Synthesis of carbon nitrogen phosphorus materials from highly-organized organic crystals

Carbon and nitrogen(CN) based semiconductors materials have gained a lot of attention as metal free materials designed from low cost and commercial available precursors. CN materials also earned a lot of interest due to their wide range of applications such as heterogeneous catalysis, sensors, water splitting, etc. Heteroatoms incorporation into CN material can tune its optical, electronic, thermal stability and (photo)electrochemical properties, only by controlling the different amounts of atoms within the material. Introducing phosphorous atoms into CN matrix enables the modification of various properties such as: electrical conductivity, photocatalytic performance and oxidation stability due to the insertion of atoms with different electronegativity and radius size, into the CN network.

The synthesis of these Phosphorous Carbon Nitrogen(PCN) materials is complicated as the phosphorus’s large covalent radius impedes its incorporation into the CN network. Furthermore, P-N bond is rarely reported in CN matrix, which presents a formidable synthetic challenge. Herein we show a facile scalable and simple way to control phosphorus insertion into CN matrix with up to 45% of phosphorus in weight, by using organic Phosphoric acid(PA): Melamine(M) single crystals as PCN materials’ precursors. The new synthetic tool allows the fine-tuning of the photocatalytic activity, chemical, thermal stability and electronic properties. These PCN materials also demonstrated a good oxidation resistance upon heating to 1000 ⁰C.