Visible light-assisted copper oxide efficient activation of peroxydisulfate for tetracycline degradation
LI Shi-jia1, PANG Er-nan2
1. Institute of Traffic Engineering, Shanxi Vocational University of Engineering Science and Technology, Taiyuan 030619, China; 2. School of Materials Science and Engineering, North University of China, Taiyuan 030051, China
Abstract：The advanced oxidation technology of persulfate (PDS) activation by CuO have been hotly sought as one of the effective strategies for degrading organic pollutants in water. However, there are still certain issues such as the low efficiency of PDS activation, the small specific surface area of CuO, and the low conversion efficiency of Cu(II)/Cu(I). Herein, the flake copper oxide (CCB-300) with high activity and large specific surface area (32.8m2/g) was successfully synthesized through a two-step hydrothermal-calcination method. Multiple characterization analysis, such as X-ray powder diffractometry (XRD), N2 adsorption-desorption analysis, Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), were utilized to analyze crystal structure, morphology and element composition of CCB-300. Furthermore, the performance of the CCB-300 for degradation of tetracycline (TC) via peroxydisulfate activation under visible light (Vis) was investigated. The findings revealed that the TC removal rate reached 96.9% within 60minutes under the circumstances of 0.05g/L CCB-300, 0.5mmol/L PDS, 50mg/L TC and unadjusted initial pH. Electron paramagnetic resonance spectroscopy (EPR) and radical quenching experiments indicated that both 1O2 produced by the non-radical pathways and SO4·- and ·OH generated via the radical pathways were involved in the degradation reaction. Ultraviolet-visible diffuse reflectance spectroscopy and photoelectrochemical tests confirmed that CCB-300 exhibited excellent visible light absorption capacity and charge transfer performance. The photogenerated electrons excited by visible light accelerate the redox cycle of Cu(II)/Cu(I), facilitating the conversion of PDS to SO4·- and ·OH, and further enhancing the efficiency of TC degradation. The repeatable experiments demonstrated that CCB-300exhibited favorable reusability and stability. Finally, the possible reaction mechanism was proposed. This study provided a novel method for tetracycline degradation through synergistic persulfate activation by visible light and heterogeneous catalysts.
[1] Ahmad F, Zhu D, Sun J. Environmental fate of tetracycline antibiotics:degradation pathway mechanisms, challenges, and perspectives[J]. Environmental Sciences Europe, 2021,33(1):66. [2] Chen A, Chen Y, Ding C, et al. Effects of tetracycline on simultaneous biological wastewater nitrogen and phosphorus removal[J]. Royal Society of Chemistry Advances, 2015,5(73):59326-59334. [3] Zhang L, Zhang Y, Wei J, et al. Perovskite LaFexCo1-xO3-λ deposited SiO2 catalytic membrane for deeply cleaning wastewater[J]. Chemical Engineering Journal, 2021,403:126386. [4] Zhang X, Guo W, Ngo H H, et al. Performance evaluation of powdered activated carbon for removing 28 types of antibiotics from water[J]. Journal of Environmental Management, 2016,172:193-200. [5] Yang J, Lin Y, Yang X, et al. Degradation of tetracycline by immobilized laccase and the proposed transformation pathway[J]. Journal of Hazardous Materials, 2017,322:525-531. [6] Wang J, Wang S. