On-Surface Polymerization of In-Plane Highly Ordered Carbon Nitride Nanosheets toward Photocatalytic Mineralization of Mercaptan Gas.

2D carbon nitride nanosheets have attracted ever-increasing interest in photocatalysis due to their unique structural advantages. However, the nanosheets synthesized by the traditional methods, such as post oxidation and liquid exfoliation, have suffered from in-plane disorder with abundant structural defects, which seriously counteracts their structural benefits for photocatalysis. Herein, it is demonstrated that polymer carbon nitride nanosheets with in-plane highly ordered structure (PCNNs-IHO) can be successfully prepared by on-surface polymerization of melamine on NaCl crystal surface at elevated temperatures. The NaCl crystals with relative high surface energy not only facilitate the adsorption and activation of melamine to undergo condensation reaction, but also function as unique substrates to orientate the assembly of 2D nanosheet structure. In addition, NaCl also acts as a reactant to provide Na+ doping into carbon nitride matrix, affording PCNNs-IHO with robust structural base sites. Benefiting from this structural basicity, PCNNs-IHO exhibits superior photocatalytic performance toward CH3 SH mineralization under visible light irradiation.

Metalated carbon nitrides as base catalysts for efficient catalytic hydrolysis of carbonyl sulfide.

A new type of base catalyst was designed and prepared by metalation of carbon nitrides with alkali metal ions. The as-prepared metalated carbon nitride composites showed enhanced basicity and efficient catalytic hydrolysis of carbonyl sulfide. The results of this study demonstrate that the metalation of carbon nitrides holds great promise for base catalysis applications.

Assembly of protonated mesoporous carbon nitrides with co-catalytic [Mo3S13]2- clusters for photocatalytic hydrogen production.

The photocatalytic activity of protonated ordered mesoporous carbon nitride (pom-CN) was significantly improved by assembling anionic [Mo3S13]2- clusters as cocatalysts onto the surface and channel of pom-CN via electrostatic interactions. This work demonstrates the feasibility of employing solution chemistry to assemble co-catalysts in the form of ionic clusters as building blocks into a photosynthetic architecture.

Carbon-Doped BN Nanosheets for the Oxidative Dehydrogenation of Ethylbenzene.

Carbon-based catalysts have demonstrated great potential for the aerobic oxidative dehydrogenation reaction (ODH). However, its widespread application is retarded by the unavoidable deactivation owing to the appearance of coking or combustion under ODH conditions. The synthesis and characterization of porous structure of BCN nanosheets as well as their application as a novel catalyst for ODH is reported. Such BCN nanosheets consist of hybridized, randomly distributed domains of h-BN and C phases, where C, B, and N were confirmed to covalent bond in the graphene-like layers. Our studies reveal that BCN exhibits both high activity and selectivity in oxidative dehydrogenation of ethylbenzene to styrene, as well as excellent oxidation resistance. The discovery of such a simple chemical process to synthesize highly active BCN allows the possibility of carbocatalysis to be explored.

Sulfur-Doped Carbon Nitride Polymers for Photocatalytic Degradation of Organic Pollutant and Reduction of Cr(VI).

As a promising conjugated polymer, binary carbon nitride has attracted extensive attention as a metal-free and visible-light-responsive photocatalyst in the area of photon-involving purification of water and air. Herein, we report sulfur-doped polymeric carbon nitride microrods that are synthesized through thermal polymerization based on trithiocyanuric acid and melamine (TM) supramolecular aggregates. By tuning the polymerization temperature, a series of sulfur-doped carbon nitride microrods are prepared. The degradation of Rhodamine B (RhB) and the reduction of hexavalent chromium Cr(VI) are selected as probe reactions to evaluate the photocatalytic activities. Results show that increasing pyrolysis temperature leads to a large specific surface area, strong visible-light absorption, and accelerated electron-hole separation. Compared to bulk carbon nitride, the highly porous sulfur-doped carbon nitride microrods fabricated at 650 °C exhibit remarkably higher photocatalytic activity for degradation of RhB and reduction of Cr(VI). This work highlights the importance of self-assembly approach and temperature-control strategy in the synthesis of photoactive materials for environmental remediation.

Decorating CoP and Pt Nanoparticles on Graphitic Carbon Nitride Nanosheets to Promote Overall Water Splitting by Conjugated Polymers.

The splitting of water into H2 and O2 using solar energy is one of the key steps in artificial photosynthesis for the future production of renewable energy. Here, we show the first use of CoP and Pt nanoparticles as dual co-catalysts to modify graphitic carbon nitride (g-C3 N4 ) polymer to achieve overall water splitting under visible light irradiation. Our findings demonstrate that loading dual co-catalysts on delaminated g-C3 N4 imparts surface redox sites on the g-C3 N4 nanosheets that can not only promote catalytic kinetics but also promote charge separation and migration in the soft interface, thus improving the photocatalytic efficiency for overall water splitting. This robust, abundant, and stable photocatalyst based on covalent organic frameworks is demonstrated to hold great promise by forming heterojunctions with CoP and Pt for catalyzing the direct splitting of water into stoichiometric H2 and O2 using energy from photons.

Helical graphitic carbon nitrides with photocatalytic and optical activities.

Graphitic carbon nitride can be imprinted with a twisted hexagonal rod-like morphology by a nanocasting technique using chiral silicon dioxides as templates. The helical nanoarchitectures promote charge separation and mass transfer of carbon nitride semiconductors, enabling it to act as a more efficient photocatalyst for water splitting and CO2 reduction than the pristine carbon nitride polymer. This is to our knowledge a unique example of chiral graphitic carbon nitride that features both left- and right-handed helical nanostructures and exhibits unique optical activity to circularly polarized light at the semiconductor absorption edge as well as photoredox activity for solar-to-chemical conversion. Such helical nanostructured polymeric semiconductors are envisaged to hold great promise for a range of applications that rely on such semiconductor properties as well as chirality for photocatalysis, asymmetric catalysis, chiral recognition, nanotechnology, and chemical sensing.