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.

多相光催化系统通常缺乏对水溶液中有机污染物降解的热力学依赖性。因此，重要的是揭示抑制表面动力学但仍被忽视的原因。_{在此，我们揭示了BiVO 4}不能降解有机物的机制，尽管它在热力学上是可行的。表面溶剂化和双层（致密层和扩散层）的形成使低极性有机物远离BiVO ₄表面。我们发现引入亚硫酸盐可以解决这个问题。_{理论计算表明，亚硫酸盐在BiVO 4}上具有较高的吸附能，可以进入致密层和较低的绝热电离势（AIP）。然后，光生空穴引发亚硫酸盐的链式转变并产生强氧化物质，这些物质可以扩散出去降解有机物。本文提供了对固液界面对有机污染物非均相光催化降解影响的理解。