Citation: Shenghui Tu, Anru Liu, Hongxiang Zhang, Lu Sun, Minghui Luo, Shan Huang, Ting Huang, Honggen Peng. Oxygen vacancy regulating transition mode of MIL-125 to facilitate singlet oxygen generation for photocatalytic degradation of antibiotics[J]. Chinese Chemical Letters, ;2024, 35(12): 109761. doi: 10.1016/j.cclet.2024.109761 shu

Oxygen vacancy regulating transition mode of MIL-125 to facilitate singlet oxygen generation for photocatalytic degradation of antibiotics

Shenghui Tu ^a ,
Anru Liu ^a ,
Hongxiang Zhang ^{b, *,} ,
Lu Sun ^a ,
Minghui Luo ^a ,
Shan Huang ^b ,
Ting Huang ^b ,
Honggen Peng ^{a, b}

a.
School of Chemistry and Chemical Engineering, Key Laboratory of Jiangxi Province for Environment and Energy Catalysis, Nanchang University, Nanchang 330031, China
b.
School of Resources and Environment, Key Laboratory of Poyang Lake Environment and Resource Utilization, Ministry of Education, Nanchang University. Nanchang 330031, China

ZhangHX@ncu.edu.cn

Received Date: 19 October 2023
Revised Date: 29 February 2024
Accepted Date: 11 March 2024
Available Online: 12 March 2024

Figures(6)

Efficient yield of ¹O₂ determines the photocatalytic degradation rate of antibiotics, but the regulatory mechanism for ¹O₂ selective generation in O₂ activation is still lacking exploration. Herein, oxygen vacancy (OV) modification strategy of MIL-125 was successfully practiced to promote the selective generation of ¹O₂. Multiple characterizations including extended X-ray absorption fine structure (EXAFS) and electron paramagnetic resonance spectra (EPR) confirmed the formation of oxygen vacancy in OV-MIL-125. The synthesized OV-MIL-125 exhibited greatly enhanced ¹O₂ selective (~90%) and antibiotics removal rate in water with high mineralization rate. Dynamics analysis of excitons by transient-steady state fluorescence and phosphorescence, transient absorption spectra (TAS) revealed that oxygen vacancy greatly enhanced the intersystem crossing (ISC) of singlet exciton, promoting triplet exciton generation. Density functional theoretical (DFT) calculation also proved the reduced gap of intersystem (ΔE_ST) and the modulated highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) population which was conducive to intersystem crossing process. Calculation of transition state further confirmed the lower energy barrier for π^* orbital spin flip of O₂ adsorbed on OV-MIL-125. The Dexter energy transfer involving triplet annihilation dominated the O₂ activation mechanism to generate ¹O₂ instead of the charge transfer to generate O₂^•− which happened in MIL-125. This study provides new thinking for photocatalytic activation of molecular oxygen and is expected to guide the design of MOF-based catalysts for water treatment.
- Photocatalytic degradation,
- Singlet oxygen,
- MOFs,
- Oxygen vacancy,
- Intersystem crossing
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