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Crystal structure and photocatalytic properties of titanate nanotubes prepared by chemical processing and subsequent annealing

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Abstract

Anatase TiO2 nanoparticles were synthesized from sol–gel processing, and they were used as a precursor for titanate nanotubes (TNT) formation. TNT were synthesized under reflux heating of anatase TiO2 in concentrated NaOH solution followed by repeated washing with distilled water and 0.1 M HCl. The nanotubular structure was preserved till 450 °C, above which nanorod formation started. The as-synthesized nanotubes were found to have mixed crystal structure of anatase and Na x H2−x Ti3O7·nH2O (where 0 < x <  2), contrary to what has been reported before. The XRD peaks of titanate were slightly shifted to higher angles upon calcination along with prominent anatase peaks. Complete transformation to nanorods occurred at 600 °C and crystal structure was transformed to Na2Ti6O13 and anatase. Sodium presence in TNT was confirmed by EDX, and Na–O and H–O–H along with Ti–OH vibrations were found by FTIR. Ti–OH/H–O–H vibrations were less prominent for samples calcined at 500 °C and above, which confirms structural water loss is associated with morphological change. The as-synthesized TNTs had a specific surface area of 157 m2 g−1, and it decreased by increasing calcination temperature. TNTs were applied to methylene blue aqueous solution to observe their decolorization capability under UV irradiation. The as-synthesized TNTs showed enhanced photocatalytic decolorization as compared to anatase titania nanoparticles due to presence of Ti–OH groups and higher specific surface area. The photocatalytic activity reduced when TNTs were annealed at high temperatures. The changes in the photocatalytic activity are related to the existence of hydroxyl groups in the structure, decrease in specific surface area of annealed nanotubes, change in morphology from nanotubes to nanorods, and bandgap shift to visible light when TNTs were calcined at higher temperatures.

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References

  1. Liu R, Yang W-D, Chueng H-J, Ren B-Q (2015) Preparation and application of titanate nanotubes on dye degradation from aqueous media by UV irradiation. J Spectrosc. doi:10.1155/2015/680183

    Google Scholar 

  2. Zhang J, Xiao X, Nan J (2010) Hydrothermal-hydrolysis synthesis and photocatalytic properties of nano-TiO2 with an adjustable crystalline structure. J Hazard Mater 176:617–622

    Article  Google Scholar 

  3. Hu K, Xiao X, Cao X, Hao R, Zuo X, Zhang X, Nan J (2010) Adsorptive separation and photocatalytic degradation of methylene blue dye on titanate nanotube powders prepared by hydrothermal process using metal Ti particles as a precursor. J Hazard Mater 192:514–520

    Article  Google Scholar 

  4. Lee C-K, Wang C-C, Lyu M-D, Juang L-C, Liu S-S, Hung S-H (2007) Effects of sodium content and calcination temperature on the morphology, structure and photocatalytic activity of nanotubular titanates. J Colloid Interf Sci 316:562–569

    Article  Google Scholar 

  5. Li J, Ma W, Chen C, Zhao J, Zhu H, Gao X (2007) Photodegradation of dye pollutants on one-dimensional TiO2 nanoparticles under UV and visible irradiation. J Mol Catal A Chem 261:131–138

    Article  Google Scholar 

  6. Carbajo J, Jiménez M, Miralles S, Malato S, Faraldos M, Bahamonde A (2016) Study of application of titania catalysts on solar photocatalysis: Influence of type of pollutants and water matrices. Chem Eng J 291:64–73

    Article  Google Scholar 

  7. Kaur A, Umar A, Kansal SK (2016) Heterogeneous photocatalytic studies of analgesic and non-steroidal anti-inflammatory drugs. Appl Catal A 510:134–155

    Article  Google Scholar 

  8. Kim DS, Kwak S-Y (2007) The hydrothermal synthesis of mesoporous TiO2 with high crystallinity, thermal stability, large surface area, and enhanced photocatalytic activity. Appl Catal A 323:110–118

    Article  Google Scholar 

  9. Gautam A, Kshirsagar A, Biswas R, Banerjee S, Khanna PK (2016) Photodegradation of organic dyes based on anatase and rutile TiO2 nanoparticles. RCS Adv 6:2746–2759

    Google Scholar 

  10. Soni h, Kumar JN, Patel K, Kumar RN (2016) Photocatalytic decoloration of three commercial dyes in aqueous phase and industrial effluents using TiO2 nanoparticles. Desalin Water Treat 57:6355–6364

