CoP助催化光芬顿中单线态氧协同表面吸附羟基自由基降解苯酚

doi:10.1016/S1872-2067(22)64117-2

催化学报 ›› 2022, Vol. 43 ›› Issue (10): 2678-2689.DOI: 10.1016/S1872-2067(22)64117-2

CoP助催化光芬顿中单线态氧协同表面吸附羟基自由基降解苯酚

俞浩然^a, 刘丹旭^a, 王恒屹^a, 于海爽^a, 闫青云^a, 嵇家辉^a^,^#(), 张金龙^a^,^b, 邢明阳^a^,^b^,^*()

^a华东理工大学化学与分子工程学院先进材料重点实验室和费林加诺贝尔奖科学家联合研究中心国际合作联合实验室, 上海 200237
^b华东理工大学上海多介质环境催化与资源化工程技术研究中心, 上海 200237

收稿日期:2022-04-05 接受日期:2022-04-27 出版日期:2022-10-18 发布日期:2022-09-30
通讯作者: 嵇家辉,邢明阳
基金资助:
国家自然科学基金(22176060)

Singlet oxygen synergistic surface-adsorbed hydroxyl radicals for phenol degradation in CoP catalytic photo-Fenton

Haoran Yu^a, Danxu Liu^a, Hengyi Wang^a, Haishuang Yu^a, Qingyun Yan^a, Jiahui Ji^a^,^#(), Jinlong Zhang^a^,^b, Mingyang Xing^a^,^b^,^*()

^aKey Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China
^bShanghai Engineering Research Center for Multi-media Environmental Catalysis and Resource Utilization, East China University of Science and Technology, Shanghai 200237, China

Received:2022-04-05 Accepted:2022-04-27 Online:2022-10-18 Published:2022-09-30
Contact: Jiahui Ji, Mingyang Xing
Supported by:
National Natural Science Foundation of China(22176060)

摘要/Abstract

摘要：

H₂O₂是一种绿色的化学试剂, 常作为氧化剂应用于水污染控制领域. 近年来, 科研工作者们通过光催化、电催化以及催化剂催化等手段开发了许多原位生成H₂O₂直接参与有机污染物降解的方法. 而在这些基于催化反应生成的H₂O₂的非均相芬顿或类芬顿反应中, 催化剂的表面或剪切面经常会发生物质吸附、H₂O₂的生成与活化以及活性氧物种(ROS)的生成等氧化还原反应. 这些反应过程和机制非常复杂, 而且多数研究并未对此给出清晰的解释. 一般来说, 不同ROS在水溶液中的氧化性、寿命和扩散距离不同. 例如, •OH的氧化性非常强(2.80 V), 但寿命短(<1×10^‒6 s), 因而扩散距离非常有限, 若在非均相催化剂表面生成便无法扩散到溶液中; 而¹O₂的氧化性相对较弱(2.20 V), 寿命较长(2×10^‒6 s), 扩散距离较长, 可扩散到溶液中(固液界面处)去氧化弱极性有机分子. 受此启发, 本文采用简单的两步法制备了光催化中常用的助催化剂CoP, 构建了能产生各种ROS的CoP/Fe²⁺/AM1.5体系, 并研究其对苯酚等各种污染物的降解能力以及降解机理.

X射线衍射、高分辨透射电子显微镜和X射线光电子能谱等表征结果表明, 成功合成了纯净的CoP材料, 且由于其性质活泼, CoP表面与空气接触后被氧化生成了一层氧化层. 通过引入Fe²⁺和模拟太阳光(AM1.5)辐射构建的CoP/Fe²⁺/AM1.5体系能有效降解染料、酚类和抗生素等多种有机污染物, 其中对主要目标污染物苯酚的降解率在2 h内达79.9%. 自由基猝灭实验和电子顺磁共振检测证实, CoP/Fe²⁺/AM1.5体系存在三种活性氧物种, 为•OH_ads, •O₂^‒和¹O₂. 进一步结合苯酚及其中间产物的液相色谱图和邻羟基苯甲酸的荧光图可以发现, 在CoP/Fe²⁺/AM1.5体系中, ¹O₂和表面吸附的•OH_ads之间存在协同效应. 一方面, CoP表面带负电荷, 容易吸附H⁺和铁离子; 利用暴露的还原中心(P^δ^‒)的还原能力, 可以在其表面控制H₂O₂的生成和活化以及铁离子的循环. 另一方面, 通过CoP表面暴露的氧化中心(Co³⁺)实现表面•O₂^‒到¹O₂的可控生成. 此外, CoP表面吸附的Fe²⁺促进了H₂O₂活化为•OH_ads, 而AM1.5辐照则促进了CoP光生电子的产生及其表面•O₂^‒向¹O₂的转化. 在降解过程中, 由于¹O₂具有迁移到剪切面的能力, 有效促进了苯酚的羟基化, 使苯酚变成了极性更强的有机物并吸附在CoP表面, 随后该有机物被其表面的•OH_ads矿化. ¹O₂和•OH_ads之间的协同作用是苯酚发生羟基化、开环和降解等反应的原因. 这一新机制的研究有望为揭示活性氧物种与有机污染物之间的表界面反应提供新的视角.

