The facile synthesis of ordered carbon nitride (CN) sheets with excellent photoactivity for hydrogen production and pollutant degradation is reported. To direct the synthesis of CN materials, sulfur‐based supramolecular assemblies composed of bismuthiol and melamine are utilized. Upon calcination at high temperature, CN materials with tunable morphology, porosity, and photophysical properties are obtained. The influence of several parameters including solvents, solubility, and monomer concentration are studied to determine their effect on the supramolecular assemblies and on the resulting CN properties and photoactivity. The best CN, prepared in dimethyl sulfoxide as the solvent, exhibits high specific surface area, beneficial electronic structure, and excellent photocatalytic activity for the hydrogen evolution reaction and the degradation of rhodamine B dye.

Polymeric carbon nitride (CN) has emerged as a promising semiconductor in photoelectrochemical devices, thanks to its unique electronic and catalytic properties, low price, stability in various chemical environments, and benign nature. Decent progress in the deposition and growth of CN layers on substrates has been achieved using several deposition and growth methods; however, the properties of the layer, including the quality of its contact with the substrate and its structural properties, are still largely dependent on the surface properties of said substrate. Here, a new approach is introduced in which a spray‐coated seeding layer composed of CN monomers directs the growth of a homogenous, thick CN layer on a substrate by calcination at high temperature in the presence of melamine vapor. Uniform CN layers with strong adhesion to the substrate are obtained. The influence of the seeding layer and the vapor composition on the photoelectrochemical, optical, and structural properties is studied in detail. The best‐performing electrode, based on urea as the seeding layer, demonstrates good activity as a photoanode in photoelectrochemical cells, reaching up to 300 µA cm−2 in the presence of a hole scavenger.

The direct conversion of CO2 into methanol through hydrogenation reactions by heterogeneous catalysts is considered a promising green approach for fuel production. The most researched catalyst for methanol formation is Cu, usually in combination with other metals dispersed on different substrates. However, several challenges, such as the low stability, activity, and selectivity of the catalyst, hinder further progress. Here, we present catalysts consisting of Cu and Fe nanoparticles deposited on lightweight carbon-phosphorous-nitrogen (CPN) materials as the support for CO2 hydrogenation to methanol. Detailed analysis reveals a correlation between the elemental composition of the CPN supports and their CO2 adsorption capability, which benefits CO2 conversion to methanol. The unique elemental composition ensures uniform dispersion of both Cu and Fe nanoparticles on CPN and prevents the oxidation of the Cu active sites during the reaction. The best performing sample of the catalysts exhibits a remarkable methanol production yield of 9.82 mol kgcat –1 h–1 at 250 °C under 20 bar, with good methanol selectivity, negligible CO formation, and good stability for 12 h under harsh conditions.

The facile synthesis of chiral materials is of paramount importance for various applications. Supramolecular preorganization of monomers for thermal polymerization has been proven as an effective tool to synthesize carbon and carbon nitride‐based (CN) materials with ordered morphology and controlled properties. However, the transfer of an intrinsic chemical property, such as chirality from supramolecular assemblies to the final material after thermal condensation, has never been shown. Here, we report the large‐scale synthesis of chiral CN materials capable of enantioselective recognition. To achieve this, we designed supramolecular assemblies with a chiral center that remains intact at elevated temperatures. The optimized chiral CN demonstrates an enantiomeric preference of ca. 14%; CN electrodes were also prepared and show stereoselective interactions with enantiomeric probes in electrochemical measurements. By adding chirality to the properties transferrable from monomers to the final product of a thermal polymerization, this study confirms the potential of using supramolecular precursors to produce carbon and CN materials and electrodes with designed chemical properties.

The facile synthesis of chiral materials is of paramount importance for various applications. Supramolecular preorganization of monomers for thermal polymerization has been proven as an effective tool to synthesize carbon and carbon nitride‐based (CN) materials with ordered morphology and controlled properties. However, the transfer of an intrinsic chemical property, such as chirality from supramolecular assemblies to the final material after thermal condensation, has never been shown. Here, we report the large‐scale synthesis of chiral CN materials capable of enantioselective recognition. To achieve this, we designed supramolecular assemblies with a chiral center that remains intact at elevated temperatures. The optimized chiral CN demonstrates an enantiomeric preference of ca. 14%; CN electrodes were also prepared and show stereoselective interactions with enantiomeric probes in electrochemical measurements. By adding chirality to the properties transferrable from monomers to the final product of a thermal polymerization, this study confirms the potential of using supramolecular precursors to produce carbon and CN materials and electrodes with designed chemical properties.