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Rational design of α-MnO2/HT-GCN nanocomposite for effective photocatalytic degradation of ciprofloxacin and pernicious activity

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Abstract

The present study is mainly concerned with the development of cost-efficient composite material utilized to produce one-dimensional manganese oxide (α-MnO2) nanoparticles coated on two-dimensional graphitic carbon nitrides (HT-GCN) as nanocomposite (α-MnO2/HT-GCN) for highly efficient CIP degradation. The α-MnO2 nanoparticles (NPs) were prepared by a simple hydrothermal technique before being decorated on HT-GCN (H denotes protonation and T represents thermal-decomposition–graphitic carbon nitride). Tauc plots were used to calculate the band gap values of the photocatalysts α-MnO2 (1.74 eV), GCN (2.84 eV), HT-GCN (2.63 eV), and α-MnO2/HT-GCN (2.31 eV). The mechanism was investigated by various scavengers, particularly isopropanol (•OH) makes a significant role in the photodegradation process. The degradation percentage for ciprofloxacin was 89.2% and the rate of reaction R2 = 0.9913. This study demonstrates a unique method for developing a heterojunction-based nanocomposite of α-MnO2/HT-GCN, which exhibit better light absorption performance.

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References

  • Ahmad I, Aslam M, Jabeen U et al (2022) ZnO and Ni-doped ZnO photocatalysts: synthesis, characterization and improved visible light driven photocatalytic degradation of methylene blue. Inorganica Chim Acta 543:121167

    Article  CAS  Google Scholar 

  • Anwer H, Mahmood A, Lee J et al (2019) Photocatalysts for Degradation of Dyes in Industrial Effluents. Oppor Challenges 12:955–972

    CAS  Google Scholar 

  • Bazrafshan E, Zarei A, Mohammadi L et al (2021) Efficient tetracycline removal from aqueous solutions using ionic liquid modified magnetic activated carbon (IL@ mAC). J Environ Chem Eng 9(6):106570

    Article  CAS  Google Scholar 

  • Bojer C, Schöbel J, Martin T, Ertl M, Schmalz H, Breu J (2017) Clinical wastewater treatment: photochemical removal of an anionic antibiotic (ciprofloxacin) by mesostructured high aspect ratio ZnO nanotubes. Appl Catal B 204:561–565

    Article  CAS  Google Scholar 

  • Cao W, Yuan Y, Yang C et al (2020) In-situ fabrication of g-C3N4/MIL-68(In)-NH2 heterojunction composites with enhanced visible-light photocatalytic activity for degradation of ibuprofen. Chem Eng J 391:123608

    Article  CAS  Google Scholar 

  • Chakma S, Moholkar VS (2015) Investigation in mechanistic issues of sonocatalysis and sonophotocatalysis using pure and doped photocatalysts. Ultrason Sonochem 22:287–299

    Article  CAS  Google Scholar 

  • Chen T, Zhong L, Yang Z et al (2020) Enhanced visible-light photocatalytic activity of g-C3N4/nitrogen-doped graphene quantum dots/TiO2 ternary heterojunctions for ciprofloxacin degradation with narrow band gap and high charge carrier mobility. Chem Res Chin Univ 36:1083–1090

    Article  CAS  Google Scholar 

  • Choi J, Kim WS, Kim HK, Yang SC, Han JH, Jeung YC, Jeong NJ (2022) Fouling behavior of wavy-patterned pore-filling membranes in reverse electrodialysis under natural seawater and sewage effluents. npj Clean Water 5(1):6

    Article  CAS  Google Scholar 

  • Cortes MALRM, Hamilton JWJ, Sharma PK et al (2019) Formal quantum efficiencies for the photocatalytic reduction of CO2 in a gas phase batch reactor. Catal Today 326:75–81

    Article  CAS  Google Scholar 

  • Deng J, Xu M, Feng S et al (2019) Iron-doped ordered mesoporous Co3O4 activation of peroxymonosulfate for ciprofloxacin degradation: performance, mechanism and degradation pathway. Sci Total Environ 658:343–356

    Article  CAS  Google Scholar 

  • Doan V-D, Huynh B-A, Pham HAL et al (2021) Cu2O/Fe3O4/MIL-101(Fe) nanocomposite as a highly efficient and recyclable visible-light-driven catalyst for degradation of ciprofloxacin. Environ Res 201:111593