    Article  Google Scholar 

  11. Barton I, Matejec V, Matousek J (2016) Photocatalytic activity of nanostructured TiO2 coating on glass slide and optical fibers for methylene blue or methyl orange decomposition under different light excitation. J Photochem Photobiol A 317:72–80

    Article  Google Scholar 

  12. Salvaggio MG, Passalacqua R, Abate S, Perathoner S, Centi G, Lanza M, Stassi A (2016) Functional nano-textured titania-coatings with self-cleaning and antireflective properties for photovoltaic surfaces. Sol Energy 125:227–242

    Article  Google Scholar 

  13. Sarkar D, Ishchuk S, Taffa DH, Kaynan N, Berke BA, Bendikov T, Yerushalmi R (2016) Oxygen-deficient titania with adjustable band positions and defects; Molecular layer deposition of hybrid organic–inorganic thin films as precursors for enhanced photocatalysis. J Phys Chem C 120:3853–3862

    Article  Google Scholar 

  14. Henkel B, Neubert T, Zabel S, Lamprecht C, Selhuber-Unkel C, Rätzke K, Strunskus T, Vergöhl M, Faupel Franz (2016) Photocatalytic properties of titania thin films prepared by sputtering versus evaporation and aging of induced oxygen vacancy defects. Appl Catal B 180:362–371

    Article  Google Scholar 

  15. Bergamonti L, Bondioli F, Alfier I, Lorenzi A, Mattarozzi M, Predieri G, Lottici PP (2016) Photocatalytic self-cleaning TiO2 coatings on carbonatic stones. Appl Phys A 122:1–12

    Article  Google Scholar 

  16. Juang Y, Liu Y, Nurhayati E, Thuy NT, Huang C, Hu C-C (2016) Anodic fabrication of advanced titania nanotubes photocatalysts for photoelectrocatalysis decolorization of Orange G dye. Chemosphere 144:2462–2468

    Article  Google Scholar 

  17. Jayamohan H, Smith YR, Gale BK, Mohanty SK, Misra M (2016) Photocatalytic microfluidic reactors utilizing titania nanotubes on titanium mesh for degradation of organic and biological contaminants. J Environ Chem Eng 4:657–663

    Article  Google Scholar 

  18. Peng Y, Li M, Zhang S, Nie G, Qi M, Pan B (2015) Improved performance and prolonged lifetime of titania-based materials: sequential use as adsorbent and photocatalyst. Sci China Chem 58:1211–1219

    Article  Google Scholar 

  19. Gao H, Shangguan W, Guoxin H, Zhu K (2016) Preparation and photocatalytic performance of transparent titania film from monolayer titania quantum dots. Appl Catal B 180:416–423

    Article  Google Scholar 

  20. Kassir M, Roques-Carmes T, Hamieh T, Toufaily J, Akil M, Barres O, Villiéras F (2015) Improvement of the photocatalytic activity of TiO2 induced by organic pollutant enrichment at the surface of the organografted catalyst. Colloid Surf A 485:73–83

    Article  Google Scholar 

  21. Feng Z, Wei W, Wang L, Hong R (2015) Hollow mesoporous titania microspheres: new technology and enhanced photocatalytic activity. Appl Surf Sci 357:759–765

    Article  Google Scholar 

  22. Vajdaa K, Saszet K, Kedves EZ, Kása Z, Danciu V, Baia K, Magyaric K, Hernádi K, Kovács G, Pap Z (2016) Shape-controlled agglomeration of TiO2 nanoparticles. New insights on polycrystallinity vs. single crystals in photocatalysis. Ceram Int 42:3077–3087

    Article  Google Scholar 

  23. Kasuga T, Hiramatsu M, Hoson A, Sekino T, Niihara K (1999) Formation of titanium oxide nanotube. Langmuir 14:3160–3163

    Article  Google Scholar 

  24. Lai CW, Hamid SBA, Tan TL, Lee WH (2015) Rapid formation of 1D titanate nanotubes using alkaline hydrothermal treatment and its photocatalytic performance. J Nanomater 2015:1

    Google Scholar 

  25. Nguyen NH, Bai H (2015) Effect of washing pH on the properties of titanate nanotubes and its activity for photocatalytic oxidation of NO and NO2. Appl Surf Sci 355:672–680

