光电催化脱氟-氧化过程实现氟芳烃污染物的高效矿化

doi:10.1016/S1872-2067(23)64559-0

催化学报 ›› 2023, Vol. 55: 171-181.DOI: 10.1016/S1872-2067(23)64559-0

光电催化脱氟-氧化过程实现氟芳烃污染物的高效矿化

池海波^a^,^b, 王旺银^b, 马江平^b^,^c, 段睿智^b^,^c, 丁春梅^b, 宋睿^b^,^c, 李灿^a^,^b^,^c^,^*()

^a中国科学技术大学化学与材料科学学院, 安徽合肥 230026
^b中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023
^c兰州大学化学与化工学院, 功能有机分子化学国家重点实验室, 甘肃省高级催化重点实验室, 甘肃兰州 730000

收稿日期:2023-09-25 接受日期:2023-11-06 出版日期:2023-12-18 发布日期:2023-12-07
通讯作者: *电子信箱: canli@dicp.ac.cn (李灿).
基金资助:
国家自然科学基金(22088102);国家自然科学基金(22372162);辽宁省兴辽英才计划(XLYC2007002);中国科学院青年创新促进会(2022178)

A synchronous defluorination-oxidation process for efficient mineralization of fluoroarenes with photoelectrocatalysis

Haibo Chi^a^,^b, Wangyin Wang^b, Jiangping Ma^b^,^c, Ruizhi Duan^b^,^c, Chunmei Ding^b, Rui Song^b^,^c, Can Li^a^,^b^,^c^,^*()

^aSchool of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, Anhui, China
^bState Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cKey Laboratory of advanced catalysis, Gansu Province; State Key Laboratory of Applied Organic Chemistry College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China

Received:2023-09-25 Accepted:2023-11-06 Online:2023-12-18 Published:2023-12-07
Contact: *E-mail: canli@dicp.ac.cn (C. Li).
Supported by:
National Natural Science Foundation of China(22088102);National Natural Science Foundation of China(22372162);LiaoNing Revitalization Talents Program(XLYC2007002);Youth Innovation Promotion Association CAS(2022178)

摘要/Abstract

摘要：

氟芳烃类化合物因其独特的理化性质, 被广泛应用于含氟医药、农药、液晶材料制备等领域. 然而, 在其生产和使用过程中会造成水污染, 目前在全球多个地区的环境水体中均检测出氟芳烃类化合物的残留. 因此, 对废水中典型的氟芳烃类化合物如氟苯酚、氟苯甲酸以及氟喹诺酮类分子的有效降解备受关注. 氟芳烃类化合物的生物毒性及环境持久性来源于分子结构中氟原子的强电负性、C‒F键的高解离能以及芳环结构的强稳定性, 而常规的降解方法存在应用条件苛刻、有毒含氟中间体残留以及有机碳矿化不完全等问题. 因此, 针对氟芳烃分子的结构特点, 设计一种可以同时促进脱氟和有机碳矿化的降解策略对降低氟芳烃废水的环境危害至关重要.

本文报道了一种基于光电催化的脱氟-氧化过程, 通过紫外光实现氟芳烃分子的自活化, 并与•OH自由基的原位产生过程进行耦合. 利用紫外光光解脱氟的高选择性和•OH自由基的强氧化性, 实现4-氟苯酚在温和条件下完全脱氟以及矿化. 研究结果表明, 苯环结构的4-氟苯酚分子可以吸收λ < 320 nm的紫外光, 且受到光激发后, 其自发光解过程可实现C‒F键断裂, 该过程具有较高的选择性, 但是形成的脱氟中间体无法通过紫外光解进一步降解. 通过构建光电催化体系, TiO₂纳米柱光阳极可原位产生•OH自由基(λ > 320 nm), 从而实现脱氟中间体的完全矿化. 利用全光谱氙灯光照下的光电催化体系可以耦合紫外光解和•OH自由基氧化过程, 对于20 ppm浓度的4-氟苯酚溶液, 其表观降解速率可达14.4 g h^-1 m^-2, 并实现4-氟苯酚完全脱氟及有机碳矿化. 此外, 该体系在不同溶液pH值 (0‒2)、外加偏压(0.5‒1.5 V_RHE)以及照射光源(氙灯、汞灯和LED灯)条件下均具有良好的降解效果和稳定性, 并可拓展至其他常见的氟芳烃类化合物如诺氟沙星等含氟医药分子的降解. 进一步构建了实验室小试装置, 实现了流动条件下氟芳烃废水的完全矿化(工业光源, 50 cm²的光阳极, 5000 mL的20 ppm 4-氟苯酚, 500 mL min^-1循环处理12 h), 证明基于光电催化的脱氟-氧化过程具有潜在的应用前景.

综上所述, 本文利用氟芳烃分子的结构特点, 设计了合理的降解路径, 构建了基于光电催化的高效脱氟-氧化过程并进行了部分应用评估, 为废水中含氟有机污染物的高效无害化处理提供参考.

