Solar energy-induced catalysis has been attracting intensive interests and its quantum efficiencies in plasmon-mediated photothermal catalysis (P-photothermal catalysis) and external heat-coupled photocatalysis (E-photothermal catalysis) are ultimately determined by the catalyst structure for photo-induced energetic hot carriers. Herein, different catalysts of supported (TiO₂-P25 and Al₂O₃) platinum quantum dots are employed in photo, thermal, and photothermal catalytic dry reforming of methane. Integrated experimental and computational results unveil different active sites (hot zones) on the two catalysts for photo, thermal, and photothermal catalysis. The hot zones of P-photothermal catalysis are identified to be the metal–support interface on Pt/P25 and the Pt surface on Pt/Al₂O₃, respectively. However, a change of the active site to the Pt surface on Pt/P25 is for the first time observed in E-photothermal catalysis (external heating temperature of 700 °C). The hot zones contribute to the significant enhancements in photothermal catalytic reactivity against thermocatalysis. This study helps to understand the reaction mechanism of photothermal catalysis to exploit efficient catalysts for solar energy utilization and fossil fuels upgrading.

Recently metal-free catalysts become very promising in environmental catalysis own to the nature of being free of metals for avoiding metal leaching-related secondary contamination. Herein, a series of boron and nitrogen co-doped graphene nanotubes were first synthesised by thermal treatment of urea, boric acid, and polyethene glycol (PEG, 2000). The materials fabricated under varied thermal conditions, e.g., different pyrolysis temperature and retention time, were characterised through advanced physiochemical techniques. The as-prepared materials showed outstanding catalytic activity for degradation of 4-hydroxybenzoic acid (HBA) via peroxymonosulfate (PMS) activation, whereas the catalyst pyrolysed at 1100 ​°C for 6 ​h (BNG-1100-6h) was found to be the best candidate for environmental remediation, thanks to its engineered surface, exposed active sites, and well-tuned functional groups. Based on the optimal carbocatalyst, reaction conditions such as catalyst loading, PMS dosage, solution pH, and reaction temperature were thoroughly investigated to make it a cost-effective catalytic system. A thermal regenerative path was adopted to enhance the catalyst stability and reusability. Quenching tests and electron paramagnetic resonance (EPR) spectroscopic analysis further revealed the dominant role of singlet oxygen (¹O₂), a non-radical reactive species, in the degradation of HBA. The current research work will not only provide a facile strategy for development of a carbocatalytic system but also open a new perspective for degradation of emerging contaminants such as HBA via a non-radical route.

Van der Waals (VDW) heterojunctions in a 2D/2D contact provide the highest area for the separation and transfer of charge carriers. In this work, a top-down strategy with a gas erosion process was employed to fabricate a 2D/2D carbon nitride VDW heterojunction in carbon nitride (g-C₃N₄) with carbon-rich carbon nitride. The created 2D semiconducting channel in the VDW structure exhibits enhanced electric field exposure and radiation absorption, which facilitates the separation of the charge carriers and their mobility. Consequently, compared with bulk g-C₃N₄ and its nanosheets, the photocatalytic performance of the fabricated carbon nitride VDW heterojunction in the water splitting reaction to hydrogen is improved by 8.6 and 3.3 times, respectively, while maintaining satisfactory photo-stability. Mechanistically, the finite element method (FEM) was employed to evaluate and clarify the contributions of the formation of VDW heterojunction to enhanced photocatalysis, in agreement quantitatively with experimental ones. This study provides a new and effective strategy for the modification and more insights to performance improvement on polymeric semiconductors in photocatalysis and energy conversion.

Photocatalytic hydrogen evolution reaction (PC-HER) provides a solution to energy crisis and environmental pollution. Herein, different graphitic carbon nitride (g-C₃N₄)-based van der Waals (vdW) type II homojunctions have been fabricated and g-C₃N₄/K-doped g-C₃N₄ nanosheets have an outstanding PC-HER rate of 1,243 μmol·h⁻¹·g⁻¹ under visible light, higher than that of bulk g-C₃N₄, doped g-C₃N₄ nanosheets, and mixed nanosheets. The enhanced PC-HER performance can be ascribed to the cooperative effects of the shortened bandgap, enlarged specific surface area, matched type II energy band structure, “face to face” vdW charge interaction, and peculiarly partite positions of the conduction and valence bands in different layers. Besides, the type II junctions were found superior to binary type II junction. This study highlights the synergistic effect of different strategies in improving the PC-HER capacities of g-C₃N₄, especially the application of particular vdW junctions, and provides new insights to the structures and mechanism.