Degradation of Perfluorooctanoic Acid with Hydrated Electron by a Heterogeneous Catalytic System

Hydrated electron (e_aq^-)-induced reduction protocols have bright prospects for the decomposition of recalcitrant organic pollutants. However, traditional e_aq^- production involves homogeneous sulfite photolysis, which has a pH-dependent reaction activity and might have potential secondary pollution risks. In this study, a heterogeneous UV/diamond catalytic system was proposed to decompose of a typical persistent organic pollutant, perfluorooctanoic acid (PFOA). In contrast to the rate constant of the advanced reduction process (ARP) of a UV/SO₃^2-, the k_obs of PFOA decomposition in the UV/diamond system showed only minor pH dependence, ranging from 0.01823 ± 0.0014 min^-1 to 0.02208 ± 0.0013 min^-1 (pH 2 to pH 11). As suggested by the electron affinity (EA) and electron configuration of the diamond catalyst, the diamond catalyst yields facile energetic photogenerated electron emission into water without a high energy barrier after photoexcitation, thus inducing e_aq^- production. The impact of radical scavengers, electron spin resonance (ESR), and transient absorption (TA) measurements verified the formation of e_aq^- in the UV/diamond system. The investigation of diamond for ejection of energetic photoelectrons into a water matrix represents a new paradigm for ARPs and would facilitate future applications of heterogeneous catalytic processes for efficient recalcitrant pollutant removal by e_aq^-.