Frustrated Lewis Pair-Induced Pre-Adsorbed Oxygen Coupled With Reactant Availability as a Design Strategy for High-Performance Single-Atom Nanozymes

Yanjun Ji; Wenhao Miao; Lin Cheng; Huan Wang; Zitong Zhu; Anjun Song; Junlin Ya; Ying Wang; Jinsong Ren; Xiaogang Qu

doi:10.1002/anie.8133162

Frustrated Lewis Pair-Induced Pre-Adsorbed Oxygen Coupled With Reactant Availability as a Design Strategy for High-Performance Single-Atom Nanozymes

Angew Chem Int Ed Engl. 2026 May 20:e8133162. doi: 10.1002/anie.8133162. Online ahead of print.

Authors

Yanjun Ji^{1

2}, Wenhao Miao³, Lin Cheng³, Huan Wang¹, Zitong Zhu^{1

2}, Anjun Song^{1

2}, Junlin Ya^{1

2}, Ying Wang^{1

2}, Jinsong Ren^{1

2}, Xiaogang Qu^{1

2}

Affiliations

¹ State Key Laboratory of Rare Earth Resource Utilization and Laboratory of Chemical Biology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin, China.
² School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui, China.
³ College of Chemical Engineering, Inner Mongolia Key Laboratory of Theoretical and Computational Chemistry Simulation, Inner Mongolia University of Technology, Hohhot, China.

PMID: 42160128
DOI: 10.1002/anie.8133162

Abstract

Single-atom nanozymes (SANs) have recently been recognized as a promising artificial counterpart to natural enzymes. Nevertheless, their catalytic performance remains hindered by insufficient intrinsic activity, which stems from the substantial energy barriers associated with substrate activation and poor mass transport, limiting reactant availability. To address this, we designed a frustrated Lewis pair (FLP)-based Fe-N-C single-atom nanozyme (FLP-Fe-N-C SAzyme) with enriched pyridinic N vacancy defects to enhance oxygen adsorption for the construction of high-performance oxidase mimics. Density functional theory calculations demonstrate that the FLP structure, with Fe as Lewis acid sites and adjacent F regions as Lewis base sites, synergistically promotes oxygen dissociation and induces a pre-adsorbed oxygen atom beside the catalytic center. Such a newly formed structure induced by the FLP sites showed an optimized electronic and geometric structure of the catalytic center, lowering the energy barrier. In addition, the abundant pyridinic-N vacancies induced an enhanced oxygen adsorption, increasing the local oxygen concentration and thereby accelerating reactant availability. Hence, the FLP-Fe-N-C SAzyme remarkably enhances the intrinsic activity of the oxidase-mimicking SANs, achieving a significantly lower Km value than conventional Fe-N-C SANs.

Keywords: frustrated Lewis pairs; pre‐adsorbed oxygen; single‐atom nanozymes.

Abstract

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