Enhanced Fenton-like process over Cu/L(+)-ascorbic acid co-doping mesoporous silica for toxicity reduction of emerging contaminants

doi:10.1007/s11783-024-1804-7

Front. Environ. Sci. Eng.

2024, Vol. 18

Issue (4) : 44 https://doi.org/10.1007/s11783-024-1804-7

RESEARCH ARTICLE

Enhanced Fenton-like process over Cu/L(+)-ascorbic acid co-doping mesoporous silica for toxicity reduction of emerging contaminants

Yuhang Liu, Wenxuan Deng, Xiaojun Wu, Chun Hu, Lai Lyu(

)

Key Laboratory for Water Quality and Conservation of the Pearl River Delta (Ministry of Education), Institute of Environmental Research at Greater Bay, Guangzhou University, Guangzhou 510006, China

Download: PDF(5025 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

● Cu-C-MSNs are developed via a co-doping step of Cu with L(+)-ascorbic acid.

● Cu-C-MSNs show superb performance in removing contaminants and purifying wastewater.

● The performance is owing to the polarization electric field and cation-π structures.

● The biological toxicity of bisphenol A is considerably weakened after the reaction.

Effective removal of emerging contaminants (ECs) to minimize their impacts on human health and the natural environment is a global priority. For the removal of ECs in water, we fabricated a seaweed spherical microsphere catalyst with Cu cation-π structures by in situ doping of Cu species and ascorbic acid in mesoporous silica (Cu-C-MSNs) via a hydrothermal method. The results indicate that bisphenol A (BPA) is substantially degraded within 5 min under natural conditions, with its biological toxicity considerably weakened. Moreover, industrial wastewater could also be effectively purified by Cu-C-MSNs/H₂O₂ system. The presence of metal sites and the complexation of ECs via cation-π interaction and π-π stacking on the catalyst surface were directly responsible for the polarization distribution of electrons, thus activating H₂O₂ and dissolved oxygen (DO). The removal of contaminants could be attributed primarily to 1) the activation of H₂O₂ into ^•OH to attack the contaminants and 2) self-cleavage because of the transfer of electrons from the contaminants to the catalysts. This study provides an innovative solution for the effective treatment of ECs and has positive implications for easing global environmental crises.

Keywords Cation-π structures Polarization electric field Fenton-like process Contaminants cleavage

Corresponding Author(s): Lai Lyu

Issue Date: 15 December 2023

Cite this article:

Yuhang Liu,Wenxuan Deng,Xiaojun Wu, et al. Enhanced Fenton-like process over Cu/L(+)-ascorbic acid co-doping mesoporous silica for toxicity reduction of emerging contaminants[J]. Front. Environ. Sci. Eng., 2024, 18(4): 44.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-024-1804-7
https://academic.hep.com.cn/fese/EN/Y2024/V18/I4/44

Fig.1 (a) Preparation process of Cu-C-MSNs. (b) and (c) SEM images of Cu-C-MSNs. (d) and (e) TEM images of Cu-C-MSNs. (f) Element mapping of O, Si, Cu and C from SEM images.

Fig.2 (a) XRD patterns of C-SiO₂ NSs and Cu-C-MSNs. (b) FT-IR spectra of Cu-C-MSNs. XPS orbit spectrum of Cu-C-MSNs and SiO₂ NSs in (c) Cu 2p_3/2, (d) Si 2p, (e) O 1s.

Fig.3 (a) Degradation of BPA in the Cu-C-MSNs, C-SiO₂, Cu-MSNs system with H₂O₂. (b) The catalytic effect of different contaminants. (c) Reusability of Cu-C-MSNs for BPA degradation. (d) Excitation-Emission-Matrix Spectra of printing and dyeing wastewater. (e) Wastewater after 120 min of degradation of Cu-C-MSNs/H₂O₂ system. (f) Wastewater after 180 min of degradation of Cu-C-MSNs/H₂O₂ system. Reaction conditions: [catalyst] = 1.0 g/L, [H₂O₂] = 0.01 mol/L, [BPA] =0.01 g/L, t = 35 °C.

