Photo-induced surface frustrated Lewis pairs for promoted photocatalytic decomposition of perfluorooctanoic acid

Highlights

● Terminal carboxylate group activation is PFOA degradation’s rate-limiting step.

● Bi₃O(OH)(PO₄)₂ with surface frustrated Lewis pairs (SFLPs) efficiently degrade PFOA.

● Photo-induced Lewis acidic sites and proximal surface hydroxyls constitute SFLPs.

● SFLPs act as collection centers to effectively adsorb PFOA.

● SFLPs endow accessible pathways for photogenerated holes rapid transfer to PFOA.

Abstract

Heterogeneous photocatalysis has gained substantial research interest in treating per- and polyfluoroalkyl substances (PFAS)-contaminated water. However, sluggish degradation kinetics and low defluorination efficiency compromise their practical applications. Here, we report a superior photocatalyst, defected Bi₃O(OH)(PO₄)₂, which could effectively degrade typical PFAS, perfluorooctanoic acid (PFOA), with high defluorination efficiency. The UV light irradiation could in situ generate oxygen vacancies on Bi₃O(OH)(PO₄)₂ through oxidation of the lattice hydroxyls, which further promotes the formation of Lewis acidic coordinately unsaturated bismuth sites. Then, the Lewis acidic sites couple with the proximal surface hydroxyls to constitute the surface frustrated Lewis pairs (SFLPs). With the in-depth spectroscopic analysis, we revealed that the photo-induced SFLPs act as collection centers to effectively adsorb PFOA and endow accessible pathways to transfer photogenerated holes to PFOA rapidly. Consequently, activation of the terminal carboxyl, a rate-limiting step for PFOA decomposition, could be easily achieved over the defected Bi₃O(OH)(PO₄)₂ photocatalyst. These results suggest that SFLPs exhibit great potential in developing highly efficient photocatalysts to degrade persistent organic pollutants.

Graphical abstract

Keywords

Heterogeneous photocatalysis / Surface frustrated Lewis pairs / Perfluorooctanoic acid / Defluorination efficiency / Environmental remediation

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Acknowledgements

This research was financially supported by the National Natural Science Foundation of China (Nos. 22006088 and 42077293), the Natural Science Foundation of Guangdong Province (China) (No. 2019QN01L797), the Shenzhen Municipal Science and Technology Innovation Committee (China) (Nos. WDZC20200817103015002 and RCYX20210609104448111), and the Tsinghua Shenzhen International Graduate School (China) (Nos. HW2020002 and QD2021010N).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11783-023-1603-6 and is accessible for authorized users.

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