    Article  CAS  Google Scholar 

  • Ganesan K, Jothi VK, Natarajan A et al (2020) Green synthesis of copper oxide nanoparticles decorated with graphene oxide for anticancer activity and catalytic applications. Arab J Chem 13:6802–6814

    Article  CAS  Google Scholar 

  • Genc R, Alas MO, Harputlu E et al (2017) High-capacitance hybrid supercapacitor based on multi-colored fluorescent carbon-dots. Sci Rep 7:11222

    Article  Google Scholar 

  • Ghamkhari A, Mohamadi L, Kazemzadeh S et al (2020) Synthesis and characterization of poly (styrene-block-acrylic acid) diblock copolymer modified magnetite nanocomposite for efficient removal of penicillin G. Compos B Eng 182:107643

    Article  CAS  Google Scholar 

  • Govinda raj M, Vijayakumar E, Preetha R et al (2022) Experimental investigation into the π-conjugated HT-g-C3N4/MoS2 (X) evokes the electron transport in type-II heterojunction to achieve high photocatalytic antibiotic removal under visible-light irradiation. Sep Purif Technol 292:121028

    Article  CAS  Google Scholar 

  • Guan H, Xie J, Chen G, Wang Y (2014) Facile synthesis of α-MnO2 nanorods at low temperature and their microwave absorption properties. Mater Chem Phys 143:1061–1068

    Article  CAS  Google Scholar 

  • Gunture KJ, Saini D et al (2021) Surface adhered fluorescent carbon dots extracted from the harmful diesel soot for sensing Fe(III) and Hg(II) ions. New J Chem 45:20164–20172

    Article  CAS  Google Scholar 

  • Guo X, Duan J, Li C et al (2020) Highly efficient Z-scheme g-C3N4/ZnO photocatalysts constructed by co-melting-recrystallizing mixed precursors for wastewater treatment. J Mater Sci 55:2018–2031

    Article  CAS  Google Scholar 

  • Hassani A, Khataee A, Karaca S (2015) Photocatalytic degradation of ciprofloxacin by synthesized TiO2 nanoparticles on montmorillonite: effect of operation parameters and artificial neural network modeling. J Mol Catal a: Chem 409:149–161

    Article  CAS  Google Scholar 

  • Jahurul Islam M, Kim HK, Amaranatha Reddy D et al (2017) Hierarchical BiOI nanostructures supported on a metal organic framework as efficient photocatalysts for degradation of organic pollutants in water. Dalton Trans 46:6013–6023

    Article  CAS  Google Scholar 

  • Ji M, Di J, Ge Y, Xia J, Li H (2017) 2D–2D stacking of graphene-like g-C3N4/Ultrathin Bi4O5Br 2 with matched energy band structure towards antibiotic removal. Appl Surf Sci 413:372–380

    Article  CAS  Google Scholar 

  • Jia Z, Li T, Zheng Z et al (2020) The BiOCl/diatomite composites for rapid photocatalytic degradation of ciprofloxacin: efficiency, toxicity evaluation, mechanisms and pathways. Chem Eng J 380:122422

    Article  CAS  Google Scholar 

  • Jiang T, Zhang L, Jin H et al (2015) In situ controlled sputtering deposition of gold nanoparticles on MnO 2 nanorods as surface-enhanced Raman scattering substrates for molecular detection. Dalton Trans 44:7606–7612

    Article  CAS  Google Scholar 

  • Jothi VK, Ganesan K, Natarajan A, Rajaram A (2021) Green synthesis of self-passivated fluorescent carbon dots derived from rice bran for degradation of methylene blue and fluorescent ink applications. J Fluoresc 31:427–436

    Article  CAS  Google Scholar 

  • Li C, Sun Z, Zhang W, Yu C, Zheng S (2018) Highly efficient g-C3N4/TiO2/kaolinite composite with novel three-dimensional structure and enhanced visible light responding ability towards ciprofloxacin and S. aureus. Appl Catal B 220:272–282

    Article  CAS  Google Scholar 

  • Lima AEB, Reis RYN, Ribeiro LS et al (2021) Microwave-assisted hydrothermal synthesis of CuWO4-palygorskite nanocomposite for enhanced visible photocatalytic response. J Alloy Compd 863:158731

    Article  CAS  Google Scholar 

  • Lin P, Hu H, Lv H et al (2018) Hybrid reduced graphene oxide/TiO2/graphitic carbon nitride composites with improved photocatalytic activity for organic pollutant degradation. Appl Phys A 124:510

