Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO2 Photoreduction

Defect engineering has being regarded as one of the effective ways to regulate chemical and electronic structure of semiconductors. Recently, our collaborative work has shown experimentally that carbon vacancy on polymeric carbon nitride (CV) can greatly improve the CO2 to CO conversion with a 45-fold improvement over the polymeric carbon nitride (Angew. Chem. Int. Ed., 2019, 58, 1134). In order to clarify the detailed mechanism of promotion, we have systematically studied the electronic properties of CV and hydrogenated CV (CV+H) as well as the effective CO2 reduction reaction through density functional theory calculations. We found that it is the synergistic effect for the CO2 reduction reaction in the CV systems, as the onset potentials of several CVs are much lower than that of the polymeric carbon nitride. In particular, the onset potentials of CV1, CV2, and CV2+H are around 0.9 similar to 1.5 eV with a strong chemisorbed CO2 on them. Combined with the analysis of the electronic properties, our results confirm that defect engineering increases the lifetime of photo-generated charges, improves photocatalytic activity, and promotes the CO2 reduction reaction on the defected polymeric carbon nitrides.