Boosting Electrocatalytic Nitrogen Reduction on Cobalt-Based Perovskite via Regulating Reaction Pathway Through Donation-Back-Donation Modulation

Ning Han; Wei Zhang; Jianxiang Wu; Kaibin Chu; Shihui Feng; Shuo Wang; Alain R Puente-Santiago; Jinlin Long; Bo Weng; Bao-Lian Su

doi:10.1002/anie.202504601

Boosting Electrocatalytic Nitrogen Reduction on Cobalt-Based Perovskite via Regulating Reaction Pathway Through Donation-Back-Donation Modulation

Angew Chem Int Ed Engl. 2025 Jun 17;64(25):e202504601. doi: 10.1002/anie.202504601. Epub 2025 May 2.

Authors

Ning Han¹, Wei Zhang², Jianxiang Wu³, Kaibin Chu⁴, Shihui Feng⁵, Shuo Wang⁶, Alain R Puente-Santiago⁷, Jinlin Long⁶, Bo Weng⁸, Bao-Lian Su^{9

10}

Affiliations

¹ The Edward S. Rogers Department of Electrical and Computer Engineering, University of Toronto, Ontario, ON, M5S 1A4, Canada.
² Institute of Energy Materials Science, University of Shanghai for Science and Technology, Shanghai, 200093, China.
³ Shanghai Key Laboratory of Materials Protection and Advanced Materials Electric Power, Shanghai University of Electric Power, Shanghai, 200090, China.
⁴ School of Materials Science and Engineering, Linyi University, Linyi, 276000, China.
⁵ Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, 10 691, Sweden.
⁶ State Key Laboratory of Chemistry for NBC Hazards Protection, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350116, China.
⁷ Department of Chemistry and Biochemistry, Florida International University, Miami, FL, USA.
⁸ State Key Laboratory of Advanced Environmental Technology, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, 361021, China.
⁹ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China.
¹⁰ Laboratory of Inorganic Materials Chemistry (CMI), University of Namur, 61 rue de Bruxelles, Namur, 5000, Belgium.

PMID: 40227956
DOI: 10.1002/anie.202504601

Abstract

The electrocatalytic approach of combining N₂ and H₂O to produce ammonia, known as the electrocatalytic N₂ reduction reaction (eNRR), has garnered significant attention due to its environmental benefits and potential for supporting a decentralized agricultural economy. However, the underlying chemistry governing the reaction pathways remains poorly understood, hindering the design of low-cost and efficient eNRR catalysts. Here we report the enhancement of the electrocatalytic eNRR activity of perovskite oxides by tuning the reaction pathway through a "donation-back-donation" mechanism. This is achieved by controlling the spin state via adjusting the distribution of d orbital electrons in low-cost transition metals, such as cobalt. Specifically, the cobalt in perovskite SrCoO₃ (SC) with a low-spin state demonstrates an 18 times higher ammonia yield rate compared to that in Co₃O₄ and 1.5 times higher than cobalt in perovskite LaCoO₃ (LC). The low spin states of cobalt in SC enable better control of the eNRR reaction pathway over the transformation of *N₂H to *NHNH or *NNH₂, resulting in alternating hydrogenation in SC rather than distal hydrogenation in LC with a high spin state. The unprecedented improvement in eNRR by regulating the spin state of Co demonstrates the bright of low-cost Co-based electrocatalysts for ammonia production.

Keywords: D orbital electron distribution; Nitrogen reduction reaction; Perovskite; Reaction pathway; Regulation of spin state.

Abstract

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