Abstract
We designed a photocatalyst and developed sustainable wastewater purification technology, which have significant advantages in effectively solving the global problem of drinking water shortage. In this study, a new nanocomposite was reported and shown to be a catalyst with excellent performance; CuO was coated successively onto functionalized nano γ-Al2O3, and this novel structure could provide abundant active sites. We evaluated the performance of the CuO@γ-Al2O3 nanocomposite catalyst for polyvinyl alcohol (PVA) degradation under visible light irradiation. Under optimized conditions (calcination temperature, 450 °C; mass ratio of γ-Al2O3:Cu(NO3)2·3H2O, 1:15; pH value, 7; catalyst dosage, 2.6 g/L; reaction temperature, 20 °C; and H2O2 dosage, 0.2 g/mL), the CuO@γ-Al2O3 nanocomposite catalyst presented an excellent PVA removal rate of 99.21%. After ten consecutive degradation experiments, the catalyst could still maintain a PVA removal rate of 97.58%, thus demonstrating excellent reusability. This study provides an efficient and easy-to-prepare photocatalyst and proposes a mechanism for the synergistic effect of the photocatalytic reaction and the Fenton-like reaction.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
The datasets used during the current study are available from the corresponding author on reasonable request.
References
Abdelaal HM, Shaikjee A, Esmat M (2020) High performing photocatalytic ZnO hollow sub-micro-spheres fabricated by microwave induced self-assembly approach. Ceram Int 46:19815–19821. https://doi.org/10.1016/j.ceramint.2020.05.034
Abudayyeh AM, Schott O, Feltham HLC et al (2021) Copper catalysts for photo- and electro-catalytic hydrogen production. Inorg Chem Front 8:1015–1029. https://doi.org/10.1039/d0qi01247e
Aghayi-Anaraki M, Safarifard V (2020) Fe3O4@MOF Magnetic nanocomposites: synthesis and applications. Eur J Inorg Chem 2020:1916–1937. https://doi.org/10.1002/ejic.202000012
Agu UA, Mendieta SN, Gerbaldo M et al (2020) Highly active heterogeneous Fenton-like system based on cobalt ferrite. Ind Eng Chem Res 59:1702–1711. https://doi.org/10.1021/acs.iecr.9b04042
Ahn K, Pham-Cong D, Choi HS et al (2016) Bandgap-designed TiO2/SnO2 hollow hierarchical nanofibers: Synthesis, properties, and their photocatalytic mechanism. Curr Appl Phys 16:251–260. https://doi.org/10.1016/j.cap.2015.12.006
Akram N, Ma W, Guo J et al (2021) Synergistic catalysis of Fe3O4/CuO bimetallic catalyst derived from Prussian blue analogues for the efficient decomposition of various organic pollutants. Chem Phys 540:110974. https://doi.org/10.1016/j.chemphys.2020.110974
Ali I, Alharbi OML, Alothman ZA, Badjah AY (2018) Kinetics, thermodynamics, and modeling of amido black dye photodegradation in water using Co/TiO 2 nanoparticles. Photochem Photobiol 94:935–941. https://doi.org/10.1111/php.12937
Ali I, Burakov AE, Melezhik AV et al (2019) Removal of copper(II) and zinc(II) ions in water on a newly synthesized polyhydroquinone/graphene nanocomposite material: kinetics, thermodynamics and mechanism. ChemistrySelect 4:12708–12718. https://doi.org/10.1002/slct.201902657
Ali I, Afshinb S, Poureshgh Y et al (2020) Green preparation of activated carbon from pomegranate peel coated with zero-valent iron nanoparticles (nZVI) and isotherm and kinetic studies of amoxicillin removal in water. Environ Sci Pollut Res 27:36732–36743. https://doi.org/10.1007/s11356-020-09310-1
Ali I, Babkin AV, Burakova IV et al (2021) Fast removal of samarium ions in water on highly efficient nanocomposite based graphene oxide modified with polyhydroquinone: Isotherms, kinetics, thermodynamics and desorption. J Mol Liq 329:115584. https://doi.org/10.1016/j.molliq.2021.115584
