Interfacial electron redistribution in a TiO₂/Mn₃O₄ hollow heterostructure for selective photocatalytic CO₂-to-CO conversion.

Authors

Yuanyuan Cheng, Xinyue Zhang, Jingwen Yu, Yunliang Liu, Yi Yang, Yishen Li, Xin Huang, Zhiquan Lang, Yixian Liu, Naiyun Liu, Xiang Liu, Yong Zhao, Haitao Li

Published in

Dalton transactions (Cambridge, England : 2003). Sep 29, 2026. Epub Sep 29, 2026.

Abstract

Selective photocatalytic CO₂-to-CO conversion remains challenging because of rapid charge recombination and insufficient CO₂ activation. Herein, a TiO₂/Mn₃O₄ hollow heterostructure was constructed through a SiO₂ hard-template strategy combined with in situ growth. The hollow hemispherical architecture provides an open and accessible structural platform for the in situ growth of Mn₃O₄ nanosheets and the construction of intimate TiO₂/Mn₃O₄ heterointerfaces. Uniformly anchored Mn₃O₄ nanosheets establish intimate heterointerfaces that induce interfacial electron redistribution and promote charge separation. As a result, TiO₂/Mn₃O₄ exhibits a CO evolution rate of 9.31 μmol g^-1 h^-1, which is 1.62 and 2.20 times higher than those of pristine TiO₂ and Mn₃O₄, respectively, together with a CO selectivity of 84.03%, an electron selectivity of 56.81%, and excellent cycling stability. X-ray photoelectron spectroscopy analysis reveals pronounced interfacial electronic redistribution between TiO₂ and Mn₃O₄, while photoelectrochemical measurements demonstrate enhanced charge separation and interfacial charge transfer. In situ diffuse reflectance infrared Fourier transform spectroscopy further confirms the preferential formation of *COOH and *CO intermediates, favoring the selective two-electron CO₂-to-CO conversion pathway. This work demonstrates that regulating interfacial electron redistribution through hollow heterostructure engineering is an effective strategy for achieving efficient and selective photocatalytic CO₂-to-CO conversion.

PMID:
42806760
Bibliographic data and abstract were imported from PubMed on 29 Sep 2026.

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