    Article  Google Scholar 

  26. Nada A, Moustafa Y, Hamdy A (2014) Improvement of titanium dioxide nanotubes through study washing effect on hydrothermal. Br J Environ Sci 2:29–40

    Google Scholar 

  27. Mostafa NY, El-Bahy ZM (2015) Effect of microwave heating on the structure, morphology and photocatalytic activity of hydrogen titanate nanotubes. J Environ Chem Eng 3:744–751

    Article  Google Scholar 

  28. Bilgin N, Agartan L, Jongee PA, Ozturk A (2015) Synthesis of TiO2 nanostructures via hydrothermal method. Ceram Trans 253:177–186

    Google Scholar 

  29. Milanović M, Stijepović I, Nikolić LM (2010) Preparation and photocatalytic activity of the layered titanates. Process Appl Ceram 4(2):69–73

    Article  Google Scholar 

  30. Xiong L, Yang Y, Mai J, Sun W, Zhang C, Wei D, Chen Q, Ni J (2010) Adsorption behavior of methylene blue onto titanate nanotubes. Chem Eng J 156:313–320

    Article  Google Scholar 

  31. Buchholcz B, Haspel H, Kukovecz Á, Kónya Z (2014) Low-temperature conversion of titanate nanotubes into nitrogen-doped TiO2 nanoparticles. CrystEngComm 16:7486–7492

    Article  Google Scholar 

  32. Wang N, Lin H, Li J, Zhang L, Lin C, Li X (2006) Crystalline Transition from H2Ti3O7 nanotubes to anatase nanocrystallines under low-temperature hydrothermal conditions. J Am Ceram Soc 89:3564–3566

    Article  Google Scholar 

  33. Chen Q, Du GH, Zhang S, Peng L-M (2002) The structure of trititanate nanotubes. Acta Cryst B 58:587–593

    Article  Google Scholar 

  34. Suzuki Y, Yoshikawa S (2004) Synthesis and thermal analyses of TiO2-derived nanotubes prepared by the hydrothermal method. J Mater Res 19:982–985

    Article  Google Scholar 

  35. Zhang M, Jin Z, Zhang J, Guo X, Yang J, Li W, Wang X, Zhang Z (2004) Effect of annealing temperature on morphology, structure and photocatalytic behavior of nanotubed H2Ti2O4(OH)2. J Mol Catal A 217:203–210

    Article  Google Scholar 

  36. Yang J, Jin Z, Wang X, Li W, Zhang J, Zhang S, Guo X, Zhang Z (2003) Study on composition, structure and formation process of nanotube Na2Ti2O4(OH)2. Dalton Trans 20:3898–3901

    Article  Google Scholar 

  37. Qamar M, Yoon CR, Oh HJ, Kim DH, Jho JH, Lee KS, Lee WJ, Lee HG, Kim SJ (2006) Effect of post treatments on the structure and thermal stability of titanate nanotubes. Nanotechnology 17:5922–5929

    Article  Google Scholar 

  38. Ferreira OP, Souza Filho AG, Mendes Filho J, Alves OL (2006) Unveiling the structure and composition of titanium oxide nanotubes through ion exchange chemical reactions and thermal decomposition processes. J Braz Chem Soc 17:393–402

    Article  Google Scholar 

  39. Tsai C-C, Teng H (2006) Structural features of nanotubes synthesized from NaOH treatment on TiO2 with different post-treatments. Chem Mater 18:367–373

    Article  Google Scholar 

  40. Morgado E Jr, de Abreu MAS, Pravia ORC, Marinkovic BA, Jardim PM, Rizzo FC, Araújo AS (2006) A study on the structure and thermal stability of titanate nanotubes as a function of sodium content. Solid State Sci 8:888–900

    Article  Google Scholar 

  41. Viana BC, Ferreira OP, Souza Filho AG, Mendes Filho J, Alves OL (2009) Structural, morphological and vibrational properties of titanate nanotubes and nanoribbons. J Braz Chem Soc 20:167–175

    Article  Google Scholar 

  42. Morgado E Jr, de Abreu MAS, Moure GT, Marinkovic BA, Jardim PM, Araujo AS (2007) Characterization of nanostructured titanates obtained by alkali treatment of TiO2-anatases with distinct crystal sizes. Chem Mater 19:665–676