Fig.4 (a) The catalytic effect of different catalyst dosages for degradation of BPA. (b) The catalytic effect of different H₂O₂ concentrations for degradation of BPA. (c) The catalytic effect of different BPA concentrations. (d) Degradation of BPA in the range pH = 5–9. (e) Influence of different anions (10 mmol/L) in degrading BPA. (f) The catalytic effect of different HA concentrations for degradation of BPA. Reaction conditions: [Catalyst] = 1.0 g/L, [H₂O₂] = 0.01 mol/L, [BPA] = 0.01 g/L, t = 35 °C.

Fig.5 (a) BMPO trapped ^?OH in various aqueous. (b) BMPO trapped O₂^?? various aqueous. (c) BPA degradation curves in Cu-C-MSNs/H₂O₂ system in the presence of TBA (?OH quenching agent) and BQ (O₂^?? quenching agent). (d) Schematic illustration of H₂O₂/O₂ activation and contaminants conversion.

Fig.6 (a) Proposed degradation pathways in the Cu-C-MSNs system. (b) Fathead minnow LC50 (96 h), (c) Daphnia magna LC50 (48 h), and (d) Developmental toxicity of BPA and its degradation intermediates.

1	C G Alimba , C Faggio . (2019). Microplastics in the marine environment: current trends in environmental pollution and mechanisms of toxicological profile. Environmental Toxicology and Pharmacology, 68: 61–74 https://doi.org/10.1016/j.etap.2019.03.001
2	S Almeida , A Raposo , M Almeida-González , C Carrascosa . (2018). Bisphenol A: food exposure and impact on human health. Comprehensive Reviews in Food Science and Food Safety, 17(6): 1503–1517 https://doi.org/10.1111/1541-4337.12388
3	J S Bing , C Hu , L L Zhang . (2017). Enhanced mineralization of pharmaceuticals by surface oxidation over mesoporous gamma-Ti-Al2O3 suspension with ozone. Applied Catalysis B: Environmental, 202: 118–126 https://doi.org/10.1016/j.apcatb.2016.09.019
4	W R Cao , C Hu , L Lyu . (2021). Efficient decomposition of organic pollutants over nZVI/FeOx/FeNy-Anchored NC Layers via a novel Dual-Reaction-Centers-Based wet air oxidation process under natural conditions. ACS ES&T Engineering, 1(9): 1333–1341 https://doi.org/10.1021/acsestengg.1c00157
5	E M Cuerda-Correa , M F Alexandre-Franco , C Fernandez-Gonzalez . (2019). Advanced oxidation processes for the removal of antibiotics from water: an overview. Water, 12(1): 102 https://doi.org/10.3390/w12010102
6	Minh T Do , J Song , A Deb , L Cha , V Srivastava , M Sillanpää . (2020). Biochar based catalysts for the abatement of emerging pollutants: a review. Chemical Engineering Journal, 394: 124856 https://doi.org/10.1016/j.cej.2020.124856
7	L H Gao , Y J Cao , L Z Wang , S L Li . (2022). A review on sustainable reuse applications of fenton sludge during wastewater treatment. Frontiers of Environmental Science & Engineering, 16(6): 77 https://doi.org/10.1007/s11783-021-1511-6
8	T Gao , C Lu , C Hu , L Lyu . (2021). H2O2 inducing dissolved oxygen activation and electron donation of pollutants over Fe-ZnS quantum dots through surface electron-poor/rich microregion construction for water treatment. Journal of Hazardous Materials, 420: 126579 https://doi.org/10.1016/j.jhazmat.2021.126579
9	M A Gebbie , W Wei , A M Schrader , T R Cristiani , H A Dobbs , M Idso , B F Chmelka , J H Waite , J N Israelachvili . (2017). Erratum: Tuning underwater adhesion with cation-π interactions. Nature Chemistry, 9(7): 723 https://doi.org/10.1038/nchem.2813
10	A Giwa , A Yusuf , H A Balogun , N S Sambudi , M R Bilad , I Adeyemi , S Chakraborty , S Curcio . (2021). Recent advances in advanced oxidation processes for removal of contaminants from water: a comprehensive review. Process Safety and Environmental Protection, 146: 220–256 https://doi.org/10.1016/j.psep.2020.08.015
