Abstract

Heterogeneous photocatalytic systems generally lack thermodynamic dependence on the degradation of organic pollutants in aqueous solution. Therefore, it is important to reveal the reasons for the inhibited surface kinetics but still be neglected. Herein, we reveal the mechanism that BiVO4 can’t degrade organics although it is thermodynamically feasible. The surface solvation and formation of double layer (compact layer and diffuse layer) makes low-polarity organics far away from the surface of BiVO4. We found that the introduction of sulfite can solve this problem. Theory calculation illustrates that sulfite can enter into the compact layer because of its higher adsorption energy on BiVO4 and lower adiabatic ionization potential (AIP). Then, photogenerated holes initiate the chain transformation of sulfite and produce strong oxidizing species which can diffuse out to degrade organics. This paper provides an insight into the understand the effects of solid-liquid interface on heterogeneously photocatalytic degradation of organic pollutants.

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