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Titania/reduced graphene oxide nanocomposites (TiO2/rGO) as an efficient photocatalyst for the effective degradation of brilliant green in aqueous media: effect of peroxymonosulfate and operational parameters

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Abstract

This study is focused on synthesis of highly efficient Titania/reduced Graphene Oxide (TiO2/rGO) nanocomposites by means of simple hydrothermal technique. The TiO2/rGO were synthesized in different ratios of 0.5, 1.0, 2.0, and 3% by varying the concentration of rGO while the concentration of TiO2 was kept constant and the obtained samples were designated as TrG0.5, TrG1, TrG2, and TrG3 respectively. Different characterization techniques (SEM, TEM, HRTEM, XRD, EDX, TGA, UV-DRS, PL, EIS, and BET) showed high crystallinity, small crystallite size (18.4 nm), high thermal stability, high purity, low band gap energy (Eg = 3.12 eV), and high surface area (65.989 m2/g) for the as-synthesized TiO2/rGO nanocomposite. The efficiencies of TiO2/rGO were determined in terms of brilliant green (BG) dye degradation in aqueous media under UV light. The results revealed that 2% TiO2/rGO (TrG2) showed high efficiency for BG degradation with the kapp of 0.023 min−1 compared to TiO2 alone (kapp of 0.006 min−1). The rate of BG degradation was further synergised by the addition of peroxymonosulfate (PMS) to the system. The degradation of BG was improved to 99.4% by the incorporation of PMS in aqueous media compared to TrG2 alone. Furthermore, the degradation of BG was also examined in various media (neutral, acidic, and basic). The results revealed that by increasing pH of the medium from 3.85 to 8.2 the degradation of BG was enhanced from 99.4 to 99.9% with the corresponding kapp of 0.0602 min−1. Moreover, the photocatalytic degradation of BG followed the pseudo-first-order kinetics. Radical scavenging experiments showed that ●OH and SO4●– were the main species responsible for the degradation of BG under UV light. Besides, for determining the efficiency of as-synthesized TrG2/PMS system, the degradation of BG was also performed in various water types (distilled water, tape water, synthetic wastewater, and industrial wastewater). The degradation products (DPs) of BG and their corresponding pathways were proposed, accordingly.

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References

  • Abdel Rahman RO, Hung Y-T (2020) Application of ionizing radiation in wastewater treatment: an overview. Water 12(1):19

    Article  CAS  Google Scholar 

  • Abdi M, Mahdikhah V, Sheibani S (2020) Visible light photocatalytic performance of La-Fe co-doped SrTiO3 perovskite powder. Opt Mater 102:109803

    Article  CAS  Google Scholar 

  • Ambrosi A, Chua CK, Khezri B, Sofer Z, Webster RD, Pumera M (2012) Chemically reduced graphene contains inherent metallic impurities present in parent natural and synthetic graphite. Proc Natl Acad Sci 109(32):12899–12904

    Article  CAS  Google Scholar 

  • Ameta R, Solanki MS, Benjamin S, Ameta SC (2018) Photocatalysis. In: Advanced oxidation processes for waste water treatment. Academic Press, pp 135–175

  • Antoniou MG, Boraei I, Solakidou M, Deligiannakis Y, Abhishek M, Lawton L, Edwards C (2018) Enhancing photocatalytic degradation of the cyanotoxin microcystin-LR with the addition of sulfate-radical generating oxidants. J Hazard Mater 360:461–470

    Article  CAS  Google Scholar 

  • Arslan I, Balcioglu IA, Tuhkanen T (1999) Advanced oxidation of synthetic dyehouse effluent by O3, H2O2/O3 and H2O2/UV processes. Environ Technol 20(9):921–931

    Article  CAS  Google Scholar 

  • Augugliaro V, Litter M, Palmisano L, Soria J (2006) The combination of heterogeneous photocatalysis with chemical and physical operations: a tool for improving the photoprocess performance. J Photochem Photobiol C Photchem Rev 7(4):127–144

    Article  CAS  Google Scholar 

  • Bakatula EN, Richard D, Neculita CM, Zagury GJ (2018) Determination of point of zero charge of natural organic materials. Environ Sci Pollut Res 25(8):7823–7833

    Article  CAS  Google Scholar 

  • Balsamo SA, Fiorenza R, Condorelli M, Pecoraro R, Brundo MV, Lo Presti F, Sciré S (2021) One-pot synthesis of TiO2-rGO photocatalysts for the degradation of groundwater pollutants. Materials 14(20):5938

