Atomic-level insight into effect of substrate concentration and relative humidity on photocatalytic degradation mechanism of gaseous styrene.

Substrate concentration and relative humidity (RH) impact the photocatalytic efficiency of industrial aromatic hydrocarbons, but how they influence intermediate formation and degradation pathway remains unclear. With the help of oxygen isotope tracing method, the effects of these two environmental parameters on degradation mechanism of styrene were revealed at atomic level. Increasing styrene concentration favored product formation, which was however inhibited by RH elevation. Gaseous products were not directly formed in gaseous phase, but originated from desorption of interfacial intermediates. The volatile aldehydes and furans further exchanged their O with O in HO. Increase of RH showed higher enhancement on O distribution in all products and pathways than that of substrate concentration. Low RH preferred high generation of O and O, dominating reaction to form 1-phenyl-1,2-ethandiol, 2-hydroxy-1-phenyl-ethanon and phenylglyoxal monohydrate in sequence. Successive production of benzyl alcohol, benzaldehyde and benzoic acid through the reaction of styrene with promoted OH by increasing RH became predominant. Hydration was firstly observed and confirmed as an important gaseous transformation step of aldehyde and furan products. Our findings provide a deep insight into photocatalytic degradation mechanism of aromatic hydrocarbons regulated by environmental parameters to further improve their industrial purification efficiency, and are helpful predicting environmental geochemistry fate of organics and preventing their negative impact on natural environment.