Promoted Hydrogen Peroxide Production from Pure Water on g-C3N4 with Nitrogen Defects Constructed through Solvent-Precursor Interactions: Exploring a Complex Story in Piezo-Photocatalysis.

Hydrogen peroxide (H2O2) production via oxygen (O2) reduction reaction (ORR) in pure water (H2O) through graphitic carbon nitrides (g-C3N4)-based piezo-photocatalysts is an exciting approach in many current studies. However, the low Lewis-acid properties of g-C3N4 limited the catalytic performance because of the low O2 adsorption efficacy. To overcome this challenge, the interaction of g-C3N4 precursors with various solvents are utilized to synthesize g-C3N4, possessing multiple nitrogen-vacant species via thermal shocking polymerization. These results suggest that the lack of nitrogen in g-C3N4 and the incident introduction of oxygen-functional groups enhance the Lewis acid-base interactions and polarize the g-C3N4 lattices, leading to the enormous enhancement. Furthermore, the catalytic mechanisms are thoroughly studied, with the formation of H2O2 proceeding via radical and water oxidation pathways, in which the roles of light and ultrasound are carefully investigated. Thus, these findings not only reinforce the potential view of metal-free photocatalysts, accelerating the understanding of g-C3N4 working principles to generate H2O2 based on the oxygen reduction and water oxidation reactions, but also propose a facile one-step way for fabricating highly efficient and scalable photocatalysts to produce H2O2 without using sacrificial agents, pushing the practical application of in situ solar H2O2 toward real-world scenarios.

Simultaneously Utilizing Excited Holes and Electrons for Piezoelectric-Enhanced Photoproduction of H2O2 from S-Scheme 2D S-Doped VOx/g-C3N4 Nanostructures.

2D/2D step-scheme (S-scheme) piezo-photocatalysts for the production of fine chemicals, such as hydrogen peroxide (H2O2), have attracted significant attention of global scientists owing to the efficiency in utilizing surface piezoelectric effects from 2D materials to overcome rapid charge recombination in photocatalytic processes. In this research, we reported the fabrication of 2D S-doped VOx deposited on 2D g-C3N4 to produce H2O2 via the piezo-photocatalytic process with high production yields at 20.19 mmol g-1 h-1, which was 1.75 and 4.87 times higher than that from solely piezo-catalytic and photocatalytic H2O2 generation. The finding pointed out that adding sulfur (S) to VOx can help to improve the catalytic outcomes by modifying the electronic properties of pristine VOx. In addition, when coupled with g-C3N4, the presence of S limits the formation of graphene in the VOx/g-C3N4 composites, causing shielding effects and pushing the cascade reactions toward water generation in the materials. Besides, the research also sheds light on the charge transport between g-C3N4 and S-VOx under irradiation and how the composites work to trigger the formation of H2O2. The presence of S in the composite systems enhances charge transfer between two semiconductors by strengthening the internal electric fields (IEF) to drive electrons moving in one direction, as demonstrated by density functional theory (DFT) calculations. Moreover, the formation of H2O2 significantly relies on the reduction of oxygen to generate oxygenic radical species at the g-C3N4 sites. Meanwhile, S-VOx provides oxidative sites in the composites to oxidize water molecules to directly or indirectly generate H2O2 or O2, which will further participate in the reactions to produce the final products. This study confirms the validation of S-scheme piezo-photocatalysts, thus encouraging further research on developing heterojunction materials with high catalytic efficiency, which can be used in practical conditions.