Constructing 3D hierarchical TiO2 microspheres with enhanced mass diffusion for efficient glucose photoreforming under modulated reaction conditions.

Three-dimensional (3D) TiO2 hierarchical microspheres (THMs) were successfully prepared via a facial template-free hydrothermal approach. The possible growth mechanism of THM was also investigated by TiCl4 concentration-, time-, and temperature-dependent experiments. The results indicate that the formation of an urchin-like hierarchical structure may follow a "nucleation-dissolution and recrystallization-assembly" process. THM was employed for photoreforming under various catalyst and glucose concentrations, solvent compositions, and pH values. The H2 production rate, glucose conversion, arabinose and formic acid selectivity reached 9.44 mmol gcat.-1h-1, 86.35%, 11.32%, and 46.87%, respectively, under the modulated condition with Pt as cocatalyst; this is attributed to the enhanced mass diffusion caused by the 3D hierarchical morphology as well as the interaction between unsaturated Ti atoms (or oxygen vacancies) in THM and the hydroxyl oxygen atoms on glucose. In addition, the enhanced light absorption induced by defects also exerts a positive effect. In this work, we present an emerging sustainable strategy for the coproduction of H2 and value-added chemicals from biomass-based glucose with economic photocatalysts under mild conditions.

Effective enhancement of electron migration and photocatalytic performance of nitrogen-rich carbon nitride by constructing fungal carbon dot/molybdenum disulfide cocatalytic system.

To find a cocatalyst that can replace noble metals, fungal carbon dot (CD) modified molybdenum disulfide (MoS2) cocatalyst system was designed. The composites were prepared by hydrothermal and calcination methods with different ratios of CDs, MoS2 and nitrogen-rich carbon nitride (p-C3N5). p-C3N5 has excellent electronic properties, and MoS2 modified by CDs (D-MoS2) can significantly enhance the photocatalytic performance of p-C3N5 by improving the photogenerated electron migration efficiency. The experiments showed that the developed CDs/MoS2/C3N5 composites exhibited excellent performance in both photocatalytic hydrogen (H2) evolution and methylene blue (MB) degradation, with CMSCN5 (D-MoS2 with 5% mass fraction) showing the best photocatalytic activity. The corresponding H2 evolution rate of CMSCN5 was 444 µmol g-1h-1 and 1.45 times higher than that of unmodified p-C3N5, by 120 min, the removal rate of MB was up to 93.51%. The 5 cycle tests showed that CMSCN5 had great stability. The high charge mobility and high density of H2 evolution active sites of MoS2 nanosheets, together with the electron storage and transfer properties of CDs can obviously improve electron migration and reduce the photogenerated carrier recombination on the p-C3N5 surface. The design and preparation of such composites offer broad prospects for the development of photocatalytic systems with noble metal-free cocatalysts.