Skip to main content
SpringerLink
Log in

Sunlight-driven photocatalytic degradation of ciprofloxacin and organic dyes by biosynthesized rGO–ZrO2 nanocomposites

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Aquatic ecology has been greatly threatened by the discharge of effluents of textile and antibiotic industries into natural waters. Herein, an efficient and easily recycled reduced graphene oxide/zirconium oxide nanocomposite has been synthesized using banana peel extract (abbreviated as rGO–ZrO2 in this work). The X-ray diffraction (XRD), field emission scanning electronic microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), Brunauer–Emmett–Teller (BET), UV–visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy were used to analyze the synthesized material. The as-prepared rGO-ZrO2 nanocomposite was employed as a photocatalyst for the decomposition of rhodamine blue (RhB) and crystal violet (CV) dyes, and ciprofloxacin (CIP) antibiotic by illumination with direct sunlight. The RhB and CV were degraded to maximum extent of around 86 and 90%, respectively, over the rGO–ZrO2 nanocomposite after exposure to direct sunlight for 120 min. On the other hand, the degradation of CIP was approximately 93.1% over the rGO–ZrO2 nanocomposite in 240 min under same experimental conditions. Further studies were performed regarding the role of parameters like pH, catalyst dose, and scavengers, in order to understand the superiority of rGO-ZrO2 nanocomposite in degrading organic pollutants. Moreover, the intermediate products and plausible CIP degradation mechanisms were examined using liquid chromatography-mass spectrometry (LC–MS). Moreover, the catalyst was easily separated from the solution and demonstrated good stability and reusability. The RhB, CV, and CIP removal efficiency were 80%, 83%, and 88%, respectively, after five cycles.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

Data availability

Not applicable.

References

  • Afzal MZ, Zu P, Zhang CM, Guan J, Song C, Sun XF, Wang SG (2022) Sonocatalytic degradation of ciprofloxacin using hydrogel beads of TiO2 incorporated biochar and chitosan. J Hazard Mater 334:128879

    Article  Google Scholar 

  • Ahmad W, Khan A, Ali N, Khan S, Uddin S, Malik S, Ali N, Khan H, Khan H, Bilal M (2020) Photocatalytic degradation of crystal violet dye under sunlight by chitosan-encapsulated ternary metal selenide microspheres. Environ Sci Pollut Res 28:8074–8087

    Article  Google Scholar 

  • Alagarsamya A, Chandrasekaran S, Manikandan A (2022) Green synthesis and characterization studies of biogenic zirconium oxide (ZrO2) nanoparticles for adsorptive removal of methylene blue dye. J Mol Struct 1247:131275

    Article  Google Scholar 

  • Ameur SB, Belhadjltaief H, Duponchel B, Leroy G, Amlouk M, Guermazi H, Guermazi S (2019) Enhanced photocatalytic activity against crystal violet dye of Co and In doped ZnO thin films grown on PEI flexible substrate under UV and sunlight irradiations. Heliyon 5:e01912

    Article  Google Scholar 

  • Anwer H, Park JW (2018) Synthesis and characterization of a heterojunction rGO/ZrO2/Ag3PO4 nanocomposite for degradation of organic contaminants. J Hazard Mater 358:416–426

    Article  CAS  Google Scholar 

  • Bano K, Mittal SK, Singh P, Kaushal S (2021) Sunlight driven photocatalytic degradation of organic pollutants using a MnV2O6/BiVO4 heterojunction: mechanistic perception and degradation pathways. Nanoscale Adv 3:6446–6458

    Article  CAS  Google Scholar 

  • Beshkar F, Niasari MS, Amiri O (2021) Facile one-pot in situ synthesis and characterization of Cu2O/Cu2(PO4)(OH) binary heterojunction nanocomposite for the efficient photocatalytic degradation of ciprofloxacin from aqueous solution under direct sunlight irradiation. Ind Eng Chem Res 60:9578–9591

    Article  CAS  Google Scholar 

  • Bonavolonta C, Vettoliere A, Falco G, Aramo C, Rendina I, Ruggiero B, Silvestrini P, Valentino M (2021) Reduced graphene oxide on silicon-based structure as novel broadband photodetector. Sci Rep 11:13015

    Article  CAS  Google Scholar 

  • Bumajdad A, Nazeer AA, Sagheer F, Nahar S, Zaki M (2018) Controlled synthesis of ZrO2 nanoparticles with tailored size, morphology and crystal phases via organic/inorganic hybrid films. Sci Rep 8:3695

    Article  Google Scholar 

  • Chau TP, Veeraragavan GR, Narayanan M, Chinnathambi A, Alharbi SA, Subramani B, Brindhadevi K, Pimpimon T, Pikulkaew S (2022) Green synthesis of Zirconium nanoparticles using Punica granatum (pomegranate) peel extract and their antimicrobial and antioxidant potency. Environ Res 209:112771