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants[J]. Chemical Engineering Journal, 2018,334:1502-1517. [7] Zhang R, Zheng X, Zhang D, et al. Insight into the roles of endogenous minerals in the activation of persulfate by graphitized biochar for tetracycline removal[J]. Science of the Total Environment, 2021,768:144281. [8] Yang D, Hong P, Hu Y, et al. Carbon framework encapsulated copper oxide particles to activate peroxymonosulfate for the efficient degradation of tetracycline[J]. Applied Surface Science, 2021,552:149424. [9] Niu L J, Zhang G M, Xian G, et al. Tetracycline degradation by persulfate activated with magnetic γ-Fe2O3/CeO2 catalyst:Performance, activation mechanism and degradation pathway[J]. Separation and Purification Technology, 2021,259:118156. [10] He H, Xiao H, Liu C, et al. Efficient degradation of tetracycline with N-rGO/CuO catalysts under high salinity condition via persulfate activation dominated by non-radical pathways[J]. Separation and Purification Technology, 2023,327:124936. [11] Chen G Y, Y Y, L L, et al. Remediation of antibiotic wastewater by coupled photocatalytic and persulfate oxidation system:a critical review[J]. Journal of Hazardous Materials, 2021,408:124461. [12] Liu Z, Lan H, Wang Y, et al. Highly efficient degradation of bisphenol A with persulfate activated by vacuum-ultraviolet/ultraviolet light (VUV/UV):Experiments and theoretical calculations[J]. Chemical Engineering Journal, 2022,429:132485. [13] Zhang L C, Wang T T, Zhang M Q, et al. Ultrasonically activated persulfate process for the degradation of phenanthrene in soil-washing effluent:experimental, DFT calculation and toxicity evaluation[J]. Journal of Environmental Chemical Engineering, 2024,12(3):113035. [14] Liu Y, Wang S, Wu Y, et al. Degradation of ibuprofen by thermally activated persulfate in soil systems[J]. Chemical Engineering Journal, 2019,356:799-810. [15] 侯先宇,陈炜鸣,李启彬,等.微波活化过硫酸盐耦合混凝处理二硝基重氮酚工业废水[J].中国环境科学, 2018,38(12):4551-4558. Hou X Y, Chen W M, Li Q B, et al. Removal of refractory organic compounds in DDNP industrial wastewater by MW activated PS coupling coagulation process[J]. China Environmental Science, 2018, 38(12):4551-4558. [16] Fu C, Yi X, Liu Y, et al. Cu2+ activated persulfate for sulfamethazine degradation[J]. Chemosphere, 2020,257:127294. [17] Zhang W X, Li Z H, Luo R, et al. Design of tandem CuO/CNTs composites for enhanced tetracycline degradation and antibacterial activity[J]. Separation and Purification Technology, 2023,306:122548. [18] 林双杰,王永全,曾静,等.非自由基主导的FeMn纳米颗粒活化过一硫酸盐降解有机污染物[J].中国环境科学, 2024,44(7):3729-3740. Lin S J, Wang Y Q, Zeng J, et al. Nonradical-dominated peroxymonosulfate activation by FeMn nanoparticles for the degradation of organic pollutants[J]. China Environmental Science, 2024,44(7):3729-3740. [19] Tian D Q, Zhou H Y, Zhang H, et al. Heterogeneous photocatalyst driven persulfate activation process under visible light irradiation:from basic catalyst design principles to novel enhancement strategies[J]. Chemical Engineering Journal, 2022,428:131166. [20] Yang J, Zhu M, Dionysiou D D. What is the role of light in persulfate-based advanced oxidation for water treatment?[J]. Water Research, 2021,189:116627. [21] Chen G Y, Yang Y, Liang L, et al. Remediation of antibiotic wastewater by coupled photocatalytic and persulfate oxidation system:a critical review[J]. Journal of Hazardous Materials, 2021,408:124461. [22] 翟文琰,李孟,张倩.过硫酸盐协同光催化纳米ZnO降解盐酸四环素的影响机制[J].