Decorating Carbon Nitride via the Integration of Phosphorylation with Carbon Self‐doping toward Enhanced Photocatalytic Hydrogen Evolution

Promoting the transfer of liquid phase protons and the separation of photo‐induced carriers can both enhance photocatalytic hydrogen production, however, their collaboration still faces challenges. In this paper, graphitic carbon nitride (g‐C 3 N 4 ) was modified by carbon self‐doping and the phosphorylation with aminotris (methylenephosphonic acid) (ATMP) for visible light‐driven photocatalytic hydrogen evolution. Experimental results and theoretical calculations indicated that carbon self‐doping could facilitate the transport and separation of charge carriers and the enhancement of visible light absorption with the formation of delocalized big π bonds among the adjacent heptazine rings. ATMP phosphorylation could not only tune the electronic structure, drive charge separation, but also greatly improve the transfer of protons to the reactive site through constructing the solid–liquid contact interface on the surface of g‐C 3 N 4 . Furthermore, the charge transport and separation in the carbon self‐doped g‐C 3 N 4 could be coupled with the proton transfer of the phosphate groups on grafted ATMP by the aid of deposited Pt nanoparticle co‐catalysts, exhibiting mutual promoting effect. Beneficial from the synergy of carbon self‐doping and phosphorylation, the optimized sample exhibited the hydrogen evolution rate of 3483.2 μmol g −1 h −1 , being 18.7 folds that of g‐C 3 N 4 and also behaved excellent recycle stability. This research supplies a reliable reference for boosting the performance of photocatalytic hydrogen production through the collaborative promotion of proton transfers and charge transports.