Ali I, Konḱova T, Kasianov V et al (2021) Preparation and characterization of nano-structured modified montmorillonite for dioxidine antibacterial drug removal in water. J Mol Liq 331:115770. https://doi.org/10.1016/j.molliq.2021.115770
Bagtache R, Meziani D, Abdmeziem K, Trari M (2021) Synthesis, physical and photo-electrochemical characterizations of a new hybrid host-guest complex [Cu-12(C2N3H2)(8)Cl][(PW12O40)]. J Mol Struct 1227:129718. https://doi.org/10.1016/j.molstruc.2020.129718
Basheer AA (2018) New generation nano-adsorbents for the removal of emerging contaminants in water. J Mol Liq 261:583–593. https://doi.org/10.1016/j.molliq.2018.04.021
Basheer AA (2020) Advances in the smart materials applications in the aerospace industries. AEAT 92:1027–1035. https://doi.org/10.1108/AEAT-02-2020-0040
Behnajady MA, Modirshahla N, Ghanbary F (2007) A kinetic model for the decolorization of CI Acid Yellow 23 by Fenton process. J Hazard Mater 148:98–102. https://doi.org/10.1016/j.jhazmat.2007.02.003
Bian H, Cao M, Wen H et al (2019) Biodegradation of polyvinyl alcohol using cross-linked enzyme aggregates of degrading enzymes from Bacillus niacini. Int J Biol Macromol 124:10–16. https://doi.org/10.1016/j.ijbiomac.2018.11.204
Bielan Z, Kowalska E, Dudziak S et al (2021) Mono- and bimetallic (Pt/Cu) titanium(IV) oxide core-shell photocatalysts with UV/Vis light activity and magnetic separability. Catal Today 361:198–209. https://doi.org/10.1016/j.cattod.2020.05.034
Chen R, Fan F, Dittrich T, Li C (2018) Imaging photogenerated charge carriers on surfaces and interfaces of photocatalysts with surface photovoltage microscopy. Chem Soc Rev 47:8238–8262. https://doi.org/10.1039/c8cs00320c
Chen BB, Liu ML, Huang CZ (2020) Carbon dot-based composites for catalytic applications. Green Chem 22:4034–4054. https://doi.org/10.1039/d0gc01014f
Chen D, Liu C, Lu J et al (2020) Enhanced phycocyanin and DON removal by the synergism of H2O2 and micro-sized ZVI: optimization, performance, and mechanisms. Sci Total Environ 738:140134. https://doi.org/10.1016/j.scitotenv.2020.140134
Chen L, Tian L, Xie J et al (2020) One-step solid state synthesis of facet-dependent contact TiO2 hollow nanocubes and reduced graphene oxide hybrids with 3D/2D heterojunctions for enhanced visible photocatalytic activity. Appl Surf Sci 504:144353. https://doi.org/10.1016/j.apsusc.2019.144353
Chen L, Tian L, Zhao X et al (2020) SPR effect of Au nanoparticles on the visible photocatalytic RhB degradation and NO oxidation over TiO2 hollow nanoboxes. Arab J Chem 13:4404–4416. https://doi.org/10.1016/j.arabjc.2019.08.011
Colmenares JC, Varma RS, Nair V (2017) Selective photocatalysis of lignin-inspired chemicals by integrating hybrid nanocatalysis in microfluidic reactors. Chem Soc Rev 46:6675–6686. https://doi.org/10.1039/c7cs00257b
Dai C, Tian X, Nie Y et al (2018) Surface facet of CuFeO2 nanocatalyst: a key parameter for H2O2 activation in Fenton-like reaction and organic pollutant degradation. Environ Sci Technol 52:6518–6525. https://doi.org/10.1021/acs.est.8b01448
Dai Q, Yuan B, Guo M et al (2020) A novel nano-fibriform C- modified niobium pentoxide by using cellulose templates with highly visible-light photocatalytic performance. Ceram Int 46:13210–13218. https://doi.org/10.1016/j.ceramint.2020.02.096
de Luna MDG, Briones RM, Su C-C, Lu M-C (2013) Kinetics of acetaminophen degradation by Fenton oxidation in a fluidized-bed reactor. Chemosphere 90:1444–1448. https://doi.org/10.1016/j.chemosphere.2012.09.003
Ding Y, Yan Y, Wang H et al (2018) Preparation of hollow Cu and CuOx, microspheres with a hierarchical structure for heterogeneous catalysis. ACS Appl Mater Interfaces 10:41793–41801. https://doi.org/10.1021/acsami.8b16246