    Article  CAS  Google Scholar 

  • Chakrabarti S, Dutta BK (2004) Photocatalytic degradation of model textile dyes in wastewater using ZnO as semiconductor catalyst. J Hazard Mater 112(3):269–278

    Article  CAS  Google Scholar 

  • Chan K-L, Lin W-H, Chen F-J, Yang M-H, Jiang C-H, Lee C-Y, Lee C-Y (2020) Photocatalytic performance of bipyramidal anatase TiO2 toward the degradation organic dyes and its catalyst poisoning effect. React Kinet Mech Catal 130:531–546

    Article  CAS  Google Scholar 

  • Chekuri RD, Tirukkovalluri SR (2017) Synthesis of cobalt doped titania nano material assisted by gemini surfactant: characterization and application in degradation of Acid Red under visible light irradiation. SAJCE 24(1):183–195

    Google Scholar 

  • Chen C-C, Lu C-S, Fan H-J, Chung W-H, Jan J-L, Lin H-D, Lin W-Y (2008) Photocatalyzed N-de-ethylation and degradation of Brilliant Green in TiO2 dispersions under UV irradiation. Desalination 219(1-3):89–100

    Article  CAS  Google Scholar 

  • Chen M, Meng Y, Zhang W, Zhou J, Xie J, Diao G (2013) β-Cyclodextrin polymer functionalized reduced-graphene oxide: application for electrochemical determination imidacloprid. Electrochim Acta 108:1–9

    Article  Google Scholar 

  • Collazzo G, Jahn S, Carreño N, Foletto E (2011) Temperature and reaction time effects on the structural properties of titanium dioxide nanopowders obtained via the hydrothermal method. Braz J Chem Eng 28:265–272

    Article  CAS  Google Scholar 

  • Dong Z, Zondag SD, Schmid M, Wen Z, Noël T (2022) A meso-scale ultrasonic milli-reactor enables gas–liquid-solid photocatalytic reactions in flow. Chem Eng J 428:130968

    Article  CAS  Google Scholar 

  • Fujisawa J-I, Eda T, Hanaya M (2017) Comparative study of conduction-band and valence-band edges of TiO2, SrTiO3, and BaTiO3 by ionization potential measurements. Chem Phys Lett 685:23–26

    Article  CAS  Google Scholar 

  • Gavgani JN, Adelnia H, Gudarzi MM (2014) Intumescent flame retardant polyurethane/reduced graphene oxide composites with improved mechanical, thermal, and barrier properties. J Mater Sci 49(1):243–254

    Article  CAS  Google Scholar 

  • Ghaly MY, Jamil TS, El-Seesy IE, Souaya ER, Nasr RA (2011) Treatment of highly polluted paper mill wastewater by solar photocatalytic oxidation with synthesized nano TiO2. Chem Eng J 168(1):446–454

    Article  CAS  Google Scholar 

  • Gul I, Sayed M, Shah NS, Khan JA, Polychronopoulou K, Iqbal J, Rehman F (2020) Solar light responsive bismuth doped titania with Ti3+ for efficient photocatalytic degradation of flumequine: Synergistic role of peroxymonosulfate. Chem Eng J 384:123255

    Article  CAS  Google Scholar 

  • Gul I, Sayed M, Shah NS, Rehman F, Khan JA, Gul S, Iqbal J (2021) A novel route for catalytic activation of peroxymonosulfate by oxygen vacancies improved bismuth-doped titania for the removal of recalcitrant organic contaminant. Environ Sci Pollut Res 28(18):23368–23385

    Article  CAS  Google Scholar 

  • Gupta B, Melvin AA (2017) TiO2/RGO composites: its achievement and factors involved in hydrogen production. Renew Sustain Energy Rev 76:1384–1392

    Article  CAS  Google Scholar 

  • Hanifah MFR, Jaafar J, Othman M, Ismail A, Rahman MA, Yusof N, Aziz F (2019) Facile synthesis of highly favorable graphene oxide: effect of oxidation degree on the structural, morphological, thermal and electrochemical properties. Materialia 6:100344

    Article  CAS  Google Scholar 

  • Hu J, He B, Lu J, Hong L, Yuan J, Song J, Niu L (2012) Facile preparation of pt/polyallylamine/reduced graphene oxide composites and their application in the electrochemical catalysis on methanol oxidation. Int J Electrochem Sci 7(10):10094–10107

    CAS  Google Scholar 

  • Huang, Y.-H., Huang, Y.-F., Huang, C.-i., & Chen, C.-Y. (2009). Efficient decolorization of azo dye Reactive Black B involving aromatic fragment degradation in buffered Co2+/PMS oxidative processes with a ppb level dosage of Co2+-catalyst. J Hazard Mater, 170(2-3), 1110-1118.