关键词: 表面羟基自由基, 单线态氧, 协同效应, 羟基化, 光芬顿

Abstract:

In recent years, there have been numerous studies on Fenton or Fenton-like reactions mediated by nonfree radicals such as singlet oxygen (¹O₂); however, there are few studies on the synergistic effect of ¹O₂ and free radicals on the degradation of organic molecules, such as phenol in Fenton reaction. In this study, a cocatalyst, CoP, commonly used in photocatalysis was synthesized using a simple two-step method, and a CoP/Fe²⁺/AM1.5 system was constructed by introducing Fe²⁺ and simulated sunlight (AM1.5) irradiation. The newly constructed CoP/Fe²⁺/AM1.5 system could effectively degrade various organic pollutants, including dyes, phenols, and antibiotics. Radical quenching experiments and electron paramagnetic resonance detection confirmed that there were three reactive oxygen species (ROS) in the CoP/Fe²⁺/AM1.5 system, including •OH_ads, •O₂^-, and ¹O₂. Further, combined with the liquid chromatogram of phenol, its intermediate products, and the fluorescence diagram of o-hydroxybenzoic acid, it can be concluded that a synergistic effect exists between ¹O₂ and the surface-adsorbed •OH_ads in the CoP/Fe²⁺/AM1.5 system. The controllable formation of surface ¹O₂ and •OH_ads was achieved through the oxidation (Co³⁺) and reduction (P^δ^-) centers exposed on the CoP surface, and the synergistic effect between them results in phenol’s hydroxylation, ring-opening, and degradation. The study of this new mechanism provides a new perspective for revealing the surface interface reaction between ROS and organic pollutants.

Key words: Surface hydroxyl radical, Singlet oxygen, Synergistic effect, Hydroxylation, Photo-Fenton

俞浩然, 刘丹旭, 王恒屹, 于海爽, 闫青云, 嵇家辉, 张金龙, 邢明阳. CoP助催化光芬顿中单线态氧协同表面吸附羟基自由基降解苯酚[J]. 催化学报, 2022, 43(10): 2678-2689.

Haoran Yu, Danxu Liu, Hengyi Wang, Haishuang Yu, Qingyun Yan, Jiahui Ji, Jinlong Zhang, Mingyang Xing. Singlet oxygen synergistic surface-adsorbed hydroxyl radicals for phenol degradation in CoP catalytic photo-Fenton[J]. Chinese Journal of Catalysis, 2022, 43(10): 2678-2689.

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图/表 4

Fig. 1. Preparation and characterization of CoP. (a) Schematic of CoP preparation process and corresponding SEM imagine. (b) Powder XRD pattern. (c) HRTEM. (d) Zeta potential at different pH. (e) High resolution Co 2p spectrum. (f) High resolution P 2p spectrum. (g) FT-IR spectrum.

Fig. 2. Degradation of organic pollutants and exploration of reactive oxygen species. (a) Difference of phenol degradation in different systems. (b) Different degradation rates of RhB, SD, 4-CP, and phenol in the CoP/Fe2+/AM1.5 system. (c) Inhibition effect of different free radical scavengers on phenol degradation in CoP/Fe2+/AM1.5 system. (d) EPR spectra of DMPO-•OH in CoP/AM1.5 and CoP/Fe2+/AM1.5 systems. (e) EPR spectra of DMPO•-O2- in CoP/AM1.5 and CoP/Fe2+/AM1.5 systems. (f) EPR spectra of TEMP-1O2 in CoP, CoP/AM1.5, and CoP/Fe2+/AM1.5 systems. (g) Changes in PMSO and PMSO2 concentrations in the CoP/Fe2+/AM1.5 system. (h) H2O2 production of the CoP, CoP/AM1.5, and CoP/Fe2+/AM1.5 systems. (i) Effect of O2 on phenol degradation in the CoP/Fe2+/AM1.5 system. General conditions: [CoP]0 = 1.0 g/L, [Fe2+]0 = 40 mg/L, pHi = 3.0, [phenol/RhB/SD/4-CP]0 = 10 mg/L, [TBA/p-BQ/TEMP]0 = 0.5 mmol/L, [PMSO]0 = 0.1 mmol/L.

