Probing ring-opening pathways for efficient photocatalytic toluene decomposition

The ring-opening process is the rate-determining step for photocatalytic decomposition of aromatic volatile organic compounds (VOCs). However, the ring-opening pathway has not been fully revealed, which enables efficient photocatalytic VOC degradation. Taking the photocatalytic toluene degradation as a typical case, the ring-opening pathway and regulation strategy were systematically investigated and proposed with an aim to regulate the rate-determining step and accelerate the reaction rates. Herein, BiOCl with tailored facets was designed as a model photocatalyst to clarify the mechanism of photocatalytic toluene degradation. Theoretical calculations and in situ DRIFTS technology were closely combined to dynamically predict and monitor the photocatalytic toluene degradation reactions. It is revealed that the lowest energy barrier was precisely located at the ring-opening of benzoic acid which was generated from toluene oxidation. This result implied that the benzyl must be fully oxidized to benzoic acid to elevate the ring-opening reaction rates. Moreover, the alternative charge arrangement on the {010} facet of BiOCl facilitated the benzyl oxidation and selectivity for benzoic acid ring-opening reactions, subsequently resulting in remarkably enhanced photocatalytic efficiency, exceeding that of the {001} facet by 100% towards toluene decomposition. This work demonstrates that probing and tailoring the ring-opening pathway are vital to increase the overall toluene decomposition efficiency and could provide new insights into the understanding of the photocatalytic reactions in VOC degradation.