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

doi:10.1007/s11783-023-1603-6

Front. Environ. Sci. Eng.

2023, Vol. 17

Issue (1) : 3 https://doi.org/10.1007/s11783-023-1603-6

SHORT COMMUNICATION

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

Xianjun Tan, Zhenying Jiang, Yuxiong Huang(

)

Tsinghua-Berkeley Shenzhen Institute (TBSI), Shenzhen International Graduate School, Tsinghua University, Shenzhen 518055, China

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Abstract

● 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.

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.

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

Corresponding Author(s): Yuxiong Huang

Just Accepted Date: 04 July 2022 Issue Date: 19 July 2022

Cite this article:

Xianjun Tan,Zhenying Jiang,Yuxiong Huang. Photo-induced surface frustrated Lewis pairs for promoted photocatalytic decomposition of perﬂuorooctanoic acid[J]. Front. Environ. Sci. Eng., 2023, 17(1): 3.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-023-1603-6
https://academic.hep.com.cn/fese/EN/Y2023/V17/I1/3

Fig.1 (a) Schematic illustration for CO₂ photoreduction to CO₂^?? on SFLPs. (b) Proposed activation mechanism for R-CO₂^? photooxidation to R-CO₂?.

Fig.2 (a) XRD pattern of the BiOHP pre-catalyst. (b) Time-dependent photodegradation of PFOA by the BiOHP pre-catalyst and corresponding kinetics fitting curves. (c) Comparison of degradation activity of the BiOHP pre-catalyst and BiOHP-V_o toward PFOA and (d) corresponding kinetic constants.

Fig.3 (a) EPR analysis of BiOHP-V_o, BiOHP-280 and BiOHP-380 at 77K. (b) Bi 4f and (c) O 1s XPS spectra and (d) ATR-FTIR spectra of the BiOHP-V_o, BiOHP-280 and BiOHP-380. (e) Comparison of the degradation performance and (f) corresponding defluorination efficiency over the BiOHP-V_o, BiOHP-280 and BiOHP-380 photocatalysts.

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