11	X S He , B D Xi , X Li , H W Pan , D An , S G Bai , D Li , D Y Cui . (2013). Fluorescence excitation-emission matrix spectra coupled with parallel factor and regional integration analysis to characterize organic matter humification. Chemosphere, 93(9): 2208–2215 https://doi.org/10.1016/j.chemosphere.2013.04.039
12	C J Hines , A L Christianson , M V Jackson , X Ye , J R Pretty , J E Arnold , A M Calafat . (2018). An evaluation of the relationship among uurine, air, and hand measures of exposure to bisphenol A (BPA) in US manufacturing workers. Annals of Work Exposures and Health, 62(7): 840–851 https://doi.org/10.1093/annweh/wxy042
13	M T Khan , I A Shah , I Ihsanullah , M Naushad , S Ali , S H A Shah , A W Mohammad . (2021). Hospital wastewater as a source of environmental contamination: an overview of management practices, environmental risks, and treatment processes. Journal of Water Process Engineering, 41: 101990 https://doi.org/10.1016/j.jwpe.2021.101990
14	S Khan , M Naushad , M Govarthanan , J Iqbal , S M Alfadul . (2022). Emerging contaminants of high concern for the environment: current trends and future research. Environmental Research, 207: 112609 https://doi.org/10.1016/j.envres.2021.112609
15	Q Q Li , C Lv , X W Xia , C Peng , Y Yang , F Guo , J F Zhang . (2022). Separation/degradation behavior and mechanism for cationic/anionic dyes by Ag-functionalized Fe3O4-PDA core-shell adsorbents. Frontiers of Environmental Science & Engineering, 16(11): 138 https://doi.org/10.1007/s11783-022-1572-1
16	F E López-Suárez , S Parres-Esclapez , A Bueno-Lopez , M J Illan-Gomez , B Ura , J Trawczynski . (2009). Role of surface and lattice copper species in copper-containing (Mg/Sr)TiO3 perovskite catalysts for soot combustion. Applied Catalysis B: Environmental, 93(1–2): 82–89 https://doi.org/10.1016/j.apcatb.2009.09.015
17	C Lu , K L Deng , C Hu , L Lyu . (2020). Dual-reaction-center catalytic process continues Fenton’s story. Frontiers of Environmental Science & Engineering, 14(5): 82 https://doi.org/10.1007/s11783-020-1261-x
18	L Lyu , W Cao , G Yu , D Yan , K Deng , C Lu , C Hu . (2020). Enhanced polarization of electron-poor/rich micro-centers over nZVCu-Cu(II)-rGO for pollutant removal with H2O2. Journal of Hazardous Materials, 383: 121182 https://doi.org/10.1016/j.jhazmat.2019.121182
19	L Lyu , C Hu . (2017). Heterogeneous Fenton catalytic water treatment technology and mechanism. Progress in Chemistry, 29(9): 981–999 (inChinese) https://doi.org/10.7536/pc170552
20	L Lyu , L Zhang , Q Wang , Y Nie , C Hu . (2015b). Enhanced Fenton catalytic efficiency of γ-Cu-Al2O3 by σ-Cu2+-Ligand complexes from aromatic pollutant degradation. Environmental Science & Technology, 49(14): 8639–8647 https://doi.org/10.1021/acs.est.5b00445
21	L Lyu , L L Zhang , G Z He , H He , C Hu . (2017). Selective H2O2 conversion to hydroxyl radicals in the electron-rich area of hydroxylated C-g-C3N4/ CuCo-Al2O3. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 5(15): 7153–7164 https://doi.org/10.1039/C7TA01583F
22	L Lyu , L L Zhang , C Hu . (2015a). Enhanced Fenton-like degradation of pharmaceuticals over framework copper species in copper-doped mesoporous silica microspheres. Chemical Engineering Journal, 274: 298–306 https://doi.org/10.1016/j.cej.2015.03.137
23	L Lyu , L L Zhang , C Hu . (2016a). Galvanic-like cells produced by negative charge nonuniformity of lattice oxygen on d-TiCuAl-SiO2 nanospheres for enhancement of Fenton-catalytic efficiency. Environmental Science. Nano, 3(6): 1483–1492 https://doi.org/10.1039/C6EN00290K
24	L Lyu , L L Zhang , C Hu , M Yang . (2016b). Enhanced Fenton-catalytic efficiency by highly accessible active sites on dandelion-like copper-aluminum-silica nanospheres for water purification. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 4(22): 8610–8619 https://doi.org/10.1039/C6TA02276F
