4.2 Article

Surface Complex and Nonradical Pathways Contributing to High-Efficiency Degradation of Perfluorooctanoic Acid on Oxygen-Deficient In2O3 Derived from an In-Based Metal Organic Framework

Journal

ACS ES&T WATER
Volume -, Issue -, Pages -

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsestwater.2c00078

Keywords

perfluorooctanoic acid; In2O3; oxygen vacancy; surface adsorption mode; DFT calculation; nonradical pathways; photocatalytic degradation

Funding

  1. Natural Science Foundation of China [51979081, 52100179]
  2. Fundamental Research Funds for the Central Universities [B200202103]
  3. National Science Funds for Creative Research Groups of China [51421006]
  4. PAPD

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This study investigates the mediating role of the surface structure of In2O3 on the adsorption and photocatalytic degradation of perfluorooctanoic acid (PFOA). It finds that In2O3 with a higher oxygen vacancy concentration exhibits enhanced adsorption capacity and degradation performance for PFOA. The study also reveals a linear correlation between the adsorption capacity and the degradation kinetic rate constant, indicating that surface adsorption is a prerequisite for PFOA degradation. Furthermore, the presence of oxygen vacancies promotes the nonradical oxidation process of PFOA.
The mediating role of surface structure of In2O3 on the adsorption and photocatalytic degradation of perfluorooctanoic acid (PFOA) is important but still unclear. Herein, In2O3 with various oxygen vacancy concentrations are designed by pyrolyzing a metal organic framework (MIL-68(In)-NH2) for PFOA degradation. The results demonstrate that the In2O3-400 obtained at a lower pyrolysis temperature of 400 degrees C possesses the highest oxygen vacancy concentration, thus exhibiting remarkably boosted adsorption capacity and degradation performance for PFOA. Adsorption kinetics, isotherm adsorption model, and Fourier transform infrared spectroscopy (FTIR) results show that PFOA is chemically adsorbed on the In2O3-400 surface in the form of monodentate mode. Notably, there is a linear correlation between the adsorption capacity and the degradation kinetic rate constant of In2O3-400 for PFOA, indicating that surface adsorption is a prerequisite for the PFOA degradation. Furthermore, density functional theory (DFT) results indicate that oxygen vacancies, as the structural characteristic for PFOA chemisorption, can promote the nonradical oxidation process of PFOA. This study provides a new perspective to explain the role of the surface structure of In2O3 in relation to its adsorption and photocatalytic performance for PFOA, which is helpful for the development of more effective PFOA adsorption coupled degradation technology.

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