Ligand-Dependent Electronic Modulation of Conjugated Metal-Organic Frameworks Enables Efficient Electrocatalytic Nitric Oxide Reduction to Ammonia.

Authors

Chenhui Yin, Wei Liao, Xinyu Qin, Yuxiao Shi, Xia Li, Xuan Chen, Mohsen Shakouri, Bin He, Huan Pang

Published in

Advanced materials (Deerfield Beach, Fla.). Pages e74943. Sep 08, 2026. Epub Sep 08, 2026.

Abstract

Electrochemical reduction of ammonia represents a highly promising approach for transforming harmful environmental pollutants into more valuable products. In this study, we successfully achieved precise control over the environment surrounding single-atom Ni sites by modifying functional groups on ligands. To validate this strategy, we constructed two similar hollow Ni-MOFs. The metal-organic frameworks (MOFs) containing the p-type tetraazanaphthotetraphene ligand (Ni-TT) demonstrated exceptional performance compared to n-type triphenylene (Ni-TP). Its overall reduction rate reached 196.9 µmol·h^-1·cm², with a Faraday efficiency as high as 90.9% at -0.4 V versus RHE. The exceptional performance of Ni-TT stems from the p-type tetranaphthalenetetracene ligand, which is nitrogen-rich and electron-deficient. The electronic properties of the ligand significantly influence the coordination environment around the single-atom Ni site, enabling precise control over proton-transfer behavior during the reaction. Theoretical calculations also indicate that hydrogen adsorption on p-type Ni-TT surfaces accelerates hydrogen transfer at Ni active sites compared to n-type Ni-TP. This significantly enhances the rate-determining step (RDS) in the NO hydrogenation process. The constructed Ni-TT-based Zn-NO battery achieved a power density of 2.1 mW cm^-2. These results provide insight into how conjugated ligand structures modulate the electronic structure and hydrogenation behavior, which may guide future studies on MOF-based electrocatalysts for nitric oxide reduction reaction (NORR).

PMID:
42706868
Bibliographic data and abstract were imported from PubMed on 08 Sep 2026.

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