Crucial roles of triazinic-N
O and C
O groups in photocatalytic water splitting on graphitic carbon nitride†
Abstract
As a typical metal-free photocatalyst, water splitting on graphitic carbon nitride (g-C3N4) has drawn increasing attention. Uncovering its reaction mechanism, which still remains a mystery despite extensive studies, would be of great help for the design of efficient metal-free photocatalysts. Through first-principles calculations we discovered that overall water splitting on g-C3N4 relies heavily on two nonadiabatic transitions and yielding of the vital active site CO. The two nonadiabatic transitions, one between two excited states while another between the excited and the ground states, trigger the reaction and split an H2O molecule into a triazinic-N–H and triazinic-N–OH pair. Formation of triazinic-N–OH stabilizes electrons in the π* orbitals of g-C3N4 and thereby facilitates the reduction reaction. C
O is developed from triazinic-N–OH. The significance of C
O lies in that it provides a site at which another H2O molecule could split spontaneously into a C–OOH and N–H pair without the aid of photons so that the oxidation evolution reaction could occur thereafter. The local electric field imposed upon the H2O molecule that is hydrogen-bonded to the triazinic N is a key factor affecting the nonadiabatic transitions and thus splitting of this H2O. To increase the water splitting efficiency, the stability of C
O should be improved as it tends to evolve into triazinic-N
O which is inactive for H2O splitting.