Construction of a Dual-Function Mo-ZIS@Ti for Photocatalytic Benzyl Alcohol Oxidation and Hydrogen Evolution Performance.

The photocatalytic oxidation of benzyl alcohol and the simultaneous evolution of hydrogen from water are efficient dual-optimal routes. It is important to develop composite catalysts that combine redox properties and facilitate electron-hole separation and transport. Herein, the bimetallic-doped Mo-ZIS@Ti photocatalyst was designed and synthesized, and the selective oxidation of benzyl alcohol and hydrogen evolution by water splitting was realized at the same time. Under visible light irradiation, benzyl alcohol was completely converted with more than 99% selectivity for benzaldehyde, and the H2 production rate was 5.6 times higher than the initial ZIS. The exceptional catalytic performance was ascribed to utilizing Ti-MIL-125 as a precursor, wherein slowly releasing-doped Ti formed robust Ti-S bonds that quickly transfer electrons and reduce sites. Meanwhile, doping Mo effectively captures photogenerated holes and acts as active sites for oxidation reactions. Both experimental characterization and work function calculations demonstrate that the bimetallic synergism effectively modulates the electronic structure of ZIS, promotes the directional separation of electrons and holes, and significantly improves the photoactivity and stability of ZIS. This work contributes a route to obtain benzaldehyde and green hydrogen at the same time and also gives new insights for the construction and mechanism study of bimetallic-doping catalysts.

Construction of a hollow heterojunction interface to accelerate the photocatalytic cleavage of lignin Cß-O bonds.

Photocatalytic splitting of the Cß-O bond is regarded as a prospective strategy for transforming lignin, and it is imperative to develop novel photocatalysts with effective photogenerated charges separation and solar absorption capacity. Herein, a novel hollow ZIF-8/CdS heterostructure photocatalyst was synthesized for the catalytic splitting of lignin Cß-O bonds. The photocatalytic cleavage rate of Cß-O bond of ligin ß-O-4 reached 30.3∙mmol∙h-1∙g-1 within 20 min under visible light exposure. It is noteworthy that the utilization of intricate natural lignin molecules in this photocatalytic system has yielded successful depolymerization. The DFT and XPS results indicate a potential unidirectional electron migration from ZIF-8 to CdS in ZIF-8/CdS composites transfer. This electron transport path follows the direct Z-scheme heterostructure mechanism, resulting in the generation of an internal electric field between ZIF-8 and CdS. Impressively, the synergistic combination of the hollow structure and Z-scheme heterostructure effectively enhances the efficiency of charge carrier separation and maintains a robust redox potential, thereby facilitating Cα-radical generation. This study proposes a novel photocatalyst design strategy that integrates hollow structures and Z-scheme heterojunctions, with the aim of targeting the depolymerization of the Cß-O bond in lignin.

Construction of one-dimensional ZnCdS(EDA)/Ni@NiO for photocatalytic hydrogen evolution.

The development of photocatalysts plays a pivotal role in facilitating the production of green hydrogen energy through water splitting. In this study, one-dimensional (1D) organic-inorganic ZnCdS(EDA)/Ni@NiO (EDA: ethylenediamine) nanorods were prepared by combining organic molecules of EDA into ZnCdS. The EDA molecule possesses two amino functional groups with strong electron-donating capacity, thereby facilitating electron transfer to ZnCdS(EDA)/Ni@NiO and enabling efficient hydrogen evolution through photocatalytic water splitting. The H2 evolution rate of ZnCdS(EDA)/Ni@NiO was 159 µmol g-1 h-1 in the absence of sacrificial agents, and its H2 evolution rate in the system with EDA as the sacrificial agent can reach 5760 µmol g-1 h-1. The combination of EDA, a S vacancy, and heterojunction was proved to be the main factor for improving the separation and transfer rate of photogenerated carriers. The incorporation of ZnCdS(EDA)/Ni@NiO enhances the participation of photogenerated electrons in the photocatalytic hydrogen evolution reaction, thereby improving the overall photocatalytic activity. The synthesis of this one-dimensional composite catalyst holds great potential for advancing the development of efficient photocatalytic materials.