中国环境科学, 2020,40(6):2483-2492. Zhai W Y, Li M, Zhang Q. Influence mechanism and synergistic effects of photocatalytic degradation of tetracycline hydrochloride by the combination of persulfate and nano-ZnO[J]. China Envrionmental Science, 2020,40(6):2483-2492. [23] Ding Y, Fu L, Peng X, et al. Copper catalysts for radical and nonradical persulfate based advanced oxidation processes:Certainties and uncertainties[J]. Chemical Engineering Journal, 2022,427:131766. [24] Li C, Goetz V, Chiron S. Peroxydisulfate activation process on copper oxide:Cu (III) as the predominant selective intermediate oxidant for phenol and waterborne antibiotics removal[J]. Journal of Environmental Chemical Engineering, 2021,9(2):105145. [25] Liang H, Zhang Y, Huang S, et al. Oxidative degradation of p-chloroaniline by copper oxidate activated persulfate[J]. Chemical Engineering Journal, 2013,218:384-391. [26] Xu H J, Zhang Y N, Liu X T, et al. Non-radical activation of persulfate by CuO catalyst for degradation of antibiotics[J]. Journal of Environmental Chemical Engineering, 2024,12:113852. [27] Xing S, Li W, Liu B, et al. Removal of ciprofloxacin by persulfate activation with CuO:a pH-dependent mechanism[J]. Chemical Engineering Journal, 2020,382:122837. [28] Li T, Ding Z Z, Shi F, et al. Facet-dependent peroxymonosulfate activity and mechanism of CuO for degradation of organic pollutants[J]. Journal of Environmental Chemical Engineering, 2024,12(2):112039. [29] Sibhatu A K, Weldegebrieal G K, Sagadevan S, et al. Photocatalytic activity of CuO nanoparticles for organic and inorganic pollutants removal in wastewater remediation[J]. Chemosphere, 2022,300:134623. [30] Zhu Y, Guan Z Y, Li X H, et al. Ultrafast short range catalytic pathway modified peroxymonosulfate activation over CuO with surface oxygen defects for tetracycline hydrochloride degradation[J]. Environmental Research, 2023,222:115322. [31] Zhao L, Zhang J, Zhang Z, et al. CuO with (00 1)-plane exposure efficiently induces peroxymonosulfate to form ≡Cu-OOSO3- intermediates directly oxidizing organic contaminants in water[J]. Chemical Engineering Journal, 2022,441:136100. [32] Wang S, Gao S, Tian J, et al. A stable and easily prepared copper oxide catalyst for degradation of organic pollutants by peroxymonosulfate activation[J]. Journal of Hazardous Materials, 2020,387:121995. [33] Y W, J M, Ge J X, et al. Ultrahigh peroxymonosulfate utilization efficiency over CuO nanosheets via heterogeneous Cu (III) formation and preferential electron transfer during degradation of phenols[J]. Environmental Science& Technology, 2022,56:8984-8992. [34] Wang M M, Liu L J, Xi J R, et al. Lattice doping of Zn boosts oxygen vacancies in Co3O4 nanocages:Improving persulfate activation via forming surface activated complex[J]. Chemical Engineering Journal, 2023,451:138605. [35] Zhong Q, Lin Q, Huang R, et al. Oxidative degradation of tetracycline using persulfate activated by N and Cu codoped biochar[J]. Chemical Engineering Journal, 2020,380:122608. [36] Wang C, Sun R, Huang R, et al. Superior fenton-like degradation of tetracycline by iron loaded graphitic carbon derived from microplastics:Synthesis, catalytic performance, and mechanism[J]. Separation and Purification Technology, 2021,270:118773. [37] 谢金伶,蒲佳兴,李思域,等.钴锰硫化物活化过硫酸盐强化降解盐酸四环素[J].中国环境科学, 2023,43(2):544-551. Xie J L, Pu J X, Li S Y, et al. Enhanced degradation of tetracycline hydrochloride by cobalt-manganese sulfide activated peroxymonosulfate[J]. China Environmental Science, 2023,43(2):544-551. [38] Mi X, Zhong H, Zhang H, et al. Facilitating redox cycles of copper species by pollutants in peroxymonosulfate activation[J]. Environmental Science& Technology, 2022,56(4):2637-2646. [39] Shi Y, Li J, Wan D, et al. Peroxymonosulfate enhanced photocatalysis by carbonyl modified g-C3N4 for effective degradation of the tetracycline hydrochloride[J]. Science of the Total Environment, 2020,749:142313. [40] Wang L, Ma X, Huang G, et al. Construction of ternary CuO/CuFe2O4/g-C3N4 composite and its enhanced photocatalytic degradation of tetracycline hydrochloride with persulfate under simulated sunlight[J]. Journal of Environmental Sciences, 2022,112:59-70.
