As a promising two-dimensional conjugated polymer, graphitic carbon nitride (g-C3 N4 ) has been utilized as a low-cost, robust, metal-free, and visible-light-active photocatalyst in the field of solar energy conversion. This Review mainly describes the latest advances in g-C3 N4 photocatalysts for water splitting. Their application in CO2 conversion, organosynthesis, and environmental purification is also briefly discussed. The methods to modify the electronic structure, nanostructure, crystal structure, and heterostructure of g-C3 N4 , together with correlations between its structure and performance are illustrated. Perspectives on the challenges and opportunities for the future exploration of g-C3 N4 photocatalysts are provided. This Review will promote the utilization of g-C3 N4 materials in the fields of photocatalysis, energy conversion, environmental remediation, and sensors.
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.
Direct splitting of pure water into H2 and O2 in a stoichiometric molar ratio of 2 : 1 by conjugated polymers via a 4-electron pathway was established for the first time, as demonstrated here using a g-C3N4 polymer and redox co-catalysts of Pt and Co species.
The generation of sustainable and stable semiconductors for solar energy conversion by photoredox catalysis, for example, light-induced water splitting and carbon dioxide reduction, is a key challenge of modern materials chemistry. Here we present a simple synthesis of a ternary semiconductor, boron carbon nitride, and show that it can catalyse hydrogen or oxygen evolution from water as well as carbon dioxide reduction under visible light illumination. The ternary B–C–N alloy features a delocalized two-dimensional electron system with sp2 carbon incorporated in the h-BN lattice where the bandgap can be adjusted by the amount of incorporated carbon to produce unique functions. Such sustainable photocatalysts made of lightweight elements facilitate the innovative construction of photoredox cascades to utilize solar energy for chemical conversion.
Polymeric or organic semiconductors are promising candidates for photocatalysis but mostly only show moderate activity owing to strongly bound excitons and insufficient optical absorption. Herein, we report a facile bottom-up strategy to improve the activity of a carbon nitride to a level in which a majority of photons are really used to drive photoredox chemistry. Co-condensation of urea and oxamide followed by post-calcination in molten salt is shown to result in highly crystalline species with a maximum π-π layer stacking distance of heptazine units of 0.292 nm, which improves lateral charge transport and interlayer exciton dissociation. The addition of oxamide decreases the optical band gap from 2.74 to 2.56 eV, which enables efficient photochemistry also with green light. The apparent quantum yield (AQY) for H evolution of optimal samples reaches 57 % and 10 % at 420 nm and 525 nm, respectively, which is significantly higher than in most previous experiments.
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.
Polymeric carbon nitride (PCN), in either triazine or heptazine form, has been regarded as a promising metal-free, environmentally benign, and sustainable photocatalyst for solar hydrogen production. However, PCN in most cases only exhibits moderate activity owing to its inherent properties, such as rapid charge carrier recombination. Herein we present a triazine-heptazine copolymer synthesized by simple post-calcination of PCN in eutectic salts, that is, NaCl/KCl, to modulate the polymerization process and optimize the structure. The construction of an internal triazine-heptazine donor-acceptor (D-A) heterostructure was affirmed to significantly accelerate interface charge transfer (CT) and thus boost the photocatalytic activity (AQY=60 % at 420 nm). This study highlights the construction of intermolecular D-A copolymers in NaCl/KCl molten salts with higher melting points but in the absence of lithium to modulate the chemical structure and properties of PCN.
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