Defect-induced in situ electron-metal-support interactions on MOFs accelerating Fe(III) reduction for high-efficiency Fenton reactions

doi:10.1016/S1872-2067(24)60047-1

Abstract

Abstract:

The inefficient reduction of Fe³⁺ and activation of H₂O₂ in the Fenton reaction severely limit its application in practical water treatment. In this study, we developed defective NH₂-UiO-66 (d-NU) with coordinated unsaturated metal sites by adjusting the coordination configuration of Zr, creating a solid-liquid interface to facilitate Fe³⁺ reduction and the sustainable generation of •OH from H₂O₂ activation. The d-NU/Fe³⁺/H₂O₂/Vis system demonstrated highly efficient removal of various organic pollutants, with a rapid Fe²⁺ regeneration rate and exceptional stability over ten cycles. The degradation rate constant of d-NU (0.16112 min^-1) was 11 times higher than that of NH₂-UiO-66 (NU) (0.01466 min^-1) without defects. Characterization combined with density functional calculations revealed that defects induced coordination unsaturation of the Zr sites, leading to in situ electron-metal-support interactions between Fe³⁺ and the support via Zr-O-Fe bridges. This accumulation of electrons from the unsaturated Zr sites enabled the adsorption of Fe³⁺ at the solid-liquid interface, promoting the formation of Fe²⁺ across a wide pH range with a reduced energy barrier. This study introduces a promising strategy for accelerating Fe³⁺ reduction in the solid-liquid interfacial Fenton process for the degradation of organic pollutants.

Key words: Defect, NH₂-UiO-66, Fe³⁺ reduction, Electron-metal-support interactions, Fenton reaction

Haifang Mao, Yang Liu, Zhenmin Xu, Zhenfeng Bian. Defect-induced in situ electron-metal-support interactions on MOFs accelerating Fe(III) reduction for high-efficiency Fenton reactions[J]. Chinese Journal of Catalysis, 2024, 61: 247-258.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60047-1

https://www.cjcatal.com/EN/Y2024/V61/I6/247

Figures/Tables 7

Fig. 1. (a) Schematic diagram of the synthesis process of d-NU. SEM images of NU (b), and d-NU (c). (d) TEM images of d-NU. (e) Elemental mapping images of d-NU.

Fig. 2. XPS spectra of O 1s (a), C 1s (b) and Zr 3d (c) for d-NU and NU. The XANES K-edge spectra (d) and the FT-EXAFS curves (e) of d-NU and NU with different references. (f) EXAFS fitting curve of d-NU. WT images for the k3-weighted Zr K-edge EXAFS signals of d-NU (g), NU (h) and ZrO2 (i).

Fig. 3. Different influencing factors of d-NU/Fe3+/H2O2 system: (a) dosage of d-NU; (b) dosage of Fe2(SO4)3; (c) dosage of H2O2; (d,e) 4-CP removal in different systems; (f) pH value influence.

Fig. 4. (a) The effect of different scavengers on 4-CP degradation. EPR spectra of DMPO-?OH (b) and TEMP-1O2 (c) for different systems. (d) Time-depended ?OH concentration test by HPLC used DMSO as indicator. The calculated concentration of ?OH (e) and 1O2 (f) in different systems.

Fig. 5. XPS spectra of Fe 2p (a), Zr 3d (b) and O 1s (c) of d-NU before and after reaction. (d) Schematic of the setup used for KPFM measurements. (e) Surface potential profiles of d-NU and NU under visible illumination. KPFM spectra of d-NU-Fe (f) and d-NU (g). (h) Reaction pathways of Fe(OH)2+ reduction on the d-NU and NU surface (inset: the corresponding intermediate structures).

Fig. 6. UV-visible absorbance spectra (a), the corresponding Tauc plots (b) and Mott-Schottky plots (c) of d-NU and NU. Photocurrent-time response profiles (d), electrochemical impedances (e) and Time-resolved PL spectra (f) of d-NU and NU.

Fig. 7. (a) The possible degradation pathway of 4-CP, (b) growth inhibition, (c) daphnia magna LC50, (d) mutagenicity and (e) bioaccumulation factor of 4-CP and intermediates. (f) Reusability tests of d-NU during successive ten-time runs. (g) Capability of the d-NU/Fe3+/H2O2 system for degrading various pollutants.

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