电化学强化钴基阴极活化过一硫酸盐的研究

doi:10.11949/0438-1157.20230146

摘要/Abstract

摘要：

在泡沫镍（NF）表面水热法生长了Co-MOF，经热处理制备了Co₃O₄@NF，通过扫描电镜、透射电镜、X射线衍射、X射线光电子能谱等手段对材料的形貌和结构进行了表征。将其作为阴极与过一硫酸盐（PMS）构成了电化学强化过一硫酸盐活化体系EC/Co₃O₄@NF/PMS，用于降解左氧氟沙星（LEV）。结果显示该体系在pH 3.0、PMS加入量3.5 mmol·L^-1、电流密度4 mA·cm^-2、40 min时LEV的降解率可达到95.8%，55 min时化学需氧量（COD）去除率为73.3%，显著优于没有施加电流的体系。对体系中活性物种产生机制的研究表明，电场主要通过加速Co₃O₄@NF阴极表面的Co³⁺—Co²⁺循环，促进了PMS活化为单线态氧¹O₂和 $S O_{4}^{• -}$ 、·OH自由基的进程，使LEV降解的非自由基途径和自由基途径均得到了加强。

关键词: 自由基, 催化剂活化, 电化学, 过硫酸盐, 高级氧化, 抗生素降解, 单线态氧, 左氧氟沙星

Abstract:

Co-MOF was grown by hydrothermal method on the surface of nickel foam (NF), and Co₃O₄@NF was prepared by heat treatment. The structure and morphology of the prepared material were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalyst as a cathode and peroxymonosulfate (PMS) constitute an electrochemically enhanced peroxosulfate activation system EC/ Co₃O₄@NF/PMS for the degradation of levofloxacin (LEV). The experimental results show that the degradation rate can reach 95.8% in 40 min, and the COD removal is 73.3% in 55 min when pH is 3.0, PMS dosage is 3.5 mmol·L^-1, and current density is 4 mA·cm^-2, which are significantly better than the system without applying current. The mechanism of the generation of active species in the system was studied. It shows that electric field promotes the activation of PMS to form singlet oxygen ¹O₂, free radicals $S O_{4}^{• -}$ and ·OH mainly by accelerating the Co³⁺—Co²⁺ cycle on the surface of the Co₃O₄@NF cathode. Therefore, both non-free radical and free radical pathways for LEV degradation are enhanced.

Key words: free radical, catalyst activation, electrochemistry, peroxymonosulfate, advanced oxidation, antibiotic degradation, singlet oxygen, levofloxacin

中图分类号:

X 703.1

李瑞康, 何盈盈, 卢维鹏, 王园园, 丁皓东, 骆勇名. 电化学强化钴基阴极活化过一硫酸盐的研究[J]. 化工学报, 2023, 74(5): 2207-2216.

Ruikang LI, Yingying HE, Weipeng LU, Yuanyuan WANG, Haodong DING, Yongming LUO. Study on the electrochemical enhanced cobalt-based cathode to activate peroxymonosulfate[J]. CIESC Journal, 2023, 74(5): 2207-2216.

图/表 8

图1 材料的形貌和结构表征

Fig.1 Characterization of structure and morphology of the prepared materials

图2 不同体系对LEV去除效果的比较(pH 3.0, LEV浓度20 mg·L-1, 有电场时电流密度4 mA·cm-2)

Fig.2 Comparison of LEV removal in different systems

图3 降解条件对LEV降解率的影响以及最佳条件下的COD去除率

Fig.3 Effect of treatment conditions on LEV degradation and COD removal under optimal conditions

表1 LEV降解效果比较

Table 1 Comparison of the LEV degradation

催化剂	反应条件	LEV降解率/COD或TOC去除率	文献
rose petal derived Co₃O₄/MC	10 mg·L^-1 LEV, 0.3 mmol·L^-1 PMS, pH 5.5	100% (12 min)	[2]
SrCoO₃/MnFe₂O₄/MoS₂	20 mg·L^-1 LEV, 1 g·L^-1 PMS, pH 6	95.1% (20 min)	[21]
CoFe₂O₄	20 mg·L^-1 LEV, 20 mmol·L^-1PMS, pH 5.6, 15 mA·cm^-2	91.7% (40 min)/30.6%(TOC 40 min)	[22]
MgO/Co₃O₄	10 mg·L^-1 LEV, 300 mg·L^-1 PMS, pH 5	96.9% (20 min)/38.5%(TOC 20 min)	[23]
Co₃O₄/NF	20 mg·L^-1 LEV, 3.5 mmol·L^-1 PMS, pH 3.0, 4 mA·cm^-2	95.8% (40 min)/73.3%(COD 55 min)	本文