25	Z Mitić, G S Nikolic, M Cakic, P Premovic, L Ilic (2009). FTIR spectroscopic characterization of Cu(II) coordination compounds with exopolysaccharide pullulan and its derivatives. Journal of Molecular Structure, 924–926: 264–273 10.1016/j.molstruc.2009.01.019
26	N Morin-Crini , E Lichtfouse , G R Liu , V Balaram , A R L Ribeiro , Z J Lu , F Stock , E Carmona , M R Teixeira , L A Picos-Corrales . et al.. (2022). Worldwide cases of water pollution by emerging contaminants: a review. Environmental Chemistry Letters, 20(4): 2311–2338 https://doi.org/10.1007/s10311-022-01447-4
27	B S Rathi , P S Kumar , P L Show . (2021). A review on effective removal of emerging contaminants from aquatic systems: current trends and scope for further research. Journal of Hazardous Materials, 409: 124413 https://doi.org/10.1016/j.jhazmat.2020.124413
28	S Sauvé , M Desrosiers . (2014). A review of what is an emerging contaminant. Chemistry Central Journal, 8(1): 15 https://doi.org/10.1186/1752-153X-8-15
29	J Scaria , A Gopinath , P V Nidheesh . (2021). A versatile strategy to eliminate emerging contaminants from the aqueous environment: heterogeneous Fenton process. Journal of Cleaner Production, 278: 124014 https://doi.org/10.1016/j.jclepro.2020.124014
30	M Taheran , M Naghdi , S K Brar , M Verma , R Y Surampalli . (2018). Emerging contaminants: here today, there tomorrow. Environmental Nanotechnology, Monitoring & Management, 10: 122–126 https://doi.org/10.1016/j.enmm.2018.05.010
31	F H M Tang , M Lenzen , A Mcbratney , F Maggi . (2021). Risk of pesticide pollution at the global scale. Nature Geoscience, 14(4): 206–210 https://doi.org/10.1038/s41561-021-00712-5
32	N H Tran, K Y H Gin (2017). Occurrence and removal of pharmaceuticals, hormones, personal care products, and endocrine disrupters in a full-scale water reclamation plant. Science of the Total Environment, 599–600: 1503–1516 10.1016/j.scitotenv.2017.05.09728531959
33	J Trivedi , U Chhaya . (2022). Bioremediation of bisphenol A found in industrial wastewater using Trametes versicolor (TV) laccase nanoemulsion-based bead organogel in packed bed reactor. Water Environment Research, 94(10): e10786 https://doi.org/10.1002/wer.10786
34	F S vom Saal , L N Vandenberg . (2021). Update on the health effects of Bisphenol A: overwhelming evidence of harm. Endocrinology, 162(3): bqaa171 https://doi.org/10.1210/endocr/bqaa171
35	B Wang , G Yu . (2022). Emerging contaminant control: from science to action. Frontiers of Environmental Science & Engineering, 16(6): 81 https://doi.org/10.1007/s11783-022-1559-y
36	J Wang , M Zheng , Y Deng , M Liu , Y Chen , N Gao , E Du , W Chu , H Guo . (2022a). Generality and diversity on the kinetics, toxicity and DFT studies of sulfate radical-induced transformation of BPA and its analogues. Water Research, 219: 118506 https://doi.org/10.1016/j.watres.2022.118506
37	X Y Wang , G Z Xu , Y Z Tu , D S Wu , A M Li , X C Xie . (2021a). BiOBr/PBCD-B-D dual-function catalyst with oxygen vacancies for Acid Orange 7 removal: evaluation of adsorption-photocatalysis performance and synergy mechanism. Chemical Engineering Journal, 411: 128456 https://doi.org/10.1016/j.cej.2021.128456
38	Y Wang , L Lyu , D Wang , H Q Yu , T Li , Y Gao , F Li , J C Crittenden , L Zhang , C Hu . (2021b). Cation-Pi induced surface cleavage of organic pollutants with ·OH formation from H2O for water treatment. iScience, 24(8): 102874 https://doi.org/10.1016/j.isci.2021.102874
