Abstract
This paper presents a systematic investigation on the growth of TiO2 nanotubes (NTs) by modifying the continuity in the applied potential through conventional one-step electrochemical anodization (CEA), paused electrochemical anodization (PEA), two-step electrochemical anodization (TEA), and pulsed electrochemical anodization (PLA). The essence of this research pertains to understanding the significance of surface solid fraction factor (ψ) in relation to the density of surface defects. Additionally, in order to comprehend and incorporate the influence of cracks on surface defects and carrier transport, the reported ψ has been modified for the first time. Moreover, this attempt involves the use of H2O2 as an electrolytic oxidizer for the first time in PEA, TEA, and PLA techniques to explore the possibility in creating ripple free NTs. UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), photoluminescence, and X-ray photoelectron spectroscopy (XPS) provided insights into the band gap and quantification of surface defects for NTs anodized via continuous and pulsed modes. The effect of voltage continuity on % porosity of the TiO2 NT arrays was investigated. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques were also carried out to determine the electrical properties of the prepared TiO2 NT arrays.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Aïnouche L, Hamadou L, Kadri A et al (2014) Interfacial barrier layer properties of three generations of TiO2 nanotube arrays. Electrochim Acta 133:597–609. https://doi.org/10.1016/j.electacta.2014.04.086
Albu SP, Roy P, Virtanen S, Schmuki P (2010) Self-organized TiO2 nanotube arrays: critical effects on morphology and growth. Isr J Chem 50:453–467. https://doi.org/10.1002/ijch.201000059
Ali Yahia SA, Hamadou L, Kadri A et al (2012) Effect of anodizing potential on the formation and EIS characteristics of TiO2 nanotube arrays. J Electrochem Soc 159:K83–K92. https://doi.org/10.1149/2.077204jes
Berger S, Albu SP, Schmidt-Stein F et al (2011) The origin for tubular growth of TiO2 nanotubes: a fluoride rich layer between tube-walls. Surf Sci 605:L57–L60. https://doi.org/10.1016/j.susc.2011.06.019
Bonatto F, Venturini J, Frantz AC et al (2018) One-step synthesis of nanograss-free TiO2 nanotubes using DTPA-enriched electrolytes. Ceram Int 44:22345–22351. https://doi.org/10.1016/j.ceramint.2018.08.360
Borbón-Nuñez HA, Dominguez D, Muñoz-Muñoz F et al (2017) Fabrication of hollow TiO2 nanotubes through atomic layer deposition and MWCNT templates. Powder Technol 308:249–257. https://doi.org/10.1016/j.powtec.2016.12.001
Chang Y-J, Lee J-W, Chen H-P et al (2011) Photocatalytic characteristics of TiO2 nanotubes with different microstructures prepared under different pulse anodizations. Thin Solid Films 519:3334–3339. https://doi.org/10.1016/j.tsf.2010.12.155
Chanmanee W, Watcharenwong A, Chenthamarakshan CR, Kajitvichyanukul P, de Tacconi NR, Rajeshwar K (2008) Formation and characterization of self-organized TiO2 nanotube arrays by pulse anodization. J Am Chem Soc 130:965–974. https://doi.org/10.1021/ja076092a
Chu D, Younis A, Li S (2012) Direct growth of TiO2 nanotubes on transparent substrates and their resistive switching characteristics. J Phys D Appl Phys 45:355306. https://doi.org/10.1088/0022-3727/45/35/355306
David TM, Sagayaraj P, Wilson P et al (2016) Room temperature hydrogen sensing of Pt loaded TiO2 nanotubes powders prepared via rapid breakdown anodization. J Electrochem Soc 163:B15–B18. https://doi.org/10.1149/2.0451603jes
David TM, Wilson P, Manju V et al (2017) Electrocatalytic investigation of group X metal nanoparticles loaded TiO2 nanotubes powder prepared by rapid breakdown anodization for selective H2O2 sensing. J Electrochem Soc 164:B356–B365. https://doi.org/10.1149/2.0611707jes
