New insight into enhanced photocatalytic selectivity of g-C3N4 by nitrogen vacancy introduction: Experimental study and theoretical calculation.

Constructing photocatalyst with both high efficiency and selectivity is highly desired in water treatment process. However, it is difficult to realize the selectivity of photocatalysis due to the non-selective oxidative species produced in this process. Herein, for the first time, the photocatalytic selectivity was achieved on g-C3N4 (CN) through N vacancy introduction for effective removal of organic pollutants, and the mechanism of vacancy induced selectivity enhancement was studied. The nitrogen vacancy modified CN (VCN) showed enhanced photocatalytic activity and unique selectivity towards phenolic compounds with electron-donating group, whose kinetic constant for p-aminophenol (p-NH2) degradation was 5.95 times higher than that over CN. Moreover, VCN photocatalytic system also displayed similar selectivity in binary pollutant systems. Characteristics and theoretical calculation results confirmed the enhanced photocatalytic performance and selectivity of VCN was mainly attributed to the effect of N vacancy. On one hand, electron-deficient N vacancy enhanced the adsorption of the O2 and phenolic compounds, which promoted the production of O2•- and strengthened the photocatalytic surface reaction. On the other hand, the N vacancy preferred to adsorb the electron-donating groups of phenolic compounds, which resulted in their selective removal.