关键词: 废水处理, 氟芳烃, 光电催化降解, 脱氟, 总有机碳移除

Abstract:

Fluoroarene (FA) derivatives are persistent, toxic, and bioaccumulative pollutants, which pose severe risks to ecosystems and human health. Efficient cleavage of C-F bonds and complete mineralization of defluorinated intermediates are the keys for the deep treatment of FAs due to the high dissociation energy of C-F bonds and the high stability of aromatic rings. Herein, we report a synchronous defluorination-oxidation process using a photoelectrocatalytic device with a TiO₂ photoanode, in which FAs are selectively cleavage of C-F bonds by photolysis and subsequently efficient oxidized by on-site generated •OH radical. Complete defluorination and mineralization (both over 99.9%) of 4-fluorophenol are achieved under irradiation at 1.0 V_RHE in 120 min, the apparent reaction rate constant is 14.4 g h^-1 m^-2. This synchronous defluorination-oxidation process provides an efficient and practical technique for the mineralization of FAs in wastewater under mild conditions.

Key words: Wastewater treatment, Fluoroarene, Photoelectrocatalytic degradation, Defluorination, Total organic carbon removal

池海波, 王旺银, 马江平, 段睿智, 丁春梅, 宋睿, 李灿. 光电催化脱氟-氧化过程实现氟芳烃污染物的高效矿化[J]. 催化学报, 2023, 55: 171-181.

Haibo Chi, Wangyin Wang, Jiangping Ma, Ruizhi Duan, Chunmei Ding, Rui Song, Can Li. A synchronous defluorination-oxidation process for efficient mineralization of fluoroarenes with photoelectrocatalysis[J]. Chinese Journal of Catalysis, 2023, 55: 171-181.

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Fig. 1. (a) UV-vis spectra of 4-FP with different concentrations in aqueous solution. Concentration of residual 4-FP during photolysis under irradiation of different light sources (b) and different incident light wavelengths of xenon lamp as light source (c). Corresponding defluorination (d) and TOC removal (e) efficiencies by photolysis under irradiation of different light sources in (b). (f) Degradation, defluorination, and TOC removal efficiencies of different FAs after 60 min direct photolysis under irradiation of xenon lamp.

Fig. 2. (a) Schematic illustration of the PEC cell for degradation of 4-FP. (b) LSV curves of TiO2 nanopillar photoanode under full spectrum xenon lamp irradiation. (c) Concentration of residual 4-FP by direct photolytic, photocatalytic, electrocatalytic, and photoelectrocatalytic process. (d) Estimating the concentration of ?OH radical by the photoluminescence intensity of TAOH formed in the PEC system. (e) EPR spectra of the samples taken from the PEC system after 15 min full spectrum irradiation at 1.0 VRHE with DMPO as spin-trapping agent. (f) Concentration of residual 4-FP in the PEC system with 0.5 mol L?1 TBA, 50 mmol L?1 Na2EDTA, and 2.5 mmol L?1 TEMPOL as scavengers for ?OH radical, h+, and ?O2- radical, respectively.

Fig. 3. F index (a) and C index (b) of 4-FP degradation in the different degradation processes. (c) Concentration of residual 4-FP as well as corresponding defluorination and TOC removal efficiencies in the PEC system. (d) Schematic illustration of synchronous defluorination-oxidation process for degradation of 4-FP. (e) Concentration of residual 4-FP in the PEC system under irradiation of different light sources.

Fig. 4. (a) HPLC plots of degradation intermediates after different degradation processes. Corresponding mass balances of fluorine (b) and carbon (c) in (a). (Oth. in (b) includes other fluorinated intermediates; FAs in (c) include 4-FP and 4-FC; Aro. in (c) represents defluorinated aromatics, and Oth. in (c) includes other carbon-containing intermediates, such as aliphatics). (d) Plausible coexisting degradation pathways of 4-FP for the synchronous defluorination-oxidation process in the PEC system.

Fig. 5. (a) Concentration of residual 4-FP as a function of time in the PEC system in five consecutive experiments. Effect of initial pH (b) and applied potential (c) on 4-FP degradation in the PEC system. (d) Concentration of residual FAs in the PEC system with an initial concentration of 20 ppm. (e) Corresponding final degradation, defluorination, and TOC removal efficiencies after reaction for 60 min in (d).

Fig. 6. (a) Schematic illustration of the small-scale pilot application system based synchronous defluorination-oxidation process. (b) Performance of the designed system for degradation of 4-FP. Concentration of residual 4-FP (c), the defluorination (d) and TOC removal (e) efficiencies of 4-FP degradation by UVC photolysis, UVA PEC, and tandem system, respectively. Reaction conditions: TiO2 nanopillar photoanode (~50 cm2) and a Ti mesh cathode (~50 cm2) in 0.1 mol L-1 Na2SO4 solution (pH = 6.0) containing 20 ppm 4-FP in a flow rate of 500 mL min-1 (totally 5000 mL for cyclic treatment), at a cell voltage of 3.0 V using a two-electrode setup.

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光电催化脱氟-氧化过程实现氟芳烃污染物的高效矿化

A synchronous defluorination-oxidation process for efficient mineralization of fluoroarenes with photoelectrocatalysis

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