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Enhanced photocatalytic degradation of norfloxacin under visible light by immobilized and modified In2O3/TiO2 photocatalyst facilely synthesized by a novel polymeric precursor method

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Abstract

Ion co-doped photocatalysts with In2O3/TiO2 heterostructure (In2O3/TiO2(m)) were prepared through a new polymeric precursor method. The In2O3/TiO2(m) precursor solution is of salient advantage in coating photocatalysts on various substrates and multiple modifications. The photocatalysts were facilely obtained after the calcination of precursors. Mass ratio of In/Ti was optimized according to their photocatalytic performances, and IT(m)-3 (wIn/Ti = 3%, modified by N, B co-doping) showed the best photocatalytic activity. The band gap was successfully narrowed to 2.37 eV, and In2O3/TiO2 heterostructure was successfully constructed in the photocatalysts. Visible light absorption and separation of photoexcited carriers were significantly enhanced. Under visible light, NOX (20 mg/L in the water) was 100% photodegraded in 10 min, with 100% TOC removed in 25 min. The IT(m)-3-loaded quartz fabrics (ITQ) also showed excellent photocatalytic performance. The photocatalytic activity of ITQ was repeatable and stable in 45 rounds of recycle without centrifugation. Synergetic effect of heterostructure and element doping was considered contributing to the outstanding photocatalysis performance. The polymeric precursor method proposed in this work showed great potential in large-scale preparation and application of immobilized photocatalysts. The synergetic improvement through co-modifications showed its proper compatibility with modifications.

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References

  1. Zhang QQ, Ying GG, Pan CG, Liu YS, Zhao JL (2015) Comprehensive evaluation of antibiotics emission and fate in the river basins of China: source analysis, multimedia modeling, and linkage to bacterial resistance. Environ Sci Technol 49:6772–6782

    Article  Google Scholar 

  2. Sarmah AK, Meyer MT, Boxall AB (2006) A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment. Chemosphere 65:725–759

    Article  Google Scholar 

  3. Zhou LJ, Ying GG, Liu S, Zhao JL, Yang B, Chen ZF, Lai HJ (2013) Occurrence and fate of eleven classes of antibiotics in two typical wastewater treatment plants in South China. Sci Total Environ 452–453:365–376

    Article  Google Scholar 

  4. Zhu YG, Johnson TA, Su JQ, Qiao M, Guo GX, Stedtfeld RD, Hashsham SA, Tiedje JM (2013) Diverse and abundant antibiotic resistance genes in Chinese swine farms. Proc Natl Acad Sci USA 110:3435–3440

    Article  Google Scholar 

  5. Peng H, Feng S, Zhang X, Li Y, Zhang X (2012) Adsorption of norfloxacin onto titanium oxide: effect of drug carrier and dissolved humic acid. Sci Total Environ 438:66–71

    Article  Google Scholar 

  6. Tan F, Sun D, Gao J, Zhao Q, Wang X, Teng F, Quan X, Chen J (2013) Preparation of molecularly imprinted polymer nanoparticles for selective removal of fluoroquinolone antibiotics in aqueous solution. J Hazard Mater 244–245:750–757

    Article  Google Scholar 

  7. Pruden A (2014) Balancing water sustainability and public health goals in the face of growing concerns about antibiotic resistance. Environ Sci Technol 48:5–14

    Article  Google Scholar 

  8. Wammer KH, Korte AR, Lundeen RA, Sundberg JE, McNeill K, Arnold WA (2013) Direct photochemistry of three fluoroquinolone antibacterials: norfloxacin, ofloxacin, and enrofloxacin. Water Res 47:439–448

    Article  Google Scholar 

  9. Dinh QT, Moreau-Guigon E, Labadie P, Alliot F, Teil MJ, Blanchard M, Chevreuil M (2017) Occurrence of antibiotics in rural catchments. Chemosphere 168:483–490

    Article  Google Scholar 

  10. Sharma VK, Johnson N, Cizmas L, McDonald TJ, Kim H (2016) A review of the influence of treatment strategies on antibiotic resistant bacteria and antibiotic resistance genes. Chemosphere 150:702–714

    Article  Google Scholar 

  11. Chen QL, Li H, Zhou XY, Zhao Y, Su JQ, Zhang X, Huang FY (2017) An underappreciated hotspot of antibiotic resistance: the groundwater near the municipal solid waste landfill. Sci Total Environ 609:966–973

    Article  Google Scholar 

  12. Liao P, Zhan Z, Dai J, Wu X, Zhang W, Wang K, Yuan S (2013) Adsorption of tetracycline and chloramphenicol in aqueous solutions by bamboo charcoal: a batch and fixed-bed column study. Chem Eng J 228:496–505

