Bi-directional charge transfer channels in highly crystalline carbon nitride enabling superior photocatalytic hydrogen evolution.

Introducing a donor-acceptor (D-A) unit is an effective approach to facilitate charge transfer in polymeric carbon nitride (PCN) and enhance photocatalytic performance. However, the introduction of hetero-molecules can lead to a decrease in crystallinity, limiting interlayer charge transfer and inhibiting further improvement. In this study, we constructed a novel D-A type carbon nitride with significantly higher crystallinity and a bi-directional charge transfer channel, which was achieved through 2,5-thiophenedicarboxylic acid (2,5-TDCA)-assisted self-assembly followed by KCl-templated calcination. The thiophene and cyano groups introduced serve as the electron donor and acceptor, respectively, enhancing in-plane electron delocalization. Additionally, introduced potassium ions are intercalated among the adjacent layers of carbon nitride, creating an interlayer charge transfer channel. Moreover, the highly ordered structure and improved crystallinity further facilitate charge transfer. As a result, the as-prepared photocatalyst exhibits superior photocatalytic hydrogen evolution (PHE) activity of 7.449 mmol h-1 g-1, which is 6.03 times higher than that of pure carbon nitride. The strategy of developing crystalline D-A-structured carbon nitride with controlled in-plane and interlayer charge transfer opens new avenues for the design of carbon nitride with enhanced properties for PHE.

Enhancing Photocatalytic Degradation via the Synergetic Effect of Vacancies and Built-In Potential in a BiOCl/BiVO4 p-n Heterojunction.

Photoinduced charge separation and surface reactions are essential for ensuring high quantum efficiency of the photochemical and photophysical processes. BiVO4-based heterojunctions are promising materials for high-performance photocatalysts; however, their photocatalytic performance is significantly lower than the theoretical limit due to the sluggish water oxidation dynamics and rapid recombination of charge carriers on the catalyst surface. To address these issues, oxygen vacancies (OVs) are introduced to a rationally designed BiVO4-based heterojunction using built-in potential and gradient OVs to promote the separation of carriers and increase the photocatalytic activity. The heterojunctions with OVs exhibit a 2-fold increase in the photocatalytic activity for phenol degradation compared with that of pristine BiVO4. Additionally, density functional theory is applied to elucidate the synergistic mechanism of light absorption and charge separation in BiOCl/BiVO4 p-n heterojunction photocatalysts containing vacancies. The obtained results demonstrate a synergistic effect of vacancies and the built-in potential, providing a pathway for defect engineering in photocatalytic processes.

Nanoarchitectonics on Z-scheme and Mott-Schottky heterostructure for photocatalytic water oxidation via dual-cascade charge-transfer pathways.

The bottleneck for water splitting to generate hydrogen fuel is the sluggish oxidation of water. Even though the monoclinic-BiVO4 (m-BiVO4)-based heterostructure has been widely applied for water oxidation, carrier recombination on dual surfaces of the m-BiVO4 component have not been fully resolved by a single heterojunction. Inspired by natural photosynthesis, we established an m-BiVO4/carbon nitride (C3N4) Z-scheme heterostructure based on the m-BiVO4/reduced graphene oxide (rGO) Mott-Schottky heterostructure, constructing the face-contact C3N4/m-BiVO4/rGO (CNBG) ternary composite to remove excessive surface recombination during water oxidation. The rGO can accumulate photogenerated electrons from m-BiVO4 through a high conductivity region over the heterointerface, with the electrons then prone to diffuse along a highly conductive carbon network. In an internal electric field at the heterointerface of m-BiVO4/C3N4, the low-energy electrons and holes are rapidly consumed under irradiation. Therefore, spatial separation of electron-hole pairs occurs, and strong redox potentials are maintained by the Z-scheme electron transfer. These advantages endow the CNBG ternary composite with over 193% growth in O2 yield, and a remarkable rise in ·OH and ·O2- radicals, compared to the m-BiVO4/rGO binary composite. This work shows a novel perspective for rationally integrating Z-scheme and Mott-Schottky heterostructures in the water oxidation reaction.

Synergetic Nanoarchitectonics of Defects and Cocatalysts in Oxygen-Vacancy-Rich BiVO4/reduced graphene oxide Mott-Schottky Heterostructures for Photocatalytic Water Oxidation.

Water oxidation process is a pivotal step of photosynthesis and stimulates the progress of high-performance catalysts for renewable fuel production. Despite the performance benefit of cocatalysts, defect engineering holds promise to settle inherent limitations of semiconductors aiming at sluggish water oxidation. Here, we modify the in situ growth pathway of monoclinic BiVO4 (m-BiVO4) on reduced graphene oxide (rGO), constructing abundant surface oxygen vacancies (OV)-incorporated m-BiVO4/rGO heterostructure toward water oxidation reaction under visible light. Owing to the OV in the m-BiVO4 component, a vacancy-related defect level allows more electrons to be photoexcited by low-energy photons to cause the electron transition, boosting photoabsorption as well as photoexcitation. Besides, the OV can reinforce surface adsorption and reduce the dissociation energy of water molecules. Particularly because of the synergy of OV and cocatalyst rGO, the OV functions as electron-trapped sites to facilitate the carrier separation; the rGO not only receives electrons from m-BiVO4 promoted by internal electric field over Mott-Schottky heterostructures but also spurs further electron diffusion along a highly conductive carbon network. These merits enable the OV-incorporated m-BiVO4/rGO heterostructure with an over 209% growth in O2 yield relative to the counterpart. The increased performance is also validated by the significant rise of •OH radicals and •O2- radicals. The current work paves a novel avenue for the integration of defect engineering and cocatalyst coupling in artificial photosynthesis.

Recent advancements in g-C3N4-based photocatalysts for photocatalytic CO2 reduction: a mini review.

Carbon dioxide (CO2) is a very important micro-molecular resource. Using CO2 captured from the atmosphere for high-output synthesis of chemicals as raw materials has great significance and potential for various industrial applications. Since the industrial revolution in the 18th century, manmade CO2 emission has increased by 45%, which negatively impacts the planetary climate by the so-called greenhouse effect. Therefore, high-efficiency photocatalysis and photocatalysts for CO2 conversion have become the most important challenges and milestones throughout the world. In consideration of this, various catalysts have been explored. Among these, graphitic carbon nitride (g-C3N4) as a semiconductor is emerging as a highly promising photocatalyst for removing CO2 from the atmosphere. Moreover, due to its excellent chemical stability and unique band structure, g-C3N4 has exhibited significant application potential for photocatalysis. This review summarizes the advancements that have been made in the synthesis and photocatalytic applications of g-C3N4-based catalysts for CO2 reduction in recent years and explains the future challenges and prospects in this vital area of research.