Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction
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
Published inACS Catalysis
DisciplineNanoscience CenterResurssiviisausyhteisöFysikaalinen kemiaNanoscience CenterSchool of Resource WisdomPhysical Chemistry
© 2022 The Authors. Published by American Chemical Society
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.
PublisherAmerican Chemical Society (ACS)
Publication in research information system
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Related funder(s)Academy of Finland
Funding program(s)Academy Project, AoF; Research post as Academy Research Fellow, AoF
Additional information about fundingT.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). ...
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