    Article  Google Scholar 

  13. Kümmerer K, Al-Ahmad A, Mersch-Sundermann V (2000) Biodegradability of some antibiotics, elimination of the genotoxicity and affection of wastewater bacteria in a simple test. Chemosphere 40:701–710

    Article  Google Scholar 

  14. Liu W, Zhang J, Zhang C, Ren L (2011) Sorption of norfloxacin by lotus stalk-based activated carbon and iron-doped activated alumina: mechanisms, isotherms and kinetics. Chem Eng J 171:431–438

    Article  Google Scholar 

  15. Sassman SA, Sarmah AK, Lee LS (2007) Sorption of tylosin A, D, and A-aldol and degradation of tylosin A in soils. Environ Toxicol Chem 26:1629–1635

    Article  Google Scholar 

  16. Zhang W, Gao H, He J, Yang P, Wang D, Ma T, Xia H, Xu X (2017) Removal of norfloxacin using coupled synthesized nanoscale zero-valent iron (nZVI) with H2O2 system: optimization of operating conditions and degradation pathway. Sep Purif Technol 172:158–167

    Article  Google Scholar 

  17. Liao W, Sharma VK, Xu S, Li Q, Wang L (2017) Microwave-enhanced photolysis of norfloxacin: kinetics, matrix effects, and degradation pathways. Int J Environ Res Public Health 14:1564

    Article  Google Scholar 

  18. Pignatello JJ, Oliveros E, MacKay A (2006) Advanced oxidation processes for organic contaminant destruction based on the fenton reaction and related chemistry. Crit Rev Env Sci Tec 36:1–84

    Article  Google Scholar 

  19. Kumar A, Sharma SK, Sharma G, AaH Al-Muhtaseb, Naushad M, Ghfar AA, Stadler FJ (2019) Wide spectral degradation of Norfloxacin by Ag@BiPO4/BiOBr/BiFeO3 nano-assembly: elucidating the photocatalytic mechanism under different light sources. J Hazard Mater 364:429–440

    Article  Google Scholar 

  20. Kumar A, Rana A, Sharma G, Naushad M, AaH Al-Muhtaseb, Guo C, Iglesias-Juez A, Stadler FJ (2018) high-performance photocatalytic hydrogen production and degradation of levofloxacin by wide spectrum-responsive Ag/Fe3O4 Bridged SrTiO3/g-C3N4 plasmonic nanojunctions: joint effect of Ag and Fe3O4. ACS Appl Mater Interfaces 10:40474–40490

    Article  Google Scholar 

  21. Sharma G, Kumar A, Naushad M, Kumar A, AaH Al-Muhtaseb, Dhiman P, Ghfar AA, Stadler FJ, Khan MR (2018) Photoremediation of toxic dye from aqueous environment using monometallic and bimetallic quantum dots based nanocomposites. J Cleaner Prod 172:2919–2930

    Article  Google Scholar 

  22. Dhiman P, Chand J, Kumar A, Kotnala RK, Batoo KM, Singh M (2013) Synthesis and characterization of novel Fe@ZnO nanosystem. J Alloys Compd 578:235–241

    Article  Google Scholar 

  23. Kumar A, Kumar A, Sharma G, Naushad M, Veses RC, Ghfar AA, Stadler FJ, Khan MR (2017) Solar-driven photodegradation of 17-β-estradiol and ciprofloxacin from waste water and CO2 conversion using sustainable coal-char/polymeric-g-C3N4/RGO metal-free nano-hybrids. New J Chem 41:10208–10224

    Article  Google Scholar 

  24. Dong H, Guo X, Yang C, Ouyang Z (2018) Synthesis of g-C3N4 by different precursors under burning explosion effect and its photocatalytic degradation for tylosin. Appl Catal B 230:65–76

    Article  Google Scholar 

  25. Wang J, Tang L, Zeng G, Deng Y, Liu Y, Wang L, Zhou Y, Guo Z, Wang J, Zhang C (2017) Atomic scale g-C3N4/Bi2WO6 2D/2D heterojunction with enhanced photocatalytic degradation of ibuprofen under visible light irradiation. Appl Catal B 209:285–294

    Article  Google Scholar 

  26. Dong S, Ding X, Guo T, Yue X, Han X, Sun J (2017) Self-assembled hollow sphere shaped Bi2WO6/RGO composites for efficient sunlight-driven photocatalytic degradation of organic pollutants. Chem Eng J 316:778–789