Fig. 3. Mechanism exploration, circulation, and anti-interference ability of CoP. (a) Liquid chromatogram of phenol and its degradation intermediates in CoP, CoP/AM1.5, CoP/Fe2+, and CoP/Fe2+/AM1.5 systems. Fluorescence spectra of hydroxybenzoic acid formed by benzoic acid capturing •OH in CoP, CoP/AM1.5, CoP/Fe2+, and CoP/Fe2+/AM1.5 systems (b), CoP + TEMP system (c), CoP/AM1.5 + TEMP system (d). (e) Cyclic degradation experiment of CoP. (f) the anti-interference ability of CoP/Fe2+/AM1.5 system. Note: the peaks of o-diphenol, m-diphenol, and p-diphenol in liquid chromatography are at 2.85, 3.30, and 3.65 min, respectively. General conditions: [CoP]0 = 1.0 g/L, [Fe2+]0 = 40 mg/L, pHi = 3.0, [phenol]0 = 10 mg/L, [benzoic acid]0 = 2.0 mmol/L, [Cl-/SO42-/NO3-/H2PO4-]0 = 10 mmol/L.

Scheme 1. Mechanism diagram of phenol degradation by the synergistic effect of 1O2 and •OHads.

参考文献

[1]	G. Gao, Y. Tian, X. Gong, Z. Pan, K. Yang, B. Zong, Chin. J. Catal., 2020, 41, 1039-1047.
[2]	L. Li, Z. Hu, J. C. Yu, Angew. Chem. Int. Ed., 2020, 59, 20538-20544.
[3]	D. Ma, H. Yi, C. Lai, X. Liu, X. Huo, Z. An, L. Li, Y. Fu, B. Li, M. Zhang, L. Qin, S. Liu, L. Yang, Chemosphere, 2021, 275, 130104.
[4]	J. An, N. Li, Y. Wu, S. Wang, C. Liao, Q. Zhao, L. Zhou, T. Li, X. Wang, Y. Feng, Environ. Sci. Technol., 2020, 54, 10916-10925.
[5]	H. Lee, H. J. Lee, J. Seo, H. E. Kim, Y. K. Shin, J. H. Kim, C. Lee, Environ. Sci. Technol., 2016, 50, 8231-8238.
[6]	J. S. Jirkovský, I. Panas, E. Ahlberg, M. Halasa, S. Romani, D. J. Schiffrin, J. Am. Chem. Soc., 2011, 133, 19432-19441.
[7]	S. Li, G. Dong, R. Hailili, L. Yang, Y. Li, F. Wang, Y. Zeng, C. Wang, Appl. Catal. B, 2016, 190, 26-35.
[8]	Y. Wang, H. Ji, W. Liu, T. Xue, C. Liu, Y. Zhang, L. Liu, Q. Wang, F. Qi, B. Xu, D. C. W. Tsang, W. Chu, ACS Appl. Mater. Inter., 2020, 12, 20522-20535.
[9]	G. K. Ziyatdinova, D. M. Gil'metdinova, G. K. Budnikov, J. Anal. Chem., 2005, 60, 49-52.
[10]	Q. Yi, J. Ji, B. Shen, C. Dong, J. Liu, J. Zhang, M. Xing, Environ. Sci. Technol., 2019, 53, 9725-9733.
[11]	D. Guo, Y. Liu, H. Ji, C. C. Wang, B. Chen, C. Shen, F. Li, Y. Wang, P. Lu, W. Liu, Environ. Sci. Technol., 2021, 55, 4045-4053.
[12]	J. Ji, Q. Yan, P. Yin, S. Mine, M. Matsuoka, M. Xing, Angew. Chem. Int. Ed., 2021, 60, 2903-2908.
[13]	Q. Yan, C. Lian, K. Huang, L. Liang, H. Yu, P. Yin, J. Zhang, M. Xing, Angew. Chem. Int. Ed., 2021, 60, 17155-17163.
[14]	J. Wang, Z. Liu, Y. Zheng, L. Cui, W. Yang, J. Liu, J. Mater. Chem. A, 2017, 5, 22913-22932.
[15]	S. T. Oyama, T. Gott, H. Zhao, Y.-K. Lee, Catal. Today, 2009, 143, 94-107.
[16]	L. Zhang, G. Wang, X. Hao, Z. Jin, Y. Wang, Chem. Eng. J., 2020, 395, 125113.