  • Irshad MA, Nawaz R, ur Rehman, M. Z., Imran, M., Ahmad, J., Ahmad, S., Ali, S. (2020) Synthesis and characterization of titanium dioxide nanoparticles by chemical and green methods and their antifungal activities against wheat rust. Chemosphere 258:127352

    Article  CAS  Google Scholar 

  • Jian Y, Liu H, Zhu J, Zeng Y, Liu Z, Hou C, Pu S (2021) Preparation of F-doped H2 Ti3O7-{104} nanorods with oxygen vacancies using TiOF2 as precursor and its photocatalytic degradation activity. RSC Adv 11(56):35215–35227

    Article  CAS  Google Scholar 

  • Khan JA, He X, Shah NS, Sayed M, Khan HM, Dionysiou DD (2017) Degradation kinetics and mechanism of desethyl-atrazine and desisopropyl-atrazine in water with OH and SO4− based-AOPs. Chem Eng J 325:485–494

    Article  CAS  Google Scholar 

  • Khan S, Sayed M, Sohail M, Shah LA, Raja MA (2019) Advanced oxidation and reduction processes. In: Advances in water purification techniques, pp 135–164

  • Khavar AHC, Moussavi G, Mahjoub AR (2018) The preparation of TiO2@rGO nanocomposite efficiently activated with UVA/LED and H2O2 for high rate oxidation of acetaminophen: catalyst characterization and acetaminophen degradation and mineralization. Appl Surf Sci 440:963–973

    Article  Google Scholar 

  • Kim YK, Rousseau R, Kay BD, White J, Dohnálek Z (2008) Catalytic dehydration of 2-propanol on (WO3) 3 clusters on TiO2 (110). J Am Chem Soc 130(15):5059–5061

    Article  CAS  Google Scholar 

  • Kim MS, Lee C, Kim JH (2021) Occurrence of unknown reactive species in UV/H2O2 system leading to false interpretation of hydroxyl radical probe reactions. Water Res 201:117338

  • Kovačić M, Perović K, Papac J, Tomić A, Matoh L, Žener B, Kušić H (2020) One-pot synthesis of sulfur-doped TiO2/reduced graphene oxide composite (S-TiO2/rGO) with improved photocatalytic activity for the removal of diclofenac from water. Materials 13(7):1621

    Article  Google Scholar 

  • Kumar R, Rashid J, Barakat M (2015) Zero valent Ag deposited TiO2 for the efficient photocatalysis of methylene blue under UV-C light irradiation. Colloids and Interface Science Communications 5:1–4

    Article  Google Scholar 

  • Le TT, Tran TD (2020) Photocatalytic degradation of rhodamine B by C and N codoped TiO2 nanoparticles under visible-light irradiation. J Chem. https://doi.org/10.1155/2020/4310513

  • Li H, Ren F, Liu J, Wang Q, Li Q, Yang J, Wang Y (2015) Endowing single-electron-trapped oxygen vacancy self-modified titanium dioxide with visible-light photocatalytic activity by grafting Fe (III) nanocluster. Appl Catal Environ 172:37–45

    Article  Google Scholar 

  • Mansingh S, Sahoo DP, Paramanik L, Sahoo M, Parida K (2022) Robust charge carrier engineering via plasmonic effect and conjugated Π-framework on Au loaded ZnCr-LDH/RGO photocatalyst towards H2 and H2O2 production. Inorg Chem Front 9(3):559–576

    Article  CAS  Google Scholar 

  • Nada AA, Tantawy HR, Elsayed MA, Bechelany M, Elmowafy ME (2018) Elaboration of nano titania-magnetic reduced graphene oxide for degradation of tartrazine dye in aqueous solution. Solid State Sci 78:116–125

    Article  CAS  Google Scholar 

  • Nainani RK, Thakur P (2016) Facile synthesis of TiO2-RGO composite with enhanced performance for the photocatalytic mineralization of organic pollutants. Water Sci Technol 73(8):1927–1936

    Article  CAS  Google Scholar 

  • Nassar I (2019) Continuous flow photodegradation of olive Zebar contaminants with simulated solar light using supported ZnO nanoparticles, MSc Thesis. An-Najah Nationa University, Nablus, Palestine

    Google Scholar 

  • Nguyen-Phan T-D, Pham VH, Shin EW, Pham H-D, Kim S, Chung JS, Hur SH (2011) The role of graphene oxide content on the adsorption-enhanced photocatalysis of titanium dioxide/graphene oxide composites. Chem Eng J 170(1):226–232