    Article  Google Scholar 

  27. Schneider J, Matsuoka M, Takeuchi M, Zhang J, Horiuchi Y, Anpo M, Bahnemann DW (2014) Understanding TiO2 photocatalysis: mechanisms and materials. Chem Rev 114:9919–9986

    Article  Google Scholar 

  28. Tan Y, Shu Z, Zhou J, Li T, Wang W, Zhao Z (2018) One-step synthesis of nanostructured g-C3N4/TiO2 composite for highly enhanced visible-light photocatalytic H2 evolution. Appl Catal B 230:260–268

    Article  Google Scholar 

  29. Zuo F, Wang L, Wu T, Zhang Z, Borchardt D, Feng P (2010) Self-doped Ti3+ enhanced photocatalyst for hydrogen production under visible light. J Am Chem Soc 132:11856–11857

    Article  Google Scholar 

  30. Cheng Y, Zhang M, Yao G, Yang L, Tao J, Gong Z, He G, Sun Z (2016) Band gap manipulation of cerium doping TiO2 nanopowders by hydrothermal method. J Alloys Compd 662:179–184

    Article  Google Scholar 

  31. Hwang YJ, Yang S, Lee H (2017) Surface analysis of N-doped TiO2 nanorods and their enhanced photocatalytic oxidation activity. Appl Catal B 204:209–215

    Article  Google Scholar 

  32. Yan X, Xing Z, Cao Y, Hu M, Li Z, Wu X, Zhu Q, Yang S, Zhou W (2017) In-situ C-N-S-tridoped single crystal black TiO2 nanosheets with exposed 001 facets as efficient visible-light-driven photocatalysts. Appl Catal B 219:572–579

    Article  Google Scholar 

  33. Zhang X, Wang Y, Liu B, Sang Y, Liu H (2017) Heterostructures construction on TiO2 nanobelts: a powerful tool for building high-performance photocatalysts. Appl Catal B 202:620–641

    Article  Google Scholar 

  34. Kwon Kaang B, Han N, Jang W, Young Koo H, Boo Lee Y, San Choi W (2018) Crossover magnetic amphiprotic catalysts for oil/water separation, the purification of aqueous and non-aqueous pollutants, and organic synthesis. Chem Eng J 331:290–299

    Article  Google Scholar 

  35. Kumar A, Kumar A, Sharma G, AaH Al-Muhtaseb, Naushad M, Ghfar AA, Stadler FJ (2018) Quaternary magnetic BiOCl/g-C3N4/Cu2O/Fe3O4 nano-junction for visible light and solar powered degradation of sulfamethoxazole from aqueous environment. Chem Eng J 334:462–478

    Article  Google Scholar 

  36. Kumar A, Kumar A, Sharma G, Naushad M, Stadler FJ, Ghfar AA, Dhiman P, Saini RV (2017) Sustainable nano-hybrids of magnetic biochar supported g-C3N4/FeVO4 for solar powered degradation of noxious pollutants- Synergism of adsorption, photocatalysis & photo-ozonation. J Cleaner Prod 165:431–451

    Article  Google Scholar 

  37. Liu G, Wang L, Yang HG, Cheng HM, Lu GQ (2010) Titania-based photocatalysts—crystal growth, doping and heterostructuring. J Mater Chem 20:831–843

    Article  Google Scholar 

  38. Giannakas AE, Antonopoulou M, Daikopoulos C, Deligiannakis Y, Konstantinou I (2016) Characterization and catalytic performance of B-doped, B-N co-doped and B–N–F tri-doped TiO2 towards simultaneous Cr(VI) reduction and benzoic acid oxidation. Appl Catal B 184:44–54

    Article  Google Scholar 

  39. Teh CY, Wu TY, Juan JC (2015) Facile sonochemical synthesis of N, Cl-codoped TiO2: synthesis effects, mechanism and photocatalytic performance. Catal Today 256:365–374

    Article  Google Scholar 

  40. Kuvarega AT, Krause RWM, Mamba BB (2015) Evaluation of the simulated solar light photocatalytic activity of N, Ir co-doped TiO2 for organic dye removal from water. Appl Surf Sci 329:127–136

    Article  Google Scholar 

  41. Wu Y, Dong Y, Xia X, Liu X, Li H (2016) Facile synthesis of N-F codoped and molecularly imprinted TiO2 for enhancing photocatalytic degradation of target contaminants. Appl Surf Sci 364:829–836

    Article  Google Scholar 

  42. Zhang J, Xiao G, Xiao FX, Liu B (2017) Revisiting one-dimensional TiO2 based hybrid heterostructures for heterogeneous photocatalysis: a critical review. Mater Chem Front 1:231–250