    Article  Google Scholar 

  • Liu B, Nie X, Tang Y et al (2021) Objective findings on the K-doped g -C 3 N 4 photocatalysts: the presence and influence of organic byproducts on K-doped g -C 3 N 4 photocatalysis. Langmuir 37:4859–4868

    Article  CAS  Google Scholar 

  • Lu X, Jin Y, Zhang X et al (2016) Controllable synthesis of graphitic C 3 N 4 /ultrathin MoS2 nanosheet hybrid nanostructures with enhanced photocatalytic performance. Dalton Trans 45:15406–15414

    Article  CAS  Google Scholar 

  • Luo J, Bo S, Qin Y et al (2020) Transforming goat manure into surface-loaded cobalt/biochar as PMS activator for highly efficient ciprofloxacin degradation. Chem Eng J 395:125063

    Article  CAS  Google Scholar 

  • Mo Z, Xu H, Chen Z et al (2019) Construction of MnO2/Monolayer g-C3N4 with Mn vacancies for Z-scheme overall water splitting. Appl Catal B 241:452–460

    Article  CAS  Google Scholar 

  • Mohammadi L, Zafar MN, Bashir M et al (2021) Modeling of phenol removal from water by NiFe2O4nanocomposite using response surface methodology and artificial neural network techniques. J Environ Chem Eng 9:105576

    Article  CAS  Google Scholar 

  • Moghaddam AA, Mohammadi L, Bazrafshan E, et al (2023) Antibiotics sequestration using metal nanoparticles: An updated systematic review and meta-analysis. InorganicaChimica Acta, 121448.

  • Nivetha raj MS, Kumar JV, Ajarem JS et al (2022) Construction of SnO2/g-C3N4 an effective nanocomposite for photocatalytic degradation of amoxicillin and pharmaceutical effluent. Environ Res 209:112809

    Article  Google Scholar 

  • Paquin F, Rivnay J, Salleo A et al (2015) Multi-phase microstructures drive exciton dissociation in neat semicrystalline polymeric semiconductors. J Mater Chem C 3:10715–10722

    Article  CAS  Google Scholar 

  • Pattnaik SP, Behera A, Martha S et al (2019) Facile synthesis of exfoliated graphitic carbon nitride for photocatalytic degradation of ciprofloxacin under solar irradiation. J Mater Sci 54:5726–5742

    Article  CAS  Google Scholar 

  • Pham T-T, Shin EW (2018) Influence of g-C 3 N 4 Precursors in g-C 3 N 4 /NiTiO 3 Composites on Photocatalytic Behavior and the Interconnection between g-C 3 N 4 and NiTiO 3. Langmuir 34:13144–13154

    Article  CAS  Google Scholar 

  • Pomilla FR, Cortes MALRM, Hamilton JWJ et al (2018) An investigation into the stability of graphitic C 3 N 4 as a photocatalyst for CO 2 reduction. J Phys Chem C 122:28727–28738

    Article  CAS  Google Scholar 

  • Prabavath LS, Muthuraj V (2019) Superior visible light driven photocatalytic degradation of fluoroquinolone drug norfloxacin over novel NiWO4 nanorods anchored on g-C3N4 nanosheets. Colloids and Surfaces A: Physicochem Eng Asp 567:43–54

    Article  Google Scholar 

  • Pradhan MR, Rath D, Sethi R et al (2021) α-MnO2 modified exfoliated porous g-C3N4 nanosheet (2D) for enhanced photocatalytic oxidation efficiency of aromatic alcohols. Inorg Chem Commun 130:108717

    Article  CAS  Google Scholar 

  • Rajiv P, Mengelizadeh N, et al (2021) Photocatalytic degradation of ciprofloxacin with Fe2O3 nanoparticles loaded on graphitic carbon nitride: mineralisation, degradation mechanism and toxicity assessment. Int J Environ Analytical Chem, 1–15.

