Surface and interface double-engineered Ti-deficient TiO2/cyano-functionalized g-C3N4 S-scheme heterojunction for artificial photosynthesis

doi:10.1016/j.jmst.2025.11.012

Abstract

Abstract: Solar-driven carbon dioxide (CO₂) reduction integrated with the oxidation of metronidazole (MNZ) through an S-scheme heterojunction presents a viable approach to tackle energy shortages and environmental issues concurrently. Nevertheless, the two primary challenges associated with conventional S-scheme heterojunctions may directly constrain their practical applicability. On the one hand, the electron transfer and separation process inevitably involves the Type II migration mode, which may reduce the thermodynamic redox potentials of photogenerated charge carriers. On the other hand, the limited availability of surface active sites may result in reduced adsorption capacity and higher activation energy for reactant molecules. Herein, a novel Ti-deficient titanium dioxide (Ti_VO₂) with cyano-functionalized graphitic carbon nitride (CCN) (labeled as Ti_VO₂/CCN) S-scheme heterojunction with interfacial Ti-N bonds and independently separated surface active sites was constructed, which not only effectively suppresses the Type II charge migration mode, but also provides abundant redox active sites for MNZ and CO₂. In this system, the formation of the interfacial Ti-N bonds not only contributes to a strongly integrated interface but also functions as an efficient electron transfer pathway between the two components, thereby promoting the formation of an S-scheme heterostructure. Meanwhile, the surface cyano group and Ti vacancies enhance the adsorption and activation capability of CO₂ and MNZ, respectively, thereby supporting the simultaneous photocatalytic reduction of CO₂ and oxidation of MNZ. Therefore, Ti_VO₂/CCN demonstrates superior photocatalytic redox performance, achieving a CO evolution rate of 5.25 µmol g^-1 h^-1 and a MNZ removal efficiency of 94.3 %, significantly surpassing that of titanium dioxide/graphitic carbon nitride (TiO₂/g-C₃N₄) without surface regulation and mechanically mixed Ti_VO₂/CCN. This approach not only advances the design of efficient S-scheme heterojunctions but also establishes a synergistic strategy for concurrently addressing the challenges associated with CO₂ reduction and antibiotic pollution mitigation.

Key words: S-scheme heterojunction, Interface chemical bond, Dual redox sites, Coupled reaction system

Qianlong Wang, Haili Lin, Xuemei Jia, Xiaoxin Feng, Haoyu Zhang, Yujie Zhang, Zhongliao Wang, Jing Cao. Surface and interface double-engineered Ti-deficient TiO₂/cyano-functionalized g-C₃N₄ S-scheme heterojunction for artificial photosynthesis[J]. J. Mater. Sci. Technol., 2026, 264: 115-129.

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Surface and interface double-engineered Ti-deficient TiO₂/cyano-functionalized g-C₃N₄ S-scheme heterojunction for artificial photosynthesis

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