Fabrication of core–shell nanostructure via novel ligand-defect reassembly strategy for efficient photocatalytic hydrogen evolution and NO removal

• Published in: Journal of colloid and interface science 2025-02, Vol.680 (Pt A), p.948-964
• Main Authors: Liu, Xingyan, Wu, Kaili, Jia, Chaogang, He, Youzhou, Qiu, Yirui, Fang, Yuyu, Ma, Hao, Wang, Song, Wei, Siping, Dong, Fan
• Format: Article
• Language: English
• Subjects: adsorption; Core–shell structure; density functional theory; electron paramagnetic resonance spectroscopy; energy conversion; Fourier transform infrared spectroscopy; Hydrogen evolution; hydrogen production; Metal–organic frameworks (MOFs); nanomaterials; NO removal; Photocatalysis; photocatalysts; photosensitivity; reactive oxygen species
• ISSN: 0021-9797; 1095-7103; 1095-7103
• DOI: 10.1016/j.jcis.2024.11.035

The special core–shell sample with the analogous mixture of MIL-125 and MIL-125-NH2 function formed via ligand-defect reassembly as an efficient dual-functional photocatalyst for hydrogen production and NO removal. [Display omitted] The core–shell structure often exhibits unique properties, resulting in superior physical and chemical performance distinct from individual component in the field of photocatalysis. However, traditional prepared methods such as template synthesis and layer-by-layer self-assembly are relatively complex. Therefore, it is necessary to explore an efficient and expedient approach. Here, we have proposed a convenient method to gradually destroy the terephthalic acid (BDC) of MIL-125 from the outer to inner layers through hydrothermal stirring, followed by reassembling with photosensitive 2-amino-terephthalic acid (BDC-NH2) into the exposed Ti-oxo clusters left by the BDC to create photocatalysts featuring a core–shell configuration. The special core–shell sample with the analogous mixture of MIL-125 and MIL-125-NH2 function as a high-performance dual-functional photocatalyst for hydrogen generation and NO elimination. The optimal core–shell material (M-125-45-N) exhibits an outstanding photocatalytic hydrogen production rate of 3.74 mmol·g−1·h−1 and an excellent photocatalytic NO removal rate of 70.15 %. The apparent quantum yield (AQY) value and solar-to-hydrogen energy conversion efficiency (STH) at specific wavelengths are also investigated. The Density functional theory (DFT) calculation, In-situ Fourier transform infrared (In-situ FT-IR) and Electron spin resonance (ESR) have suggested that the enhanced photocatalytic activity of optimal core–shell material arised from its stronger adsorption capacity towards reactants, promoting the production of reactive oxygen species (ROS) conducive to photocatalytic reactions. This study represents the first investigation of a dual functional core–shell MOFs formed via ligand-defect reassembly, showcasing the excellent efficacy in photocatalytic hydrogen evolution and NO removal, which contributes to the feasible development of novel dual-functional photocatalysts with core–shell structures.