  • Raza N, Raza W, Gul H et al (2020) Solar-light-active silver phosphate/titanium dioxide/silica heterostructures for photocatalytic removal of organic dye. J Clean Prod 254:120031

    Article  CAS  Google Scholar 

  • Rong Z, Qiu J, Jiang J, Rong T, Pan T, Zhang D (2016) Yang, Preparation of ternary combined ZnO-Ag2O/porous g-C3N4 composite photocatalyst and enhanced visible-light photocatalytic activity for degradation of ciprofloxacin. Chem Eng Res Des 111:253–61

    Article  CAS  Google Scholar 

  • Salari H, Yaghmaei H (2020) Z-scheme 3D Bi2WO6/MnO2 heterojunction for increased photoinduced charge separation and enhanced photocatalytic activity. Appl Surf Sci 532:147413

    Article  CAS  Google Scholar 

  • Sannasi V, Subbian K (2020) Influence of Moringa oleifera gum on two polymorphs synthesis of MnO2 and evaluation of the pseudo-capacitance activity. J Mater Sci: Mater Electron 31:17120–17132

    CAS  Google Scholar 

  • Shanmugam V, Muppudathi AL, Jayavel S, Jeyaperumal KS (2020) Construction of high efficient g-C3N4 nanosheets combined with Bi2MoO6-Ag photocatalysts for visible-light-driven photocatalytic activity and inactivation of bacterias. Arab J Chem 13:2439–2455

    Article  CAS  Google Scholar 

  • Shen C-H, Wen X-J, Fei Z-H et al (2020) Visible-light-driven activation of peroxymonosulfate for accelerating ciprofloxacin degradation using CeO2/Co3O4 p-n heterojunction photocatalysts. Chem Eng J 391:123612

    Article  CAS  Google Scholar 

  • Song S, Wu K, Wu H et al (2020) Synthesis of Z-scheme multi-shelled ZnO/AgVO3 spheres as photocatalysts for the degradation of ciprofloxacin and reduction of chromium(VI). J Mater Sci 55:4987–5007

    Article  CAS  Google Scholar 

  • Sriram B, Govindasamy M, Wang S-F, Joseph XB (2020) A ternary nanocomposite based on nickel(III) oxide@f-CNF/rGO for efficient electrochemical detection of an antipsychotic drug (Klonopin) in biological samples. New J Chem 44:10250–10257

    Article  Google Scholar 

  • Sultana S, Ahmad N, Ahmad E et al (2020) Electrochemical synthesis of novel aluminium oxyhydroxide-decorated MnO2/chitosan nanocomposite with efficient photocatalytic and antibacterial activity. Nanotechnol Environ Eng 5:20

    Article  CAS  Google Scholar 

  • Tamaddon F, Nasiri A, Yazdanpanah G (2020) Photocatalytic degradation of ciprofloxacin using CuFe2O4@methyl cellulose based magnetic nanobiocomposite. MethodsX 7:100764

    Article  CAS  Google Scholar 

  • Triquet T, Tendero C, Latapie L et al (2020) TiO2 MOCVD coating for photocatalytic degradation of ciprofloxacin using 365 nm UV LEDs - kinetics and mechanisms. J Environ Chem Eng 8:104544

    Article  CAS  Google Scholar 

  • Vijayakumar E, Govinda Raj M, Narendran MG et al (2022) Promoting spatial charge transfer of ZrO 2 nanoparticles: embedded on layered MoS 2 /g-C 3 N 4 nanocomposites for visible-light-induced photocatalytic removal of tetracycline. ACS Omega 7:5079–5095

    Article  CAS  Google Scholar 

  • Vikrant K, Park CM, Kim KH et al (2019) Recent advancements in photocatalyst-based platforms for the destruction of gaseous benzene: performance evaluation of different modes of photocatalytic operations and against adsorption techniques. J Photochem Photobiol C Photochem Rev 41:100316

    Article  CAS  Google Scholar 

  • Vinoth Kumar J, Kavitha G, Arulmozhi R et al (2021) Cyan color-emitting nitrogen-functionalized carbon nanodots (NFCNDs) from Indigofera tinctoria and their catalytic reduction of organic dyes and fluorescent ink applications. RSC Adv 11:27745–27756

    Article  CAS  Google Scholar 

  • Vinoth Kumar J, Arul V, Arulmozhi R, Abirami N (2022) Boron doped fluorescent carbon nano dots for the reduction of ionic dyes and as encryption/decryption QR security code labels. New J Chem 46:7464–7476

    Article  CAS  Google Scholar 

  • Wang K, Zhang G, Li J, Li Y, Wu X (2017) 0D/2D Z-scheme heterojunctions of bismuth tantalate quantum dots/ultrathin g-C3N4 nanosheets for highly efficient visible light photocatalytic degradation of antibiotics. ACS Appl Mater Interfaces 9(50):43704–43715