Dong Y, Tao F, Wang L et al (2020) One-pot preparation of hierarchical Cu2O hollow spheres for improved visible-light photocatalytic properties. RSC Adv 10:22387–22396. https://doi.org/10.1039/d0ra02460k
Esmaeili S, Zanjanchi MA, Golmojdeh H, Shariati S (2020) Synthesis, characterization and photocatalytic studies of MCM-41 mesoporous silica core-shells doped with selenium oxide and lanthanum ions. Microporous Mesoporous Mat 292:109714. https://doi.org/10.1016/j.micromeso.2019.109714
Gao C, Wang J, Xu H, Xiong Y (2017) Coordination chemistry in the design of heterogeneous photocatalysts. Chem Soc Rev 46:2799–2823. https://doi.org/10.1039/c6cs00727a
Ghafoori S, Mehrvar M, Chan PK (2014) Photoreactor scale-up for degradation of aqueous poly(vinyl alcohol) using UV/H2O2 process. Chem Eng J 245:133–142. https://doi.org/10.1016/j.cej.2014.01.055
Gholizadeh EM, Prasad SKK, Teh ZL, et al (2020) Photochemical upconversion of near-infrared light from below the silicon bandgap. Nat Photonics 14:585-+. https://doi.org/10.1038/s41566-020-0664-3
Gui W, Lin J, Liang Y et al (2019) A two-step strategy for high-efficiency fluorescent dye removal from wastewater. NPJ Clean Water 2:16. https://doi.org/10.1038/s41545-019-0041-2
Hodges BC, Cates EL, Kim J-H (2018) Challenges and prospects of advanced oxidation water treatment processes using catalytic nanomaterials. Nat Nanotechnol 13:642–650. https://doi.org/10.1038/s41565-018-0216-x
Huang Z, Liu J, Huang L et al (2020) One-step synthesis of dandelion-like lanthanum titanate nanostructures for enhanced photocatalytic performance. NPG Asia Mater 12:11. https://doi.org/10.1038/s41427-019-0194-y
Islam MR, Saiduzzaman M, Nishat SS et al (2021) Synthesis, characterization and visible light-responsive photocatalysis properties of Ce doped CuO nanoparticles: a combined experimental and DFT plus U study. Colloid Surf A-Physicochem Eng Asp 617:126386. https://doi.org/10.1016/j.colsurfa.2021.126386
Kadi MW, Mohamed RM, Ismail AA (2020) Uniform dispersion of CuO nanoparticles on mesoporous TiO2 networks promotes visible light photocatalysis. Ceram Int 46:8819–8826. https://doi.org/10.1016/j.ceramint.2019.12.124
Kamat PV (2017) Semiconductor surface chemistry as holy grail in photocatalysis and photovoltaics. Accounts Chem Res 50:527–531. https://doi.org/10.1021/acs.accounts.6b00528
Kanjana N, Maiaugree W, Poolcharuansin P, Laokul P (2020) Size controllable synthesis and photocatalytic performance of mesoporous TiO2 hollow spheres. J Mater Sci Technol 48:105–113. https://doi.org/10.1016/j.jmst.2020.03.013
Kinetics, Thermodynamics, and modeling of amido black dye photodegradation in water using Co/TiO2 nanoparticles - Ali - 2018 - Photochemistry and Photobiology - Wiley Online Library. https://webvpn1.jiangnan.edu.cn/https/77726476706e69737468656265737421fff94d95293564597c1a88be811b343cb55cc5e3193677/doi/https://doi.org/10.1111/php.12937. Accessed 24 Mar 2022
Kisch H (2017) Semiconductor photocatalysis for chemoselective radical coupling reactions. Accounts Chem Res 50:1002–1010. https://doi.org/10.1021/acs.accounts.7b00023
Li X, Huang R, Hu Y et al (2012) A templated method to Bi2WO6 Hollow microspheres and their conversion to double-shell bi2o3/bi2wo6 hollow microspheres with improved photocatalytic performance. Inorg Chem 51:6245–6250. https://doi.org/10.1021/ic300454q
Li A, Zhu W, Li C et al (2019) Rational design of yolk-shell nanostructures for photocatalysis. Chem Soc Rev 48:1874–1907. https://doi.org/10.1039/c8cs00711j