    Article  CAS  Google Scholar 

  • Ouedraogo S, Chouchene B, Gries T, Desmarets C, Balan L, Gaumet J-J, Schneider R (2022) Bismuth oxybromide/reduced graphene oxide heterostructure sensitized with Zn-tetracarboxyphthalocyanine as a highly efficient photocatalyst for the degradation of Orange II and phenol. J Environ Chem Eng 10(2):107332

    Article  CAS  Google Scholar 

  • Pei F, Xu S, Zuo W, Zhang Z, Liu Y, Cao S (2014) Effective improvement of photocatalytic hydrogen evolution via a facile in-situ solvothermal N-doping strategy in N-TiO2/N-graphene nanocomposite. Int J Hydrogen Energy 39(13):6845–6852

    Article  CAS  Google Scholar 

  • Pelaez M, Armah A, O’Shea K, Falaras P, Dionysiou DD (2011) Effects of water parameters on the degradation of microcystin-LR under visible light-activated TiO2 photocatalyst. Water Res 45(12):3787–3796

    Article  CAS  Google Scholar 

  • Pichon A, Lazuen-Garay A, James SL (2006) Solvent-free synthesis of a microporous metal–organic framework. CrystEngComm 8(3):211–214

    Article  CAS  Google Scholar 

  • Preetha S, Pillai R, Ramamoorthy S, Mayeen A, Archana K, Kalarikkal N, Lekshmi I (2022) TiO2–rGO nanocomposites with high rGO content and luminescence quenching through green redox synthesis. Surf Interfaces 30:101812

    Article  CAS  Google Scholar 

  • Qi K, Cheng B, Yu J, Ho W (2017) Review on the improvement of the photocatalytic and antibacterial activities of ZnO. J Alloys Compd 727:792–820

    Article  CAS  Google Scholar 

  • Rahman M, Tang Y, Kwong P (2018) Reduced recombination and low-resistive transport of electrons for photo-redox reactions in metal-free hybrid photocatalyst. Appl Phys Lett 112(25):253902

    Article  Google Scholar 

  • Rehman F, Sayed M, Khan JA, Shah NS, Khan HM, Dionysiou DD (2018) Oxidative removal of brilliant green by UV/S2O82–, UV/HSO5–and UV/H2O2 processes in aqueous media: a comparative study. J Hazard Mater 357:506–514

    Article  CAS  Google Scholar 

  • Rehman F, Ahmad W, Sayed M (2021) Mechanistic investigations on the removal of diclofenac sodium by UV/S2O82−/Fe2+, UV/HSO5−/Fe2+ and UV/H2O2/Fe2+-based advanced oxidation processes. Environ Technol 42(25):3995–4005

  • Sayed M, Khan A, Rauf S, Shah NS, Rehman F, Al-Kahtani A, A., Gul, I. (2020) Bismuth-doped nano zerovalent iron: a novel catalyst for chloramphenicol degradation and hydrogen production. ACS omega 5(47):30610–30624

    Article  CAS  Google Scholar 

  • Sher Shah MSA, Park AR, Zhang K, Park JH, Yoo PJ (2012) Green synthesis of biphasic TiO2–reduced graphene oxide nanocomposites with highly enhanced photocatalytic activity. ACS Appl Mater Interfaces 4(8):3893–3901

    Article  CAS  Google Scholar 

  • Shukla P, Fatimah I, Wang S, Ang H, Tadé MO (2010) Photocatalytic generation of sulphate and hydroxyl radicals using zinc oxide under low-power UV to oxidise phenolic contaminants in wastewater. Catalysis Today 157(1-4):410–414

    Article  CAS  Google Scholar 

  • Simon T, Carlson MT, Stolarczyk JK, Feldmann J (2016) Electron transfer rate vs recombination losses in photocatalytic H2 generation on Pt-decorated CdS nanorods. ACS energy letters 1(6):1137–1142

    Article  CAS  Google Scholar 

  • Sood S, Umar A, Mehta SK, Sinha A, Kansal SK (2015) Efficient photocatalytic degradation of brilliant green using Sr-doped TiO2 nanoparticles. Ceram Int 41(3):3533–3540

    Article  CAS  Google Scholar 

  • Sun L, Yan M, Xiao L, Liu Y, Bai H, Xie L, Shi W (2018) Synthesis of C/Co3O4 composite mesoporous hollow sphere sandwich graphene films for high-performance supercapacitors. Inorg Chem Front 5(10):2554–2562

    Article  CAS  Google Scholar 

  • Szczepanik B (2017) Photocatalytic degradation of organic contaminants over clay-TiO2 nanocomposites: a review. Applied Clay Science 141:227–239

