The structural differences of perovskite ATiO3 (A = Ca, Sr) dictate the photocatalytic VOCs mineralization efficiency.

[Display omitted] • Efficient and stable photocatalytic VOCs decomposition was achieved on SrTiO 3. • The perovskites with special electronic structures dictate photocatalysis efficiency. • The electronic structure of SrTiO 3 could promote the activation of O 2 and H 2 O. • The DFT and In situ DRIFTS are combined to reveal the ring-opening mechanism. • The reaction mechanisms of photocatalytic decomposition of VOCs was proposed. Considering that the structural differences could dictate the photocatalytic efficiency, the cubic SrTiO 3 (STO) and tetragonal CaTiO 3 (CTO) were developed to illustrate the structure–activity relationship. The STO with cubic structure demonstrates much higher photocatalytic toluene removal efficiency (ca. 80.0%) than that of CTO (ca. 20.0%), which can be ascribed to boosted formation of reactive oxygen species (ROS), increased selectivity of intermediates, and promoted ring-opening and mineralization rate. Combining theoretical simulation and experimental characterization, the results reveal that the O 2 and H 2 O molecules tend to be adsorbed on the cubic STO, which boosts the formation of ROS. Also, highly selective formation of intermediate (benzoic acid) has been realized to accelerate ring-open and mineralization process as evidenced by the smooth conversion of STO as indicated by Gibbs free energy. This work provides new perspectives on the understanding of relationship between intrinsic structure and photocatalytic performance. [ABSTRACT FROM AUTHOR]