    Article  CAS  Google Scholar 

  • Chu HJ, Lee CY, Tai NH (2014) Green reduction of graphene oxide by Hibiscus sabdariffa L. to fabricate flexible graphene electrode. Carbon 80:725–733

    Article  CAS  Google Scholar 

  • Dmochowska A, Czajkowska J, Jędrzejewski R, Stawiński W, Migdał P, Toboła M (2020) Pectin based banana peel extract as a stabilizing agent in zinc oxide nanoparticles synthesis. Int J Biol Macromol 165:1581–1592

    Article  CAS  Google Scholar 

  • Gurushantha K, Anantharaju KS, Renuka L, Sharma SC, Nagaswarupa HP, Prashantha SC, Vidya YS, Nagabhushana H (2017) New green synthesized reduced graphene oxide– ZrO2 composite as high performance photocatalyst under sunlight. RSC Adv 7:12690–12703

    Article  CAS  Google Scholar 

  • Hu L, Chen F, Hu P, Zou L, Hu X (2016) Hydrothermal synthesis of SnO2-ZnS nanocomposite as a photocatalyst for degradation of rhodamine B under simulated and natural sunlight. J Mol Catal A Chem 411:203–213

    Article  CAS  Google Scholar 

  • Jing L, Xu Y, Liu J, Zhou M, Xu H, Xie M, Li H, Xie J (2020) Direct Z-scheme red carbon nitride/rod-like lanthanum vanadate composites with enhanced photodegradation of antibiotic contaminants. Appl Catalysis b: Environ 277:119245

    Article  CAS  Google Scholar 

  • Kang J, Jin C, Li Z, Wang M, Chen Z, Wang Y (2020) Dual Z-scheme MoS2/g-C3N4/Bi24O31Cl10 ternary heterojunction photocatalysts for enhanced visible-light photodegradation of antibiotic. J Alloy Compd 825:153975

    Article  CAS  Google Scholar 

  • Kaur N, Kaur J, Badru R, Kaushal S, Singh P (2020) BGO/AlFu MOF core shell nano-composite based bromide ion-selective electrode. J Environ Chem Eng 8:104375

    Article  CAS  Google Scholar 

  • Kaushal S, Badru R, Kumar S, Sharma PK, Mittal SK, Singh P (2016) Electrochemical behavior of a membrane based on zirconium (IV) phosphoborate nanocomposite and its application in dye removal. RSC Adv 6(112):111606–111615

    Article  CAS  Google Scholar 

  • Kaushal S, Badru R, Kumar S, Kaur H, Singh P (2018) Efficient removal of cationic and anionic dyes from their binary mixtures by organic–inorganic hybrid material. J Inorg Organomet Polym Mater 28(3):968–977

    Article  CAS  Google Scholar 

  • Kaushal S, Kaur N, Kaur M, Singh P (2020) Dual-responsive pectin/graphene oxide (Pc/GO) nano-composite as an efficient adsorbent for Cr (III) ions and photocatalyst for degradation of organic dyes in waste water. J Photochem Photobiol 403:112841

    Article  CAS  Google Scholar 

  • Kaushal S, Kurichh P, Singh P (2021) Novel 3D flower like ZnO/MnV2O6 heterojunction as an efficient adsorbent for the removal of imidacloprid and photocatalyst for degradation of organic dyes in waste water. Polyhedron 201:115161

    Article  CAS  Google Scholar 

  • Kaushal S, Kumar A, Bains H, Singh P (2022) Photocatalytic degradation of tetracycline antibiotic and organic dyes using biogenic synthesized CuO/Fe2O3 nanocomposite: pathways and mechanism insights. Environ Sci Pollut Res. https://doi.org/10.1007/s11356-022-24848-y

    Article  Google Scholar 

  • Kaushal S, Singh P, Kaur N (2022) Metal organic framework-derived Zr/Cu bimetallic photocatalyst for the degradation of tetracycline and organic dyes. Environ Nanotechnol Monit Manag 18:100727

    CAS  Google Scholar 

  • Khan SA, Arshad Z, Shahid S, Arshad I, Rizwan K, Sher M, Fatima U (2019) Synthesis of TiO2/graphene oxide nanocopmosites for their enhanced photocatalytic activity against methylene blue dye and ciprofloxacin. Compos B Eng 175:107120

    Article  CAS  Google Scholar 

  • Kokila T, Ramesh PS, Geetha D (2015) Biosynthesis of silver nanoparticles from Cavendish banana peel extract and its antibacterial and free radical scavenging assay: a novel biological approach. Appl Nanosci 5:911–920

