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Updated: Sep 15, 2026

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Dynamic Asymmetry in O/N-Coordinated Zn Single-Atom Catalysts Promotes Sabatier-Favorable Urea and Urea Peroxide
Shengbo Zhang1, Ke Li2, Hui Xu3
1Macao Institute of Materials Science and Engineering (MIMSE), Faculty of Innovation Engineering, Macau University of Science and Technology, Taipa, Macao, China.
Abstract:
Precise regulation of metal‒intermediate binding is essential for selective electrocatalysis, yet conventional symmetric single-atom coordination often limits directional adsorption control. Here we report an asymmetric O/N-co-coordinated Zn single-atom catalyst, Zn-O3N1-C, using symmetric Zn-O4-C as a structural counterpart. Structural characterization and x-ray absorption spectroscopy (XAS) confirm atomically dispersed Zn‒O3N1 sites, in which replacing one O ligand with less electronegative N not only breaks local symmetry, but also enriches Zn electron density and lowers the Zn oxidation state. Operando XAS further reveals that Zn-O3N1 undergoes cathodic-bias-induced electronic enrichment and anisotropic Zn─N/Zn─O bond response, amplifying local coordination polarization while preserving the isolated Zn─O/N framework. This dynamically polarized asymmetric coordination shifts Zn‒adsorbate interactions toward a Sabatier-favorable regime, enabling two adsorption-governed transformations. For CO2/nitrate co-reduction, Zn-O3N1-C promotes *NO/*NHO-mediated C‒N coupling. The same catalyst also demonstrates excellent electrocatalytic activity toward two-electron oxygen reduction reaction (2e- ORR). The electrosynthesized urea and H2O2 are further coupled to produce urea peroxide. Operando spectroscopy and density functional theory calculations reveal that asymmetric Zn-O3N1 coordination optimizes *NO/*NHO and *OOH binding, establishing dynamic coordination polarization as a design principle for selective single-atom electrocatalysis.
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