    Article  Google Scholar 

  43. Quarto FD, Sunseri C, Piazza S, Romano MC (1997) Semiempirical correlation between optical band gap values of oxides and the difference of electronegativity of the elements. Its importance for a quantitative use of photocurrent spectroscopy in corrosion studies. J Phys Chem B 101:333–340

    Article  Google Scholar 

  44. Lv J, Kako T, Li Z, Zou Z, Ye J (2010) Synthesis and photocatalytic activities of NaNbO3 rods modified by In2O3 nanoparticles. J Phys Chem C 114:6157–6162

    Article  Google Scholar 

  45. Wang Z, Huang B, Dai Y, Qin X, Zhang X, Wang P, Liu H, Yu J (2009) Highly photocatalytic ZnO/In2O3 heteronanostructures synthesized by a coprecipitation method. J Phys Chem C 113:4612–4617

    Article  Google Scholar 

  46. Mu J, Chen B, Zhang M, Guo Z, Zhang P, Zhang Z, Sun Y, Shao C, Liu Y (2012) Enhancement of the visible-light photocatalytic activity of In2O3-TiO2 nanofiber heteroarchitectures. ACS Appl Mater Interfaces 4:424–430

    Article  Google Scholar 

  47. Kadi MW, Ismail AA, Mohamed RM, Bahnemann DW (2018) Photodegradation of the herbicide imazapyr over mesoporous In2O3-TiO2 nanocomposites with enhanced photonic efficiency. Sep Purif Technol 205:66–73

    Article  Google Scholar 

  48. Du Q, Ma J, Shao X, Wang W, Tian G (2019) Core-shell structured TiO2@In2O3 for highly active visible-light photocatalysis. Chem Phys Lett 714:208–212

    Article  Google Scholar 

  49. Singh S, Mahalingam H, Singh PK (2013) Polymer-supported titanium dioxide photocatalysts for environmental remediation: a review. Appl Catal A 462–463:178–195

    Article  Google Scholar 

  50. An GW, Mahadik MA, Piao G, Chae WS, Park H, Cho M, Chung HS, Jang JS (2019) Hierarchical TiO2@In2O3 heteroarchitecture photoanodes: mechanistic study on interfacial charge carrier dynamics through water splitting and organic decomposition. Appl Surf Sci 480:1–12

    Article  Google Scholar 

  51. Yu H, Ye L, Zhang T, Zhou H, Zhao T (2017) Synthesis, characterization and immobilization of N-doped TiO2 catalysts by a reformed polymeric precursor method. RSC Adv 7:15265–15271

    Article  Google Scholar 

  52. Cong Y, Zhang J, Chen F, Anpo M (2007) Synthesis and characterization of nitrogen-doped TiO2 nanophotocatalyst with high visible light activity. J Phys Chem C 111:6976–6982

    Article  Google Scholar 

  53. Yu S, Wu X, Wang Y, Guo X, Tong L (2017) 2D Materials for optical modulation: challenges and opportunities. Adv Mater 29:1606128

    Article  Google Scholar 

  54. Wang F, Feng Y, Chen P, Wang Y, Su Y, Zhang Q, Zeng Y, Xie Z, Liu H, Liu Y, Lv W, Liu G (2018) Photocatalytic degradation of fluoroquinolone antibiotics using ordered mesoporous g-C3N4 under simulated sunlight irradiation: kinetics, mechanism, and antibacterial activity elimination. Appl Catal B 227:114–122

    Article  Google Scholar 

  55. Xu M, Wang Y, Geng J, Jing D (2017) Photodecomposition of NOx on Ag/TiO2 composite catalysts in a gas phase reactor. Chem Eng J 307:181–188

    Article  Google Scholar 

  56. Li Z, Zhang P, Li J, Shao T, Wang J, Jin L (2014) Synthesis of In2O3 porous nanoplates for photocatalytic decomposition of perfluorooctanoic acid (PFOA). Catal Commun 43:42–46

    Article  Google Scholar 

  57. Xing MY, Li WK, Wu YM, Zhang JL, Gong XQ (2011) Formation of new structures and their synergistic effects in boron and nitrogen codoped TiO2 for enhancement of photocatalytic performance. J Phys Chem C 115:7858–7865

    Article  Google Scholar 

  58. Patel N, Jaiswal R, Warang T, Scarduelli G, Dashora A, Ahuja BL, Kothari DC, Miotello A (2014) Efficient photocatalytic degradation of organic water pollutants using V-N-codoped TiO2 thin films. Appl Catal B 150–151:74–81

