Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction
Abstract
Electrochemical N2 reduction (NRR) to ammonia is seriously limited by the competing hydrogen evolution reaction (HER), but atomic-scale factors controlling HER/NRR competition are unknown. Herein we unveil the mechanism, thermodynamics, and kinetics determining the HER/NRR efficiency on the state-of-the-art NRR electrocatalyst, Ru-N4, using grand canonical ensemble density functional theory (GCE-DFT). We show that NRR/HER intermediates coadsorb on the catalyst where NRR intermediates suppress HER and selectivity is determined by the initial step forming *NNH or *H. Our results provide crucial insight into the complex NRR/HER competition, show the necessity of using GCE-DFT calculations, and suggest ways to improve NRR selectivity.
Main Authors
Format
Articles
Research article
Published
2022
Series
Subjects
Publication in research information system
Publisher
American Chemical Society (ACS)
The permanent address of the publication
https://urn.fi/URN:NBN:fi:jyu-202202081442Käytä tätä linkitykseen.
Review status
Peer reviewed
ISSN
2155-5435
DOI
https://doi.org/10.1021/acscatal.1c05820
Language
English
Published in
ACS Catalysis
Citation
- Wu, T., Melander, M. M., & Honkala, K. (2022). Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction. ACS Catalysis, 12(4), 2505-2512. https://doi.org/10.1021/acscatal.1c05820
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Funder(s)
Research Council of Finland
Research Council of Finland
Funding program(s)
Academy Project, AoF
Academy Research Fellow, AoF
Akatemiahanke, SA
Akatemiatutkija, SA
Additional information about funding
T.W. acknowledges the support by the National Natural Science Foundation of China (No. 11874005), the China National Postdoctoral Program for Innovative Talents (No. BX2021053), China Postdoctoral Science Foundation (No.2021M700680) and China Scholarship Council (No. 201906070128). T.W. also acknowledges the support of the Shang Hai Tong Ji Gao Ting Yao Environment Science and Technology Development Foundation. M.M.M. and K.H. gratefully acknowledge support by the Academy of Finland (grant numbers 317739 and 338228), and the Jane and Aatos Erkko Foundation (funding to the LACOR project).
Copyright© 2022 The Authors. Published by American Chemical Society