图4 EC/Co3O4@NF/PMS体系的适用性及其循环稳定性

Fig.4 Applicability and reusability of EC/Co3O4@NF/PMS system

图5 活化PMS产生的活性物种研究

Fig.5 Study on the active species produced by activating PMS

图6 反应前后材料的XPS谱图

Fig.6 XPS spectra of the materials before and after reaction

图7 EC/Co3O4@NF体系中活性物种产生途径示意图

Fig.7 Schematic diagram of generation pathway of the active species in EC/Co3O4@NF system

参考文献 35

1	Hirsch R, Ternes T, Haberer K, et al. Occurrence of antibiotics in the aquatic environment[J]. Science of the Total Environment, 1999, 225(1/2): 109-118.
2	Xu Z Q, Jiang J, Wang M, et al. Enhanced levofloxacin degradation by hierarchical porous Co₃O₄ with rich oxygen vacancies activating peroxymonosulfate: performance and mechanism[J]. Separation and Purification Technology, 2023, 304: 122055.
3	Wang J L, Wang S Z. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants[J]. Chemical Engineering Journal, 2018, 334: 1502-1517.
4	Olmez-Hanci T, Arslan-Alaton I. Comparison of sulfate and hydroxyl radical based advanced oxidation of phenol[J]. Chemical Engineering Journal, 2013, 224: 10-16.
5	Qi C D, Liu X T, Ma J, et al. Activation of peroxymonosulfate by base: implications for the degradation of organic pollutants[J]. Chemosphere, 2016, 151: 280-288.
6	Zhang X K, Liu J, Zhang H Z, et al. Uncovering the pathway of peroxymonosulfate activation over Co_0.5Zn_0.5O nanosheets for singlet oxygen generation: performance and membrane application[J]. Applied Catalysis B: Environmental, 2023, 327: 122429.
7	Lu C, Zhang S L, Wang J, et al. Efficient activation of peroxymonosulfate by iron-containing mesoporous silica catalysts derived from iron tailings for degradation of organic pollutants[J]. Chemical Engineering Journal, 2022, 446: 137044.
8	Han X L, Zhang W, Li S, et al. Mn-MOF derived manganese sulfide as peroxymonosulfate activator for levofloxacin degradation: an electron-transfer dominated and radical/nonradical coupling process[J]. Journal of Environmental Sciences, 2023, 130: 197-211.
9	Mi X Y, Zhong H, Zhang H X, et al. Facilitating redox cycles of copper species by pollutants in peroxymonosulfate activation[J]. Environmental Science & Technology, 2022, 56(4): 2637-2646.
10	Wang F X, Zhang Z C, Yi X H, et al. A micron-sized Co-MOF sheet to activate peroxymonosulfate for efficient organic pollutant degradation[J]. CrystEngComm, 2022, 24(31): 5557-5561.
11	Zhang W W, He Y C, Li C, et al. Persulfate activation using Co/AC particle electrodes and synergistic effects on humic acid degradation[J]. Applied Catalysis B: Environmental, 2021, 285: 119848.
12	Li Z L, Wang M, Jin C Y, et al. Synthesis of novel Co₃O₄ hierarchical porous nanosheets via corn stem and MOF-Co templates for efficient oxytetracycline degradation by peroxymonosulfate activation[J]. Chemical Engineering Journal, 2020, 392: 123789.
13	Sun X P, Liu Z B, Sun Z R. Electro-enhanced degradation of atrazine via Co-Fe oxide modified graphite felt composite cathode for persulfate activation[J]. Chemical Engineering Journal, 2022, 433: 133789.
14	Yan C, Liu L. Oxidation of gas phase ammonia via accelerated generation of radical species and synergy of photo electrochemical catalysis with persulfate activation by CuO-Co₃O₄ on cathode electrode[J]. Journal of Hazardous Materials, 2020, 388: 121793.
15	Tang S F, Zhao M Z, Yuan D L, et al. MnFe₂O₄ nanoparticles promoted electrochemical oxidation coupling with persulfate activation for tetracycline degradation[J]. Separation and Purification Technology, 2021, 255(7): 117690.
16	Zhao C, Meng L H, Chu H Y, et al. Ultrafast degradation of emerging organic pollutants via activation of peroxymonosulfate over Fe₃C/Fe@N-C-x: singlet oxygen evolution and electron-transfer mechanisms[J]. Applied Catalysis B: Environmental, 2023, 321: 122034.
17	Chen M M, Niu H Y, Niu C G, et al. Metal-organic framework-derived CuCo/carbon as an efficient magnetic heterogeneous catalyst for persulfate activation and ciprofloxacin degradation[J]. Journal of Hazardous Materials, 2022, 424: 127196.