    Article  CAS  Google Scholar 

  • Tanhaei B, Ayati A, Lahtinen M, Sillanpää M (2015) Preparation and characterization of a novel chitosan/Al2O3/magnetite nanoparticles composite adsorbent for kinetic, thermodynamic and isotherm studies of Methyl Orange adsorption. Chem Eng J 259:1–10

    Article  CAS  Google Scholar 

  • Tian L, Yang X, Liu Q, Qu F, Tang H (2018) Anchoring metal-organic framework nanoparticles on graphitic carbon nitrides for solar-driven photocatalytic hydrogen evolution. Appl Surf Sci 455:403–409

    Article  CAS  Google Scholar 

  • Tolosana-Moranchel A, Casas J, Bahamonde A, Pascual L, Granone L, Schneider J, Bahnemann D (2019a) Nature and photoreactivity of TiO2-rGO nanocomposites in aqueous suspensions under UV-A irradiation. Appl Catal Environ 241:375–384

    Article  CAS  Google Scholar 

  • Tolosana-Moranchel Á, Manassero A, Satuf ML, Alfano OM, Casas JA, Bahamonde A (2019b) Influence of TiO2-rGO optical properties on the photocatalytic activity and efficiency to photodegrade an emerging pollutant. Appl Catal Environ 246:1–11

    Article  CAS  Google Scholar 

  • Trojanowicz M, Bobrowski K, Szreder T, Bojanowska-Czajka A (2018) Gamma-ray, X-ray and electron beam based processes. In: Advanced oxidation processes for waste water treatment. Academic Press, pp 257–331

  • Viet TQQ, Nhu TH, Thinh DB, Trinh DN, Giang NTH, Dat NM, Hieu NH (2021) Optimization of TiO2 immobilized–reduce graphene oxide photocatalyst toward organic compounds in aqueous medium. Synth Met 280:116867

    Article  CAS  Google Scholar 

  • Wang JL, Xu LJ (2012) Advanced oxidation processes for wastewater treatment: formation of hydroxyl radical and application. Crit Rev Environ Sci Technol 42(3):251–325

    Article  Google Scholar 

  • Wang P, Wang J, Wang X, Yu H, Yu J, Lei M, Wang Y (2013) One-step synthesis of easy-recycling TiO2-rGO nanocomposite photocatalysts with enhanced photocatalytic activity. Appl Catal Environ 132:452–459

    Article  Google Scholar 

  • Xu D, Li L, He R, Qi L, Zhang L, Cheng B (2018) Noble metal-free RGO/TiO2 composite nanofiber with enhanced photocatalytic H2-production performance. Appl Surf Sci 434:620–625

    Article  CAS  Google Scholar 

  • Yu C, Tan L, Shen S, Fang M, Yang L, Fu X, Sun J (2021) In situ preparation of g-C3N4/polyaniline hybrid composites with enhanced visible-light photocatalytic performance. J Environ Sci 104:317–325

    Article  CAS  Google Scholar 

  • Zhang X, Liu Y, Li C, Tian L, Yuan F, Zheng S, Sun Z (2022) Fast and lasting electron transfer between γ-FeOOH and g-C3N4/kaolinite containing N vacancies for enhanced visible-light-assisted peroxymonosulfate activation. Chem Eng J 429:132374

    Article  CAS  Google Scholar 

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Acknowledgements

The authors are highly thankful to the Higher Education Commission (HEC) of Pakistan for funding this research project. Moreover, the authors extend their appreciation to the National Centre of Excellence in Physical Chemistry, University of Peshawar, Pakistan for providing research facilities. Authors are also thankful to Ms. Sadia Rehman of School of Environment, Tsinghua University, Beijing, China, for BET analysis.

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  1. Radiation and Environmental Chemistry lab, National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar, Pakistan

    Qaiser Khan, Murtaza Sayed & Ikhtiar Gul

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The individual contributions by all the authors to this paper can be summarized below: Qaiser Khan: conceptualization; data curation; formal analysis; investigation; methodology; original draft writing. Murtaza Sayed: project administration; supervision; funding acquisition. Ikhtiar Gul: formal analysis; investigation; validation; editing.

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Khan, Q., Sayed, M. & Gul, I. Titania/reduced graphene oxide nanocomposites (TiO2/rGO) as an efficient photocatalyst for the effective degradation of brilliant green in aqueous media: effect of peroxymonosulfate and operational parameters. Environ Sci Pollut Res 30, 71025–71047 (2023). https://doi.org/10.1007/s11356-023-27316-3

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