39	Y M Wang , P Zhang , L Lyu , W X Liao , C Hu . (2022b). Efficient destruction of humic acid with a self-purification process in an Fe-O-FeyCz/Fe-x-GZIF-8-rGO aqueous suspension. Chemical Engineering Journal, 446: 136625 https://doi.org/10.1016/j.cej.2022.136625
40	C Xiao , L Wang , Q Zhou , X Huang . (2020). Hazards of bisphenol A (BPA) exposure: a systematic review of plant toxicology studies. Journal of Hazardous Materials, 384: 121488 https://doi.org/10.1016/j.jhazmat.2019.121488
41	J Xing , S Zhang , M Zhang , J Hou . (2022a). A critical review of presence, removal and potential impacts of endocrine disruptors bisphenol A. Comparative Biochemistry and Physiology. Toxicology & Pharmacology: CBP, 254: 109275 https://doi.org/10.1016/j.cbpc.2022.109275
42	X Xing , N Li , D D Liu , J Cheng , Z P Hao . (2022b). Effect of Cu-ZSM-5 catalysts with different CuO particle size on selective catalytic oxidation of N,N-Dimethylformamide. Frontiers of Environmental Science & Engineering, 16(10): 125 https://doi.org/10.1007/s11783-022-1557-0
43	R Yamaguchi , S Kurosu , M Suzuki , Y Kawase . (2018). Hydroxyl radical generation by zero-valent iron/Cu (ZVI/Cu) bimetallic catalyst in wastewater treatment: heterogeneous Fenton/Fenton-like reactions by Fenton reagents formed in-situ under oxic conditions. Chemical Engineering Journal, 334: 1537–1549 https://doi.org/10.1016/j.cej.2017.10.154
44	S Yazici Guvenc , G Varank . (2021). Degradation of refractory organics in concentrated leachate by the Fenton process: central composite design for process optimization. Frontiers of Environmental Science & Engineering, 15(1): 2 https://doi.org/10.1007/s11783-020-1294-1
45	H Zhang , C Tang , Y Lv , C Sun , F Gao , L Dong , Y Chen . (2012). Synthesis, characterization, and catalytic performance of copper-containing SBA-15 in the phenol hydroxylation. Journal of Colloid and Interface Science, 380(1): 16–24 https://doi.org/10.1016/j.jcis.2012.04.059
46	H X Zhang , C W Li , L Lyu , C Hu . (2020a). Surface oxygen vacancy inducing peroxymonosulfate activation through electron donation of pollutants over cobalt-zinc ferrite for water purification. Applied Catalysis B: Environmental, 270: 118874 https://doi.org/10.1016/j.apcatb.2020.118874
47	J Zhang , B Lv , M Xing , J Yang . (2015). Tracking the composition and transformation of humic and fulvic acids during vermicomposting of sewage sludge by elemental analysis and fluorescence excitation-emission matrix. Waste Management, 39: 111–118 https://doi.org/10.1016/j.wasman.2015.02.010
48	X Zhang , J Liang , Y Sun , F Zhang , C Li , C Hu , L Lyu . (2020b). Mesoporous reduction state cobalt species-doped silica nanospheres: an efficient Fenton-like catalyst for dual-pathway degradation of organic pollutants. Journal of Colloid and Interface Science, 576: 59–67 https://doi.org/10.1016/j.jcis.2020.05.007
49	S Y Zhao , C X Chen , J Ding , S S Yang , Y N Zang , N Q Ren . (2022). One-pot hydrothermal fabrication of BiVO4/Fe3O4/rGO composite photocatalyst for the simulated solar light-driven degradation of Rhodamine B. Frontiers of Environmental Science & Engineering, 16(3): 36 https://doi.org/10.1007/s11783-021-1470-y
50	W Zheng , S You , Z Chen , B Ding , Y Huang , N Ren , Y Liu . (2023). Copper nanowire networks: an effective electrochemical peroxymonosulfate activator toward nitrogenous pollutant abatement. Environmental Science & Technology, 57(27): 10127–10134 https://doi.org/10.1021/acs.est.3c03201

[1]

FSE-23101-OF-LYH_suppl_1

Download

[1]	Shicheng Wei, Cuiping Zeng, Yaobin Lu, Guangli Liu, Haiping Luo, Renduo Zhang. Degradation of antipyrine in the Fenton-like process with a La-doped heterogeneous catalyst[J]. Front. Environ. Sci. Eng., 2019, 13(5): 66-.

Viewed

Full text

Abstract

Cited

Shared

Discussed