18	Zhou H J, Lu D X, Fang S Q, et al. Prompting direct single electron transfer to produce non-radical ¹O₂/H^* by electro-activating peroxydisulfate process with core-shell cathode[J]. Journal of Environmental Management, 2021, 287: 112294.
19	Di J, Zhu M Z, Jamakanga R, et al. Electrochemical activation combined with advanced oxidation on NiCo₂O₄ nanoarray electrode for decomposition of Rhodamine B[J]. Journal of Water Process Engineering, 2020, 37: 101386.
20	Dang Y, Bai Y Y, Zhang Y C, et al. Tannic acid reinforced electro-Fenton system based on GO-Fe₃O₄/NF cathode for the efficient catalytic degradation of PNP[J]. Chemosphere, 2022, 289: 133046.
21	He Y X, Qian J, Wang P F, et al. Acceleration of levofloxacin degradation by combination of multiple free radicals via MoS₂ anchored in manganese ferrite doped perovskite activated PMS under visible light[J]. Chemical Engineering Journal, 2022, 431: 133933.
22	Zhang Q Y, Sun X Q, Dang Y, et al. A novel electrochemically enhanced homogeneous PMS-heterogeneous CoFe₂O₄ synergistic catalysis for the efficient removal of levofloxacin[J]. Journal of Hazardous Materials, 2022, 424: 127651.
23	Xue X J, Liao W D, Liu D L, et al. MgO/Co₃O₄ composite activated peroxymonosulfate for levofloxacin degradation: role of surface hydroxyl and oxygen vacancies[J]. Separation and Purification Technology, 2023, 306: 122560.
24	Ren W, Zhou P, Nie G, et al. Hydroxyl radical dominated elimination of plasticizers by peroxymonosulfate on metal-free boron: kinetics and mechanisms[J]. Water Research, 2020, 186: 116361.
25	Dong Z T, Niu C G, Guo H, et al. Anchoring CuFe₂O₄ nanoparticles into N-doped carbon nanosheets for peroxymonosulfate activation: built-in electric field dominated radical and non-radical process[J]. Chemical Engineering Journal, 2021, 426: 130850.
26	Wang Z P, Wang J W, Xiong B, et al. Application of cobalt/peracetic acid to degrade sulfamethoxazole at neutral condition: efficiency and mechanisms[J]. Environmental Science & Technology, 2020, 54(1): 464-475.
27	Liu G F, Li X C, Han B J, et al. Efficient degradation of sulfamethoxazole by the Fe(Ⅱ)/HSO 5 - process enhanced by hydroxylamine: efficiency and mechanism[J]. Journal of Hazardous Materials, 2017, 322: 461-468.
28	Ahn Y Y, Bae H, Kim H I, et al. Surface-loaded metal nanoparticles for peroxymonosulfate activation: efficiency and mechanism reconnaissance[J]. Applied Catalysis B: Environmental, 2019, 241: 561-569.
29	Jin Y Z, Feng X J, Yang A Q, et al. Peroxymonosulfate activation by brownmillerite-type oxide Ca₂Co₂O₅ for efficient degradation of pollutants via direct electron transfer and radical pathways[J]. Separation and Purification Technology, 2021, 278: 119619.
30	Zhou J H, Li X S, Yuan J, et al. Efficient degradation and toxicity reduction of tetracycline by recyclable ferroferric oxide doped powdered activated charcoal via peroxymonosulfate (PMS) activation[J]. Chemical Engineering Journal, 2022, 441: 136061.
31	Huang Q Q, Zhang J Y, He Z Y, et al. Direct fabrication of lamellar self-supporting Co₃O₄/N/C peroxymonosulfate activation catalysts for effective aniline degradation[J]. Chemical Engineering Journal, 2017, 313: 1088-1098.
32	Kim D G, Ko S O. Effects of thermal modification of a biochar on persulfate activation and mechanisms of catalytic degradation of a pharmaceutical[J]. Chemical Engineering Journal, 2020, 399: 125377.
33	Yuan X J, Shen D Y, Zhang Q, et al. Z-scheme Bi₂WO₆/CuBi₂O₄ heterojunction mediated by interfacial electric field for efficient visible-light photocatalytic degradation of tetracycline[J]. Chemical Engineering Journal, 2019, 369: 292-301.
34	Zhang H X, Li C W, Lyu L, et al. Surface oxygen vacancy inducing peroxymonosulfate activation through electron donation of pollutants over cobalt-zinc ferrite for water purification[J]. Applied Catalysis B: Environmental, 2020, 270: 118874.
35	Wu L P, Li B, Li Y, et al. Preferential growth of the cobalt (200) facet in Co@N-C for enhanced performance in a Fenton-like reaction[J]. ACS Catalysis, 2021, 11(9): 5532-5543.

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