Li Y, Peng Y-K, Hu L et al (2019) Photocatalytic water splitting by N-TiO2 on MgO (111) with exceptional quantum efficiencies at elevated temperatures. Nat Commun 10:4421. https://doi.org/10.1038/s41467-019-12385-1
Li M, Gao X, Liu H et al (2020) Preparation of heterogeneous Fenton catalyst gamma-Cu-Ce-Al2O3 and the evaluation on degradation of phenol. Environ Sci Pollut Res 27:21476–21486. https://doi.org/10.1007/s11356-020-08648-w
Li Y, Shen Q, Guan R et al (2020) A C@TiO2 yolk-shell heterostructure for synchronous photothermal-photocatalytic degradation of organic pollutants. J Mater Chem C 8:1025–1040. https://doi.org/10.1039/c9tc05504e
Li L, Hu C, Zhang L, Shi B (2021) More octahedral Cu+ and surface acid sites in uniformly porous Cu-Al2O3 for enhanced Fenton catalytic performances. J Hazard Mater 406:124739. https://doi.org/10.1016/j.jhazmat.2020.124739
Li X, Min X, Hu X et al (2021) In-situ synthesis of highly dispersed Cu-CuxO nanoparticles on porous carbon for the enhanced persulfate activation for phenol degradation. Sep Purif Technol 276:119260. https://doi.org/10.1016/j.seppur.2021.119260
Liang Q, Gao W, Liu C et al (2020) A novel 2D/1D core-shell heterostructures coupling MOF-derived iron oxides with ZnIn2S4 for enhanced photocatalytic activity. J Hazard Mater 392:122500. https://doi.org/10.1016/j.jhazmat.2020.122500
Liang Y, Chen Y, Lin L et al (2020) An in situ ion exchange grown visible-light-driven Z-scheme AgVO3/AgI graphene microtube for enhanced photocatalytic performance. New J Chem 44:1579–1587. https://doi.org/10.1039/c9nj05376j
Liang Q, Liu X, Wang J et al (2021) In-situ self-assembly construction of hollow tubular g-C3N4 isotype heterojunction for enhanced visible-light photocatalysis: experiments and theories. J Hazard Mater 401:123355. https://doi.org/10.1016/j.jhazmat.2020.123355
Muthukrishnaraj A, Kalaivani SS, Manikandan A et al (2020) Sonochemical synthesis and visible light induced photocatalytic property of reduced graphene oxide@ZnO hexagonal hollow rod nanocomposite. J Alloy Compd 836:155377. https://doi.org/10.1016/j.jallcom.2020.155377
(2021) Preparation and characterization of oxidized graphene for actinides and rare earth elements removal in nitric acid solutions from nuclear wastes. Journal of Molecular Liquids 335:116260. https://doi.org/10.1016/j.molliq.2021.116260
Raees A, Jamal MA, Ahmed I et al (2021) Synthesis and characterization of CeO2/CuO nanocomposites for photocatalytic degradation of methylene blue in visible light. Coatings 11:305. https://doi.org/10.3390/coatings11030305
Ren X, Wang J, Yu J et al (2021) Waste valorization: transforming the fishbone biowaste into biochar as an efficient persulfate catalyst for degradation of organic pollutant. J Clean Prod 291:125225. https://doi.org/10.1016/j.jclepro.2020.125225
Shang S, Jiao X, Chen D (2012) Template-free fabrication of TiO2 Hollow spheres and their photocatalytic properties. ACS Appl Mater Interfaces 4:860–865. https://doi.org/10.1021/am201535u
Shuang Z, Gza B, Xin WC, Mga B (2020) Enhanced catalytic degradation of polyvinyl alcohol from aqueous solutions by novel synthesis of MnCoO 3 @γ-Al 2 O 3 nanocomposites: performance, degradation intermediates and mechanism. J Mol Liq 323:114569. https://doi.org/10.1016/j.molliq.2020.114569
Smith JD, Jamhawi AM, Jasinski JB et al (2019) Organopolymer with dual chromophores and fast charge-transfer properties for sustainable photocatalysis. Nat Commun 10:1837. https://doi.org/10.1038/s41467-019-09316-5
(2018) Stereoselective uptake and degradation of (±)‐o,p‐DDD pesticide stereomers in water‐sediment system. Chirality 30:1088–1095. https://doi.org/10.1002/chir.22989
Strieth-Kalthoff F, James MJ, Teders M et al (2018) Energy transfer catalysis mediated by visible light: principles, applications, directions. Chem Soc Rev 47:7190–7202. https://doi.org/10.1039/c8cs00054a