    Article  Google Scholar 

  59. Umare SS, Charanpahari A, Sasikala R (2013) Enhanced visible light photocatalytic activity of Ga, N and S codoped TiO2 for degradation of azo dye. Mater Chem Phys 140:529–534

    Article  Google Scholar 

  60. Zeng L, Lu Z, Li M, Yang J, Song W, Zeng D, Xie C (2016) A modular calcination method to prepare modified N-doped TiO2 nanoparticle with high photocatalytic activity. Appl Catal B 183:308–316

    Article  Google Scholar 

  61. Ling Q, Sun J, Zhou Q (2008) Preparation and characterization of visible-light-driven titania photocatalyst co-doped with boron and nitrogen. Appl Surf Sci 254:3236–3241

    Article  Google Scholar 

  62. Feng N, Zheng A, Wang Q, Ren P, Gao X, Liu S-B, Shen Z, Chen T, Deng F (2011) Boron environments in B-doped and (B, N)-codoped TiO2 photocatalysts: a combined solid-state NMR and theoretical calculation study. J Phys Chem C 115:2709–2719

    Article  Google Scholar 

  63. Li Z, Zhang P, Shao T, Wang J, Jin L, Li X (2013) Different nanostructured In2O3 for photocatalytic decomposition of perfluorooctanoic acid (PFOA). J Hazard Mater 260:40–46

    Article  Google Scholar 

  64. Zhou W, Du G, Hu P, Li G, Wang D, Liu H, Wang J, Boughton RI, Liu D, Jiang H (2011) Nanoheterostructures on TiO2 nanobelts achieved by acid hydrothermal method with enhanced photocatalytic and gas sensitive performance. J Mater Chem 21:7937–7945

    Article  Google Scholar 

  65. Zhang W, Xiao X, Li Y, Zeng X, Zheng L, Wan C (2016) Liquid-exfoliation of layered MoS2 for enhancing photocatalytic activity of TiO2/g-C3N4 photocatalyst and DFT study. Appl Surf Sci 389:496–506

    Article  Google Scholar 

  66. Wei Z, Liang F, Liu Y, Luo W, Wang J, Yao W, Zhu Y (2017) Photoelectrocatalytic degradation of phenol-containing wastewater by TiO2/g-C3N4 hybrid heterostructure thin film. Appl Catal B 201:600–606

    Article  Google Scholar 

  67. Wei Z, Liu Y, Wang J, Zong R, Yao W, Wang J, Zhu Y (2015) Controlled synthesis of a highly dispersed BiPO4 photocatalyst with surface oxygen vacancies. Nanoscale 7:13943–13950

    Article  Google Scholar 

  68. Lee H, Choi W (2002) Photocatalytic oxidation of arsenite in TiO2 suspension: kinetics and mechanisms. Environ Sci Technol 36:3872–3878

    Article  Google Scholar 

  69. Liu W, Wang M, Xu C, Chen S, Fu X (2013) Significantly enhanced visible-light photocatalytic activity of g-C3N4 via ZnO modification and the mechanism study. J Mol Catal A Chem 368–369:9–15

    Article  Google Scholar 

  70. Scanlon DO, Dunnill CW, Buckeridge J, Shevlin SA, Logsdail AJ, Woodley SM, Catlow CR, Powell MJ, Palgrave RG, Parkin IP, Watson GW, Keal TW, Sherwood P, Walsh A, Sokol AA (2013) Band alignment of rutile and anatase TiO2. Nat Mater 12:798–801

    Article  Google Scholar 

  71. Xu Y, Schoonen MAA (2000) The absolute energy positions of conduction and valence bands of selected semiconducting minerals. Am Mineral 85:543–556

    Article  Google Scholar 

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Acknowledgements

This work was financially supported by National Science Foundation of China (Nos. 21604090 and 51403218).

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Authors and Affiliations

  1. Laboratory of Advanced Polymeric Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, People’s Republic of China

    Han Yu, Fenghua Chen, Li Ye, Heng Zhou & Tong Zhao

  2. University of Chinese Academy of Sciences, Beijing, 100049, People’s Republic of China

    Han Yu, Fenghua Chen, Li Ye, Heng Zhou & Tong Zhao

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  1. Han Yu
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Yu, H., Chen, F., Ye, L. et al. Enhanced photocatalytic degradation of norfloxacin under visible light by immobilized and modified In2O3/TiO2 photocatalyst facilely synthesized by a novel polymeric precursor method. J Mater Sci 54, 10191–10203 (2019). https://doi.org/10.1007/s10853-019-03636-z

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