Circumventing Scaling Relations via Gradient Orbital Coupling Promotes Ammonia Electrosynthesis on Cobalt Catalyst
Abstract
Abstract Highly efficient electrocatalytic nitrate reduction to ammonia (NH 3 ) 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 3 O 4 ) 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 3 while suppressing hydrogen evolution reaction. It exhibits a faradaic efficiency of 97.8% and a high yield rate of 3423.0 µg h −1 cm −2 under alkaline conditions. Furthermore, Ce/Co 3 O 4 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 3 − ‐to‐NH 3 activity on cobalt catalysts.
Article Details
Authors (19)
Hanle Liu
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Shunhan Jia
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Limin Wu
School of Chemistry and Chemical Engineering
Ruhan Wang
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Libing Zhang
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Xinning Song
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Xingxing Tan
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Xiaodong Ma
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Xiangyuan Jin
Beijing National Laboratory for Molecular Sciences Key Laboratory of Colloid and Interface and Thermodynamics Center for Carbon Neutral Chemistry Institute of Chemistry Chinese Academy of Sciences Beijing 100190 China
Hang Guo
Xiqing Sui
Beijing National Laboratory for Molecular Sciences CAS Laboratory of Colloid and Interface and Thermodynamics CAS Research/Education Center for Excellence in Molecular Sciences Center for Carbon Neutral Chemistry Institute of Chemistry Chinese Academy of Sciences Beijing 100190 China
Qian Li
Rongjuan Feng
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Lihong Jing
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Qingli Qian
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Jianling Zhang
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Lei He
State Key Laboratory of Chemical Resource Engineering
Xiaofu Sun
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Buxing Han
Institute of Chemistry, Chinese Academy of Sciences , , ,