Su Z, Li J, Zhang D et al (2019) Novel flexible Fenton-like catalyst: unique CuO nanowires arrays on copper mesh with high efficiency across a wide pH range. Sci Total Environ 647:587–596. https://doi.org/10.1016/j.scitotenv.2018.08.022
Wang J, Xiong Z, Zheng J et al (2018) Light-driven micro/nanomotor for promising biomedical tools: principle, challenge, and prospect. Accounts Chem Res 51:1957–1965. https://doi.org/10.1021/acs.accounts.8b00254
Wang H, Tang Q, Chen Z et al (2020) Recent advances on silica-based nanostructures in photocatalysis. Sci China-Mater 63:2189–2205. https://doi.org/10.1007/s40843-020-1381-y
Wang H, Wang H, Wang Z et al (2020) Covalent organic framework photocatalysts: structures and applications. Chem Soc Rev 49:4135–4165. https://doi.org/10.1039/d0cs00278j
Wang J, Li B, Li Y et al (2021) Easily regenerated CuO/gamma-Al2O3 for persulfate-based catalytic oxidation: insights into the deactivation and regeneration mechanism. ACS Appl Mater Interfaces 13:2630–2641. https://doi.org/10.1021/acsami.0c19013
Xiao M, Wang Z, Lyu M et al (2019) Hollow Nanostructures for photocatalysis: advantages and challenges. Adv Mater 31:1801369. https://doi.org/10.1002/adma.201801369
Yang X, Wang D (2018) Photocatalysis: from fundamental principles to materials and applications. ACS Appl Energ Mater 1:6657–6693. https://doi.org/10.1021/acsaem.8b01345
Zhang H, Duan S, Radjenovic PM et al (2020) Core-shell nanostructure-enhanced raman spectroscopy for surface catalysis. Accounts Chem Res 53:729–739. https://doi.org/10.1021/acs.accounts.9b00545
Zhao X, Su Y, Qi X, Han X (2017) A facile method to prepare novel Ag2O/Ag2CO3 three-dimensional hollow hierarchical structures and their water purification function. ACS Sustain Chem Eng 5:6148–6158. https://doi.org/10.1021/acssuschemeng.7b01040
Zhao H, Cui S, Li G et al (2020) 1T-and 2H-mixed phase MoS2 nanosheets coated on hollow mesoporous TiO2 nanospheres with enhanced photocatalytic activity. J Colloid Interface Sci 567:10–17. https://doi.org/10.1016/j.jcis.2020.01.100
Zhou Z, Zhang Y, Shen Y et al (2018) Molecular engineering of polymeric carbon nitride: advancing applications from photocatalysis to biosensing and more. Chem Soc Rev 47:2298–2321. https://doi.org/10.1039/c7cs00840f
Zhou Y, Lu J, Liu Q et al (2020) A novel hollow-sphere cyclodextrin nanoreactor for the enhanced removal of bisphenol A under visible irradiation. J Hazard Mater 384:121267. https://doi.org/10.1016/j.jhazmat.2019.121267
Funding
We gratefully acknowledge the support of this research by the Natural Science Foundation of Jiangsu Province (BK20200620), Natural Science Foundation of China (52103140), National High-tech R&D Program of China (No.2016YFB0302901), nand Fundamental Research Funds for the Central Universities (No.JUSRP51723B) for the financial support of the work.
Author information
Authors and Affiliations
Contributions
Gaofeng Zhu: conceptualization, methodology, software, formal analysis, writing – original draft. Yang Jin: funding acquisition, formal analysis. Mingqiao Ge: writing – review and editing, supervision, funding acquisition.
Corresponding author
Ethics declarations
Ethics approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Guilherme L. Dotto
Publisher's note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Zhu, G., Jin, Y. & Ge, M. Simple preparation of a CuO@γ-Al2O3 Fenton-like catalyst and its photocatalytic degradation function. Environ Sci Pollut Res 29, 68636–68651 (2022). https://doi.org/10.1007/s11356-022-20698-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-022-20698-w