    Article  CAS  Google Scholar 

  • Kumari V, Badru R, Singh S, Kaushal S, Singh P (2020) Synthesis and electrochemical behaviour of GO doped ZrP nanocomposite membranes. J Environ Chem Eng 8:103690

    Article  CAS  Google Scholar 

  • Kumari V, Kaushal S, Singh P (2022) Green synthesis of a CuO/rGO nanocomposite using a Terminalia arjuna bark extract and its catalytic activity for the purification of water. Mater Adv 3(4):2170–2184

    Article  CAS  Google Scholar 

  • Li W, Zuo Y, Jiang L, Yao D, Chen Z, He G, Chen H (2020) Bi2Ti2O7/TiO2/RGO composite for the simulated sunlight-driven photocatalytic degradation of ciprofloxacin. Mater Chem Phys 256:123650

    Article  CAS  Google Scholar 

  • Li Y, Fu Y, Zhu M (2020) Green synthesis of 3D tripyramid TiO2 architectures with assistance of aloe extracts for highly efficient photocatalytic degradation of antibiotic ciprofloxacin. Appl Catal B 260:118149

    Article  CAS  Google Scholar 

  • Li K, Ma S, Xu S, Fu H, Li Z, Liu S, Du J (2021) The mechanism changes during bisphenol A degradation in three iron functionalized biochar/peroxymonosulfate systems: the crucial roles of iron contents and graphitized carbon layers. J Hazard Mater 404:124145

    Article  CAS  Google Scholar 

  • Ma W, Yao B, Zhang W, He Y, Yu Y, Niu J, Wang C (2018) A novel multi-flaw MoS2 nanosheet piezocatalyst with super high degradation efficiency for ciprofloxacin. Environ Sci Nano 5(12):2876–2887

    Article  CAS  Google Scholar 

  • Majedi A, Abbasi A, Davar F (2016) Green synthesis of zirconia nanoparticles using the modified pechini method and characterization of its optical and electrical properties. J Sol-Gel Sci Technol 77:542–552

    Article  CAS  Google Scholar 

  • Manikandan V, Elancheran R, Revathi P, Suganya P, Krishnasamy K (2020) Efficient photocatalytic degradation of crystal violet by using graphene oxide/nickel sulphide nanocomposites. Bull Mater Sci 43:265

    Article  CAS  Google Scholar 

  • Morrison SR (1980) Electrochemistry at semiconductor and oxidized metal electrode. Plenum, New York

    Book  Google Scholar 

  • Mukharjee I, Cilamkoti V, Dutta RK (2021) Sunlight-driven photocatalytic degradation of ciprofloxacin by carbon dots embedded in ZnO nanostructures. ACS Appl Nano Mater 4(8):7686–7697

    Article  Google Scholar 

  • Pirzada BM, Pushpendra, Kunchala RK, Naidu BS (2019) Synthesis of LaFeO3/Ag2CO3 nanocomposites for photocatalytic degradation of rhodamine B and p-chlorophenol under natural sunlight. ACS Omega 4:2618–2629

    Article  CAS  Google Scholar 

  • Rani S, Kumar A, Steplinpaulselvin S, Rajaram R, Silambarasan TS, Lydia S, Chen Y (2020) Survival assessment of simple food webs for dye wastewater after photocatalytic degradation using SnO2/GO nanocomposites under sunlight irradiation. Sci Total Environ 721:137805

    Article  Google Scholar 

  • Rashid J, Abbas A, Chang LC, Iqbal A, Haq I, Rehman A, Awan SU, Arshad M, Rafique M, Barakat MA (2019) Butterfly cluster like lamellar BiOBr/TiO2 nanocomposite for enhanced sunlight photocatalytic mineralization of aqueous ciprofloxacin. Sci Total Environ 665:668–677

    Article  CAS  Google Scholar 

  • Shanthi S, Tharani N (2016) Green synthesis of zirconium dioxide (ZrO2) nano particles using Acalypha indica leaf extract. Int J Appl Sci 3:23–25

    Google Scholar 

  • Sharma A, Verma K, Kaushal S, Badru R (2021) Selective N-alkylation of amines with DMC over biogenic Cu–Zr bimetallic nanoparticles. ACS Omega 6:15300–15307

    Article  CAS  Google Scholar 

  • Singh M, Kaushal S, Singh P, Sharma J (2018) Boron doped graphene oxide with enhanced photocatalytic activity for organic pollutants. J Photochem Photobiol 364(2018):130–139

    Article  CAS  Google Scholar 

  • Singh Y, Singh R, Kaushal S (2020) Biogenic synthesis of silver nanoparticles using cyanobacterium Leptolyngbya sp. WUC 59 cell-free extract and their effects on bacterial growth and seed germination. Nanoscale Adv 2:3972–3982

