Removal of norfloxacin from high salinity wastewater by Hf-porphyrin MOF with missing linker defects: Insights into anion trapping and photoinduced charge transfer effects

卟啉 连接器 水溶液 光化学 电子顺磁共振 离子 吸附 光催化 化学 猝灭(荧光) 荧光 催化作用 有机化学 核磁共振 物理 量子力学 计算机科学 操作系统
作者
Zhiwei Wang,Jiaying Huang,Wei Wang,Xinfeng Wang,Yan Wang,Baoyu Gao,Qian Li
出处
期刊:Chemical Engineering Journal [Elsevier BV]
卷期号:466: 143194-143194 被引量:49
标识
DOI:10.1016/j.cej.2023.143194
摘要

• Hf-porphyrin MOF with missing linker defects promoted NFX removal in high saline water. • Missing-linkers defects facilitated the photoinduced charge transfer (PICT). • Missing-linkers defects captured anions to trigger ligand − metal charge transfer. Treatment of saline wastewater with advanced oxidation technologies has been an urgent challenge due to the inhibitory effect of coexisting ions on reactive oxygen species in real wastewater. Herein, monocarboxylic acids with varying acidity coefficient were employed to modulate the number of missing-linker defects in Hf-porphyrin MOFs (Hf-TCPP-X) to regulate their performance in removing norfloxacin (NFX) from complex aqueous matrices. The missing-linker defect density in Hf-MOFs promoted the removal efficiency of NFX from 8.5 % to 93.6 %. In various anion surroundings, the adsorption and photocatalysis performance of Hf-TCPP-FA with missing-linker defects was enhanced significantly. Quenching tests and the electron paramagnetic resonance (EPR) exhibited that O 2 ∙− , 1 O 2 , and ∙OH dominated NFX removal and their content rising in Hf-TCPP-FA/NaCl/visible-light (Hf-TCPP-FA/NaCl/vis) system. Density functional theory (DFT) calculations displayed that the adsorption energy of Hf-TCPP-FA for NFX decreased from −12.128 eV to −19.157 eV after adding Cl − . The missing-linker defects of catalysts facilitated the photoinduced charge transfer (PICT) under the visible-light irradiation and increased the number of active sites (Hf) in high salinity water. Additionally, favorable NFX removal efficiency could be sustained in Hf-TCPP-FA/visible-light (Hf-TCPP-FA/VIS) system from a wide pH range of aqueous solutions, high coexisting ion concentrations, and in the actual water matrices, and be performed well in cycling tests. This work suggests a promising route to tailor MOF-based photocatalysts by defect engineering and thus improve the removal performance of contaminants in highly saline water.
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