A1 Journal article (refereed)
Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction (2022)

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

JYU authors or editors

Publication details

All authors or editors: Wu, Tongwei; Melander, Marko M.; Honkala, Karoliina

Journal or series: ACS Catalysis

ISSN: 2155-5435

eISSN: 2155-5435

Publication year: 2022

Publication date: 03/02/2022

Volume: 12

Issue number: 4

Pages range: 2505-2512

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acscatal.1c05820

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/79690

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.

Keywords: electrolysis; oxidation-reduction reaction; hydrogen; electrochemistry; catalysis; catalysts

Free keywords: hydrogen evolution reaction; electrochemical N2 reduction; grand canonical ensemble density functional theory

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Ministry reporting: Yes

Reporting Year: 2022

JUFO rating: 2