    Article  Google Scholar 

  43. Ma R, Bando Y, Sasaki T (2003) Nanotubes of lepidocrocite titanates. Chem Phys Lett 380:577–582

    Article  Google Scholar 

  44. Brunatova T, Popelkova D, Wan W, Oleynikov P, Danis S, Zou X, Kuzel R (2014) Study of titanate nanotubes by X-ray and electro diffraction and electron microscopy. Mater Charact 87:166–171

    Article  Google Scholar 

  45. Nakahira A, Kato W, Tamai M, Isshiki T, Nishio K (2004) Synthesis of nanotube from a layered H2Ti4O9·H2O in a hydrothermal treatment using various titania sources. J Mater Sci 9:4239–4245. doi:10.1023/B:JMSC.0000033405.73881.7c

    Article  Google Scholar 

  46. Wang YQ, Hu GQ, Duan XF, Sun HL, Xue QK (2002) Microstructure and formation mechanism of titanium dioxide nanotubes. Chem Phys Lett 365:427–431

    Article  Google Scholar 

  47. Yao BD, Chan YF, Zhang XY, Zhang WF, Yang ZY, Wang N (2003) Formation mechanism of TiO2 nanotubes. Appl Phys Lett 82:281–283

    Article  Google Scholar 

  48. Sauvet A-L, Baliteau S, Lopez C, Fabry P (2004) Synthesis and characterization of sodium titanates Na2Ti3O7 and Na2Ti6O13. J Solid State Chem 177:4508–4515

    Article  Google Scholar 

  49. Haimi E, Lipsonen H, Larismaa J, Kapulainen M, Krzak-Ros J, Hannula S-P (2011) Optical and structural properties of nanocrystalline anatase (TiO2) thin films prepared by non-aqueous sol–gel dip-coating. Thin Solid Films 519:5882–5886

    Article  Google Scholar 

  50. Gao T, Jelle BP (2013) Thermal conductivity of TiO2 nanotubes. J Phys Chem C 117:1401–1408

    Article  Google Scholar 

  51. Chen Q, Zhou WZ, Du GH, Peng LM (2002) Trititanate nanotubes made via a single alkali treatment. Adv Mater 14:1208–1211

    Article  Google Scholar 

  52. Du GH, Chen Q, Che RC, Yuan ZY, Peng LM (2001) Preparation and structure analysis of titanium oxide nanotubes. Appl Phys Lett 79:3702–3704

    Article  Google Scholar 

  53. Gao Y, Masudaa Y, Seo W-S, Ohta H, Koumoto K (2004) TiO2 nanoparticles prepared using an aqueous peroxotitanate solution. Ceram Int 30:1365–1368

    Article  Google Scholar 

  54. Toledo-Antonio JA, Capula S, Cortés-Jácome MA, Angeles-Chávez C, López-Salinas E, Ferrat G, Navarrete J, Escobar J (2007) Low-temperature FTIR study of CO adsorption on titania nanotubes. J Phys Chem C 111:10799–10805

    Article  Google Scholar 

  55. Byrne MT, McCarthy JE, Bent M, Blake R, Gun’ko YK, Horvath E, Konya Z, Kukovecz A, Kiricsi I, Coleman JN (2007) Chemical functionalisation of titania nanotubes and their utilisation for the fabrication of reinforced polystyrene composites. J Mater Chem 17:2351–2358

    Article  Google Scholar 

  56. Nikolić LM, Maletin M, Ferreira P, Vilarinho PM (2008) Synthesis and characterization of one-dimensional titanate structure. Process Appl Ceram 2:109–114

    Article  Google Scholar 

  57. Sun X, Li Y (2003) Synthesis and characterization of ion-exchangeable titanate nanotubes. Chem Eur J 9:2229–2238

    Article  Google Scholar 

  58. Thorne A, Kruth A, Tunstall D, Irvine JTS, Zhou W (2005) Formation, structure, and stability of titanate nanotubes and their proton conductivity. J Phys Chem B 109:5439–5444

    Article  Google Scholar 

  59. Bao-Li T, Zu-Liang DU, Yan-Mei MA, Xue-Fei LI, Qi-Liang CUI, Tian CUI, Bing-Bing LIU, Guang-Tian ZOU (2010) Raman investigation of sodium titanate nanotubes under hydrostatic pressures up to 26.9 GPa. Chin Phys Lett 27:026103

    Article  Google Scholar 

  60. Hodos M, Horváth E, Haspel H, Kukovecz Á, Kónya Z, Kiricsi I (2004) Photosensitization of ion-exchangeable titanate nanotubes by CdS nanoparticles. Chem Phys Lett 399:512–515