    Article  CAS  Google Scholar 

  • Wang Y, Gao B, Yue Q, Wang Z (2020) Graphitic carbon nitride (g-C 3 N 4)-based membranes for advanced separation. J Mater Chem A 8:19133–19155

    Article  CAS  Google Scholar 

  • Wang L, Li Y, Han P (2021) Electrospinning preparation of g-C3N4/Nb2O5 nanofibers heterojunction for enhanced photocatalytic degradation of organic pollutants in water. Sci Rep 11:22950

    Article  CAS  Google Scholar 

  • Wang J, Fan J, Yao J et al (2023) Facet tailoring and Cu doping promoted photo-assisted peroxymonosulfate activation by oxygen-deficient α-MnO2 for efficient mineralization of bisphenol a. Chem Eng J 461:142024

    Article  CAS  Google Scholar 

  • Xu J, Li X, Niu J et al (2020) Synthesis of direct Z-Scheme Bi3TaO7/CdS composite photocatalysts with enhanced photocatalytic performance for ciprofloxacin degradation under visible light irradiation. J Alloy Compd 834:155061

    Article  CAS  Google Scholar 

  • Yang Z, Yan J, Lian J et al (2016) g-C 3 N 4 /TiO 2 Nanocomposites for degradation of ciprofloxacin under visible light irradiation. ChemistrySelect 1:5679–5685

    Article  CAS  Google Scholar 

  • Younis SA, Kwon EE, Qasim M et al (2020) Metal-organic framework as a photocatalyst: Progress in modulation strategies and environmental/energy applications. Prog Energy Combust Sci 81:100870

    Article  Google Scholar 

  • Yu X, Zhang J, Zhang J et al (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 

  • Yu L, Mo Z, Zhu X et al (2021) Construction of 2D/2D Z-scheme MnO2-x/g-C3N4 photocatalyst for efficient nitrogen fixation to ammonia. Green Energy Environ 6:538–545

    Article  CAS  Google Scholar 

  • Zafar B, Shafqat SS, Zafar MN et al (2022) NaHCO3 assisted multifunctional Co3O4, CuO and Mn2O3 nanoparticles for tartrazine removal from synthetic wastewater and biological activities. Mater Today Commun 33:104946

    Article  CAS  Google Scholar 

  • Zhang Q, Peng Y, Deng F et al (2020) Porous Z-scheme MnO2/Mn-modified alkalinized g-C3N4 heterojunction with excellent Fenton-like photocatalytic activity for efficient degradation of pharmaceutical pollutants. Sep Purif Technol 246:116890

    Article  CAS  Google Scholar 

  • Zhao R, Sun X, Jin Y et al (2019) Au/Pd/g-C3N4 nanocomposites for photocatalytic degradation of tetracycline hydrochloride. J Mater Sci 54:5445–5456

    Article  CAS  Google Scholar 

  • Zia J, Aazam ES, Riaz U (2020) Synthesis of nanohybrids of polycarbazole with α-MnO2 derived from Brassica oleracea: a comparison of photocatalytic degradation of an antibiotic drug under microwave and UV irradiation. Environ Sci Pollut Res 27:24173–24189

    Article  CAS  Google Scholar 

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Funding

Financial support is provided by the Department of Chemistry, SRMIST, Kattankulathur-603203, Tamil Nadu, India

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  1. Department of Chemistry, Faculty of Engineering and Technology, SRM Institute of Science & Technology, Tamil Nadu, Kattankulathur, 603203, India

    Sherlin Nivetha Michael Raj, Vinoth Kumar Jothi, Arulmozhi Rajaram, Pavithra Suresh, Komal Murugan & Abirami Natarajan

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  1. Sherlin Nivetha Michael Raj
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  2. Vinoth Kumar Jothi
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  4. Pavithra Suresh
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Contributions

Sherlin Nivetha Michael Raj: writing, conceptualization, writing—original draft; Vinoth Kumar Jothi: validation; Arulmozhi Rajaram: data curation; Pavithra Suresh: formal analysis; Komal Murugan: formal analysis; Abirami Natarajan: supervision, review and editing.

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Correspondence to Abirami Natarajan.

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Raj, S.N.M., Jothi, V.K., Rajaram, A. et al. Rational design of α-MnO2/HT-GCN nanocomposite for effective photocatalytic degradation of ciprofloxacin and pernicious activity. Environ Sci Pollut Res 30, 90689–90707 (2023). https://doi.org/10.1007/s11356-023-28636-0

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