    Article  CAS  Google Scholar 

  • Srakar P, Roy D, Bera B, De S, Neogi S (2022) Efficient photocatalytic degradation of ciprofloxacin using novel dual Z-scheme gCN/CuFe2O4/MoS2 mediated peroxymonosulphate activation. Chem Eng J 430:132834

    Article  Google Scholar 

  • Trikkaliotis DG, Mitropoulos AC, Kyzas GZ (2020) Low-cost route for top-down synthesis of over- and low-oxidized graphene oxide. Colloids Surf A 600:124928

    Article  CAS  Google Scholar 

  • Trikkaliotis DG, Christoforidis AK, Mitropoulos AC, Kyzas GZ (2021) Graphene oxide synthesis, properties and characterization techniques: a comprehensive review. Chem Eng 5(64):1–24

    Google Scholar 

  • Xie G, Zhang K, Guo B, Liu Q, Fang L, Gong JR (2013) Graphene-based materials for hydrogen generation from light-driven water splitting. Adv Mater 25:3820–3839

    Article  CAS  Google Scholar 

  • Xu Y, Liu J, Xie M, Jing L, Xu H, She X, Li H, Xie J (2019) Construction of novel CNT/LaVO4 nanostructures for efficient antibiotic photodegradation. Chem Eng J 357:487–497

    Article  CAS  Google Scholar 

  • Yan D, Zhang H, Chen L, Zhu G, Wang Z, Xu H, Yu A (2014) Supercapacitive properties of Mn3O4 nanoparticles bio-synthesized from banana peel extract. RSC Adv 4:23649–23652

    Article  CAS  Google Scholar 

  • Yu H, Zhang B, Bulin C, Li R, Xing R (2016) High-efficient synthesis of graphene oxide based on improved hummer’s method. Sci Rep 6:36143

    Article  CAS  Google Scholar 

  • Yu X, Zhang J, Niu J, Zhao J, Wei Y, Yao B (2019) Photocatalytic degradation of ciprofloxacin using Zn-doped Cu2O particles: analysis of degradation pathways and intermediates. Chem Eng J 374:316–327

    Article  CAS  Google Scholar 

  • Zhang S, Wang Y, Cao Z, Hu J, Huang Y, Cui C, Liu H, Wang H (2020) Simultaneous enhancements of light-harvesting and charge transfer in UiO-67/CdS/rGO composites toward ofloxacin photo-degradation. Chem Eng J 381:122771

    Article  CAS  Google Scholar 

  • Zhou Q, Huang J, Wang J, Yang Z, Liu S, Wang Z, Yang S (2015) Preparation of a reduced graphene oxide/zirconia nanocomposite and its application as a novel lubricant oil additive. RSC Adv 5:91802–91812

    Article  CAS  Google Scholar 

  • Zhou Y, Yu M, Liang H, Chen J, Xu L, Niu J (2021) Novel dual-effective Z-scheme heterojunction with g-C3N4, Ti3C2 MXene and black phosphorus for improving visible light-induced degradation of ciprofloxacin. Appl Catalysis b: Environ 291:120105

    Article  CAS  Google Scholar 

  • Zhu S, Wang Z, Ye C, Deng J, Ma X, Wang L, Tang Z, Luo H, Li X (2022) Magnetic Co/Fe nanocomposites derived from ferric sludge as an efficient peroxymonosulfate catalyst for ciprofloxacin degradation. Chem Eng J 432:134180

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Sri Guru Granth Sahib World University, Fatehgarh Sahib, Punjab, India

    Sandeep Kaushal, Vanita Kumari & Prit Pal Singh

Authors
  1. Sandeep Kaushal
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Vanita Kumari
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Prit Pal Singh
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Conceptualization: Sandeep Kaushal and Prit Pal Singh; methodology: Sandeep Kaushal and Vanita Kumari; validation: Sandeep Kaushal and Prit Pal Singh; formal analysis: Sandeep Kaushal and Vanita Kumari; writing—original draft: Sandeep Kaushal; writing—review and editing: Sandeep Kaushal and Prit Pal Singh; supervision: Sandeep Kaushal and Prit Pal Singh. All the authors have read and agreed to the published version of the manuscript.

Corresponding author

Correspondence to Sandeep Kaushal.

Ethics declarations

Ethics approval and consent to participate

Not applicable.

Informed consent

Not applicable.

Consent for publication

Not applicable.

Conflict of interest

The authors declare no competing interests.

Additional information

Responsible Editor: George Z. Kyzas

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.

Supplementary file1 (DOCX 2858 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kaushal, S., Kumari, V. & Singh, P.P. Sunlight-driven photocatalytic degradation of ciprofloxacin and organic dyes by biosynthesized rGO–ZrO2 nanocomposites. Environ Sci Pollut Res 30, 65602–65617 (2023). https://doi.org/10.1007/s11356-023-27000-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-023-27000-6

Keywords

Search

Navigation