Cooperation Projects (2020A0505100036), and Shenzhen Science and Technology Program (JCYJ20210324142010029 and GJHZ20210705143204014). We thank the Nanostructure Research Centre (NRC) for the S/TEM work. M.D.S. thanks the Royal Society for a University Research Fellowship (UF150104).
Keywords:Materials Chemistry, General Chemical Engineering, General Chemistry
Glasgow Author(s) Enlighten ID:Symes, Professor Mark
Authors: Dong, Y., Chen, J.-B., Ying, J., Xiao, Y.-X., Tian, G., Symes, M. D., and Yang, X.-Y.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry of Materials
Publisher:American Chemical Society
ISSN (Online):1520-5002
Published Online:13 September 2022
Copyright Holders:Copyright © 2022 American Chemical Society
First Published:First published in Chemistry of Materials 34(18): 8271-8279
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
173495Driving energetically uphill processes using metal-ligand coordination complexesMark SymesThe Royal Society (ROYSOC)UF150104Chemistry