Overcoming the *H-NOx Coupling Bottleneck via Palladium-Enabled Relay Catalysis on CuCo₂O₄ Toward Ampere-Level Nitrate-to-Ammonia.
- 1Hebei Key Laboratory of Analytical Science and Technology, and College of Chemistry and Materials Science, Hebei University, Baoding, People's Republic of China.
- 2Key Laboratory of Automobile Materials, Ministry of Education, and School of Materials Science and Engineering, Jilin University, Changchun, People's Republic of China.
- 3Institutes of Physical Science and Information Technology, Anhui University, Hefei, People's Republic of China.
Abstract
Electrocatalytic nitrate reduction reaction (NO₃RR) represents a sustainable route for both ammonia (NH₃) production and nitrate-contaminated water remediation, yet its practical application is crippled by the kinetically sluggish multi-electron/proton transfer and insufficient targeted active hydrogen (*H) supply. Herein, a Pd-doped CuCo₂O₄ (Pd-CuCo₂O₄) hollow spiny microsphere catalyst is designed to tackle this challenge via a synergistic relay catalysis mechanism coupled with rapid *H replenishment. Kinetics studies and theoretical calculations collectively demonstrate a clear tandem pathway for NH₃ synthesis: NO₃ ⁻ is preferentially reduced to NO₂ ⁻ on Cu sites, and then migrates to neighboring Co sites for further conversion to NH₃. Crucially, the incorporated Pd dopants promote NO₃ ⁻ adsorption on Cu sites and *H generation on Co sites precisely. The efficient *H supply and co-adsorption for intermediates eliminates the intrinsic kinetic bottleneck of poor *H-NOx coupling, ensuring the tandem catalysis proceeds smoothly without interruption. Benefiting from the *H-spillover boosted relay mechanism, an ultra-high current density over -2.0 A cm⁻² and a remarkable NH₃ yield rate of 100.43 mg h⁻¹ cm⁻² are achieved. This study underscores the synergistic interplay among the three active sites and provides a blueprint for designing high-rate, practical NO₃RR electrocatalysts.
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BibTeX
@article{cui2026overcoming,
title = {{Overcoming the *H-NOx Coupling Bottleneck via Palladium-Enabled Relay Catalysis on CuCo₂O₄ Toward Ampere-Level Nitrate-to-Ammonia.}},
author = {Yuhuan Cui and Yingying Xu and Jingyao Guo and Yao Liu and Yuxuan Li and Zixuan Feng and Yitong Zhou and Yongjun Gao and Zhili Wang},
journal = {Advanced science (Weinheim, Baden-Wurttemberg, Germany)},
year = {2026},
month = oct,
doi = {10.1002/advs.78576},
url = {https://europepmc.org/article/MED/42958761},
note = {CC BY},
}
RIS
TY - JOUR
TI - Overcoming the *H-NOx Coupling Bottleneck via Palladium-Enabled Relay Catalysis on CuCo₂O₄ Toward Ampere-Level Nitrate-to-Ammonia.
AU - Yuhuan Cui
AU - Yingying Xu
AU - Jingyao Guo
AU - Yao Liu
AU - Yuxuan Li
AU - Zixuan Feng
AU - Yitong Zhou
AU - Yongjun Gao
AU - Zhili Wang
PY - 2026
DA - 2026/10/29
JO - Advanced science (Weinheim, Baden-Wurttemberg, Germany)
DO - 10.1002/advs.78576
UR - https://europepmc.org/article/MED/42958761
AB - Electrocatalytic nitrate reduction reaction (NO₃RR) represents a sustainable route for both ammonia (NH₃) production and nitrate-contaminated water remediation, yet its practical application is crippled by the kinetically sluggish multi-electron/proton transfer and insufficient targeted active hydrogen (*H) supply. Herein, a Pd-doped CuCo₂O₄ (Pd-CuCo₂O₄) hollow spiny microsphere catalyst is designed to tackle this challenge via a synergistic relay catalysis mechanism coupled with rapid *H replenishment. Kinetics studies and theoretical calculations collectively demonstrate a clear tandem pathway for NH₃ synthesis: NO₃ ⁻ is preferentially reduced to NO₂ ⁻ on Cu sites, and then migrates to neighboring Co sites for further conversion to NH₃. Crucially, the incorporated Pd dopants promote NO₃ ⁻ adsorption on Cu sites and *H generation on Co sites precisely. The efficient *H supply and co-adsorption for intermediates eliminates the intrinsic kinetic bottleneck of poor *H-NOx coupling, ensuring the tandem catalysis proceeds smoothly without interruption. Benefiting from the *H-spillover boosted relay mechanism, an ultra-high current density over -2.0 A cm⁻² and a remarkable NH₃ yield rate of 100.43 mg h⁻¹ cm⁻² are achieved. This study underscores the synergistic interplay among the three active sites and provides a blueprint for designing high-rate, practical NO₃RR electrocatalysts.
SN - 2198-3844
ER -