[17]	H. Kim, J. Lim, S. Lee, H. H. Kim, C. Lee, J. Lee, W. Choi, Environ. Sci. Technol., 2019, 53, 2918-2925.
[18]	P. Wang, S. Zhan, H. Wang, Y. Xia, Q. Hou, Q. Zhou, Y. Li, R. R. Kumar, Appl. Catal. B, 2018, 230, 210-219.
[19]	X. Yue, S. Yi, R. Wang, Z. Zhang, S. Qiu, Small, 2017, 13, 1603301.
[20]	W. Li, Q. Yang, S. Chou, J. Wang, H. Liu, J. Power Sources, 2015, 294, 627-632.
[21]	T. Liu, K. Wang, G. Du, A. M. Asiri, X. Sun, J. Mater. Chem. A, 2016, 4, 13053-13057.
[22]	R. Liang, Y. Wang, C. Qin, X. Chen, Z. Ye, L. Zhu, Langmuir, 2021, 37, 3321-3330.
[23]	H. B. M. Sidek, X. Jin, M. S. Islam, S. J. Hwang, ChemCatChem, 2019, 11, 6099-6104.
[24]	D. Zhu, L. Wang, M. Qiao, J. Liu, Chem. Commun., 2020, 56, 7159-7162.
[25]	D. Zhu, Q. Zhen, J. Xin, H. Ma, L. Tan, H. Pang, X. Wang, Sensor. Actuat. B, 2020, 321, 128541.
[26]	B. Pradhan, G. S. Kumar, A. Dalui, A. H. Khan, B. Satpati, Q. Ji, L. K. Shrestha, K. Ariga, S. Acharya, J. Mater. Chem. C, 2016, 4, 4967-4977.
[27]	W. Maneeprakorn, M. A. Malik, P. O'Brien, J. Mater. Chem. A, 2010, 20, 2329-2335.
[28]	D. Dai, H. Xu, L. Ge, C. Han, Y. Gao, S. Li, Y. Lu, Appl. Catal. B, 2017, 217, 429-436.
[29]	H. Li, J. Shang, Z. Yang, W. Shen, Z. Ai, L. Zhang, Environ. Sci. Technol., 2017, 51, 5685-5694.
[30]	X. Xu, X. Li, X. Li, H. Li, Sep. Purif. Technol., 2009, 68, 261-266.
[31]	L. Clarizia, D. Russo, I. Di Somma, R. Marotta, R. Andreozzi, Appl. Catal. B, 2017, 209, 358-371.
[32]	M. P. Bradshaw, C. Barril, A. C. Clark, P. D. Prenzler, G. R. Scollary, Crit. Rev. Food Sci. Nutr., 2011, 51, 479-498.
[33]	L. Xu, L. Meng, X. Zhang, X. Mei, X. Guo, W. Li, P. Wang, L. Gan, J. Hazard. Mater., 2019, 379, 120795.
[34]	K. Maeda, H. Hashiguchi, H. Masuda, R. Abe, K. Domen, J. Phys. Chem. C, 2008, 112, 3447-3452.
[35]	R. C. Gilson, K. C. Black, D. D. Lane, S. Achilefu, Angew. Chem. Int. Ed., 2017, 129, 10857-10860.
[36]	T. Liu, L. Zou, D. Feng, Y. Chen, S. Fordham, X. Wang, Y. Liu, H. Zhou, J. Am. Chem. Soc., 2014, 136, 7813-7816.
[37]	L. Chen, X. Li, J. Zhang, J. Fang, Y. Huang, P. Wang, J. Ma, Environ. Sci. Technol., 2015, 49, 10373-10379.
[38]	G. Huang, J. Si, C. Qian, W. Wang, S. Mei, C. Wang, H. Yu, Anal. Chem., 2018, 90, 14439-14446.
[39]	K. Briviba, T. P. A. Devasagayam, H. Sies, S. Steenken, Chem. Res. Toxicol., 1993, 6, 548-553.
[40]	Y. Zhou, J. Jiang, Y. Gao, S. Pang, Y. Yang, J. Ma, J. Gu, J. Li, Z. Wang, L. Wang, L. Yuan, Y. Yang,, Water Res., 2017, 125, 209-218.
[41]	A. Takayanagi, M. Kobayashi, Y. Kawase, Environ. Sci. Pollut. Res., 2017, 24, 8087-8097.

CoP助催化光芬顿中单线态氧协同表面吸附羟基自由基降解苯酚

Singlet oxygen synergistic surface-adsorbed hydroxyl radicals for phenol degradation in CoP catalytic photo-Fenton

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