Graphitic carbon nitride (g-CN) is an emerging metal-free photocatalyst for solar energy conversion via water splitting and CO2 fixation. Herein, we used preheated melamine as a starting material in combination with the salt melt method to synthesize a crystalline tri-s-triazine-based g-CN. The as-obtained sample exhibited high stability and photocatalytic activity toward hydrogen and oxygen production from water splitting. In addition, by adding phosphate to mimic natural photosynthetic environment, the apparent quantum yield (AQY) for the hydrogen production reached 50.7% at 405 nm, which is the highest value ever reported for conjugated carbon nitride polymers in hydrogen evolution photocatalysis. The results of this study demonstrate that crystalline covalent tri-s-triazine frameworks hold great promise for solar energy applications.

Tri-s-triazine-based crystalline carbon nitride nanosheets (CCNNSs) have been successfully extracted via a conventional and cost-effective sonication-centrifugation process. These CCNNSs possess a highly defined and unambiguous structure with minimal thickness, large aspect ratios, homogeneous tri-s-triazine-based units, and high crystallinity. These tri-s-triazine-based CCNNSs show significantly enhanced photocatalytic hydrogen generation activity under visible light than g-C N , poly (triazine imide)/Li Cl , and bulk tri-s-triazine-based crystalline carbon nitrides. A highly apparent quantum efficiency of 8.57% at 420 nm for hydrogen production from aqueous methanol feedstock can be achieved from tri-s-triazine-based CCNNSs, exceeding most of the reported carbon nitride nanosheets. Benefiting from the inherent structure of 2D crystals, the ultrathin tri-s-triazine-based CCNNSs provide a broad range of application prospects in the fields of bioimaging, and energy storage and conversion.

Metal-free heterostructure photocatalysts composed of black phosphorus (BP) and polymeric carbon nitride (CN) are successfully synthesized via a one-step liquid exfoliation method assisted by sonication. The combination of BP with CN strengthens the visible-light harvesting ability, facilitates the charge separation in the photocatalytic process, and renders promoted activity of photoinduced molecular oxygen activation, such as superoxide radicals (·O 2 − ) evolution and H 2 O 2 production. This work highlights that coupling semiconductors with well-matched band levels provide a flexible route to enhance the performance of photocatalysts for producing reactive oxygen species, and gives ideas for the design of highly active and metal-free materials toward sustainable solar-to-chemical energy conversion and environmental remediation.

The delamination of layered crystals that produces single or few-layered nanosheets while enabling exotic physical and chemical properties, particularly for semiconductor functions in optoelectronic applications, remains a challenge. Here, we report a facile and green approach to prepare few-layered polymeric carbon nitride (PCN) semiconductors by a one-step carbon/nitrogen steam reforming reaction. Bulky PCN, obtained from typical precursors including urea, melamine, dicyandiamide, and thiourea, are exfoliated into few-layered nanosheets, while engineering its surface carbon vacancies. The unique sheet structures with strengthened surface properties endow PCNs with more active sites, and an increased charge separation efficiency with a prolonged charge lifetime, drastically promoting their photoredox performance. After an assay of a H evolution reaction, an apparent quantum yield of 11.3 % at 405 nm was recorded for the PCN nanosheets, which is much higher than those of PCN nanosheets. This delamination method is expandable to other carbon-based 2D materials for advanced applications.

Aerogel structures have attracted increasing research interest in energy storage and conversion owing to their unique structural features, and a variety of materials have been engineered into aerogels, including carbon-based materials, metal oxides, linear polymers and even metal chalcogenides. However, manufacture of aerogels from nitride-based materials, particularly the emerging light-weight carbon nitride (CN) semiconductors is rarely reported. Here, we develop a facile method based on self-assembly to produce self-supported CN aerogels, without using any cross-linking agents. The combination of large surface area, incorporated functional groups and three-dimensional (3D) network structure, endows the resulting freestanding aerogels with high photocatalytic activity for hydrogen evolution and H O production under visible light irradiation. This work presents a simple colloid chemistry strategy to construct 3D CN aerogel networks that shows great potential for solar-to-chemical energy conversion by artificial photosynthesis.