    Article  Google Scholar 

  61. Gao T, Fjellvåg H, Norby P (2009) Crystal structures of titanate nanotubes: a Raman scattering study. Inorg Chem 48:1423–1432

    Article  Google Scholar 

  62. Gupta SK, Desai R, Jha PK, Sahoo S, Kirin D (2010) Titanium dioxide synthesized using titanium chloride: size effect study using Raman spectroscopy and photoluminescence. J Raman Spectrosc 41:350–355

    Google Scholar 

  63. Ohsaka T, Izumi F, Fujiki Y (1978) Raman spectrum of anatase TiO2. J Raman Spectrosc 7:321–324

    Article  Google Scholar 

  64. Balachandran U, Eror NG (1982) Raman spectra of titanium dioxide. J Solid State Chem 42:276–282

    Article  Google Scholar 

  65. Tian F, Zhang YP, Zhang J, Pan CX (2012) Raman spectroscopy: a new approach to measure the percentage of anatase TiO2 exposed (001) facets. J Phys Chem C 116:7515–7519

    Article  Google Scholar 

  66. Asapu VR, Palla VM, Wang B, Guo Z, Sadu R, Chen DH (2011) Phosphorus-doped titania nanotubes with enhanced photocatalytic activity. J Photochem Photobiol A 225:81–87

    Article  Google Scholar 

  67. Fen LB, Han TK, Nee NM, Ang BC, Johan MR (2011) Physico-chemical properties of titania nanotubes synthesized via hydrothermal and annealing treatment. Appl Surf Sci 258:431–435

    Article  Google Scholar 

  68. Wang N, Lin H, Li J, Yang X, Chi B, Lin C (2006) Effect of annealing temperature on phase transition and optical property of titanate nanotubes prepared by ion exchange approach. J Alloys Compd 424:311–314

    Article  Google Scholar 

  69. Xiong L, Sun W, Yang Y, Chen C, Ni Jinren (2011) Heterogeneous photocatalysis of methylene blue over titanate nanotubes: effect of adsorption. J Colloid Interf Sci 356:211–216

    Article  Google Scholar 

  70. Yu J, Yu H, Cheng B, Trapalis C (2006) Effect of calcination temperature on microstructures and photocatalytic activity of titanate nanotubes. J Mol Catal A 249:135–142

    Article  Google Scholar 

  71. Feng J, Zhu J, Lv W, Li J, Yan W (2015) Effect of hydroxyl group of carboxylic acids on the adsorption of acid red G and methylene blue on TiO2. Chem Eng J 269:316–322

    Article  Google Scholar 

  72. Vuk AŠ, Ješe R, Orel B, Dražič G (2005) The effect of surface hydroxyl groups on the adsorption properties of nanocrystalline TiO2 films. Int J Photoenergy 7:163–168

    Article  Google Scholar 

  73. Chatterjee S, Tyagi AK, Ayyub P (2014) Efficient photocatalytic degradation of Rhodamine B dye by aligned arrays of self-assembled hydrogen titanate nanotubes. J Nanomater 2014:7

    Article  Google Scholar 

  74. Inagaki M, Kondo N, Nonaka R, Ito E, Toyoda M, Sogabe K, Tsumura T (2009) Structure and photoactivity of titania derived from nanotubes and nanofibers. J Hazard Mater 161:1514–1521

    Article  Google Scholar 

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Acknowledgements

The authors would like to acknowledge the facilities provided by Aalto University Nanomicroscopy Center (Aalto-NMC) for FTIR and UV/Vis spectroscopy measurements. Raman spectroscopy work was carried out at Low Temperature Laboratory, Aalto University, and we are thankful to them. Help of Ajay Iyer for Raman spectroscopy is acknowledged.

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  1. Department of Materials Science and Engineering, Aalto University School of Chemical Technology, P.O. Box 16200, FI-00076, Aalto, Finland

    Saima Ali, Henrika Granbohm, Yanling Ge, Vivek Kumar Singh, Frans Nilsén & Simo-Pekka Hannula

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  1. Saima Ali
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  2. Henrika Granbohm
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Ali, S., Granbohm, H., Ge, Y. et al. Crystal structure and photocatalytic properties of titanate nanotubes prepared by chemical processing and subsequent annealing. J Mater Sci 51, 7322–7335 (2016). https://doi.org/10.1007/s10853-016-0014-5

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