Circumventing Scaling Relations via Gradient Orbital Coupling Promotes Ammonia Electrosynthesis on Cobalt Catalyst

Highly efficient electrocatalytic nitrate reduction to ammonia (NH<sub>3</sub>) relies on the balanced activation of various substrates including nitrate and water, but is currently hindered by the inherent scaling relations governing the adsorption of key reaction intermediates, such as *NO and *H. Herein, we develop a strategy to circumvent these limitations by introducing f-d-p gradient orbital coupling in cobalt oxide (Co<sub>3</sub>O<sub>4</sub>) through Ce doping. Density functional theory calculations indicate that the lattice strain triggered by the dopant redistributes electron density at the Co and O sites, thereby modulating the adsorption strengths of *NO and *H, which favors the production of NH<sub>3</sub> while suppressing hydrogen evolution reaction. It exhibits a faradaic efficiency of 97.8% and a high yield rate of 3423.0 µg h<sup>-1</sup> cm<sup>-2</sup> under alkaline conditions. Furthermore, Ce/Co<sub>3</sub>O<sub>4</sub> catalyst shows robust performance over a wide range of nitrate concentrations (from 5 to 200 mM) and excellent cycling stability. Our findings also suggest that the gradient orbital coupling approach can be extended to other lanthanide dopants (e.g., Pr and Nd), offering a broadly applicable platform to break scaling relations and improve NO<sub>3</sub> <sup>-</sup>-to-NH<sub>3</sub> activity on cobalt catalysts.

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Publication Details

Journal
Angewandte Chemie International Edition
Published
2025-06-03
DOI
https://doi.org/10.1002/anie.202510478
Citations
9
Primary Topic
Ammonia Synthesis and Nitrogen Reduction
Type
article
Field-Weighted Citation Impact
3.50

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article

Circumventing Scaling Relations via Gradient Orbital Coupling Promotes Ammonia Electrosynthesis on Cobalt Catalyst

Lihong Jing, Shunhan Jia, Xinning Song, Rongjuan Feng et al.
9 citations
Angewandte Chemie International Edition
Ammonia Synthesis and Nitrogen Reduction
3.50
article

Circumventing Scaling Relations via Gradient Orbital Coupling Promotes Ammonia Electrosynthesis on Cobalt Catalyst

Lihong Jing, Shunhan Jia, Xinning Song, Rongjuan Feng, Libing Zhang, Xingxing Tan, Lei He, Xiangyuan Jin, Ruhan Wang, Xiaofu Sun, Jianling Zhang, Hanle Liu, Qian Li, Limin Wu, Xiaodong Ma, Hang Guo, Xiqing Sui, Qingli Qian, Buxing Han
article en
9 citations

Abstract

Highly efficient electrocatalytic nitrate reduction to ammonia (NH<sub>3</sub>) relies on the balanced activation of various substrates including nitrate and water, but is currently hindered by the inherent scaling relations governing the adsorption of key reaction intermediates, such as *NO and *H. Herein, we develop a strategy to circumvent these limitations by introducing f-d-p gradient orbital coupling in cobalt oxide (Co<sub>3</sub>O<sub>4</sub>) through Ce doping. Density functional theory calculations indicate that the lattice strain triggered by the dopant redistributes electron density at the Co and O sites, thereby modulating the adsorption strengths of *NO and *H, which favors the production of NH<sub>3</sub> while suppressing hydrogen evolution reaction. It exhibits a faradaic efficiency of 97.8% and a high yield rate of 3423.0 µg h<sup>-1</sup> cm<sup>-2</sup> under alkaline conditions. Furthermore, Ce/Co<sub>3</sub>O<sub>4</sub> catalyst shows robust performance over a wide range of nitrate concentrations (from 5 to 200 mM) and excellent cycling stability. Our findings also suggest that the gradient orbital coupling approach can be extended to other lanthanide dopants (e.g., Pr and Nd), offering a broadly applicable platform to break scaling relations and improve NO<sub>3</sub> <sup>-</sup>-to-NH<sub>3</sub> activity on cobalt catalysts.

Angewandte Chemie International EditionVol. 64(32)
Chinese Academy of Sciences (CN), Beijing National Laboratory for Molecular Sciences (CN), Interface (United Kingdom) (GB), University of Chinese Academy of Sciences (CN), Beijing University of Chemical Technology (CN)
National Natural Science Foundation of China, Youth Innovation Promotion Association of the Chinese Academy of Sciences, National Key Research and Development Program of China
Clean water and sanitation
Openalex Percentile: Top 7%
Ammonia Synthesis and Nitrogen Reduction
3.50
DOISourceOpenAlex
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