Duan Y, Fu N, Liu Q et al (2012) Sn-doped TiO2 photoanode for dye-sensitized solar cells. J Phys Chem C 116:8888–8893. https://doi.org/10.1021/jp212517k
Ghicov A, Schmuki P (2009) Self-ordering electrochemistry: a review on growth and functionality of TiO2 nanotubes and other self-aligned MOx structures. Chem Commun 2791. https://doi.org/10.1039/b822726h
Gong D, Grimes CA, Varghese OK et al (2001) Titanium oxide nanotube arrays prepared by anodic oxidation. J Mater Res 16:3331–3334. https://doi.org/10.1557/JMR.2001.0457
Joseph S, Sagayaraj P (2015) A cost effective approach for developing substrate stable TiO 2 nanotube arrays with tuned morphology: a comprehensive study on the role of H 2 O 2 and anodization potential. New J Chem 39:5402–5409. https://doi.org/10.1039/C5NJ00565E
Khudhair D, Amani Hamedani H, Gaburro J, Shafei S, Nahavandi S, Garmestani H, Bhatti A (2017) Enhancement of electro-chemical properties of TiO2 nanotubes for biological interfacing. Mater Sci Eng C 77:111–120. https://doi.org/10.1016/j.msec.2017.03.112
Kim D, Ghicov A, Schmuki P (2008) TiO2 nanotube arrays: elimination of disordered top layers (“nanograss”) for improved photoconversion efficiency in dye-sensitized solar cells. Electrochem Commun 10:1835–1838. https://doi.org/10.1016/j.elecom.2008.09.029
Knorr FJ, Mercado CC, McHale JL (2008) Trap-state distributions and carrier transport in pure and mixed-phase TiO2: influence of contacting solvent and interphasial electron transfer. J Phys Chem C 112:12786–12794. https://doi.org/10.1021/jp8039934
Ku SJ, Jo GC, Bak CH, Kim SM, Shin YR, Kim KH, Kwon SH, Kim JB (2013) Highly ordered freestanding titanium oxide nanotube arrays using Si-containing block copolymer lithography and atomic layer deposition. Nanotechnology 24:085301. https://doi.org/10.1088/0957-4484/24/8/085301
Lai CW, Sreekantan S (2012) Dimensional control of titanium dioxide nanotube arrays with hydrogen peroxide content for high photoelectrochemical water splitting performance. Micro Nano Lett 7:443–447. https://doi.org/10.1049/mnl.2012.0237
Lee H, Park T-H, Jang D-J (2016) Preparation of anatase TiO2 nanotube arrays dominated by highly reactive facets via anodization for high photocatalytic performances. New J Chem 40:8737–8744. https://doi.org/10.1039/C6NJ01625A
Li J, Zhang M, Guan Z et al (2017) Synergistic effect of surface and bulk single-electron-trapped oxygen vacancy of TiO2 in the photocatalytic reduction of CO2. Appl Catal B Environ 206:300–307. https://doi.org/10.1016/j.apcatb.2017.01.025
Liang S, He J, Sun Z et al (2012) Improving photoelectrochemical water splitting activity of TiO2 nanotube arrays by tuning geometrical parameters. J Phys Chem C 116:9049–9053. https://doi.org/10.1021/jp300552s
Lin J, Chen X (2012) Synthesis of high-aspect-ratio, top-open and ultraflat-surface TiO2 nanotubes through double-layered configuration. physica status solidi (RRL) - Rapid Research Letters 6:28–30. https://doi.org/10.1002/pssr.201105461
Lin J, Liu X, Zhu S, Chen X (2015) TiO2 nanotube structures for the enhancement of photon utilization in sensitized solar cells. Nanotechnol Rev 4:209–238. https://doi.org/10.1515/ntrev-2014-0028
Liu R, Sun Z, Zhang Y et al (2017) Polyoxometalate-modified TiO2 nanotube arrays photoanode materials for enhanced dye-sensitized solar cells. J Phys Chem Solids 109:64–69. https://doi.org/10.1016/j.jpcs.2017.05.018
López R, Gómez R (2012) Band-gap energy estimation from diffuse reflectance measurements on sol–gel and commercial TiO2: a comparative study. J Sol-Gel Sci Technol 61:1–7. https://doi.org/10.1007/s10971-011-2582-9
Ly NT, Nguyen VC, Dao TH et al (2013) Optical properties of TiO2 nanotube arrays fabricated by the electrochemical anodization method. Adv Nat Sci Nanosci Nanotechnol 5:015004. https://doi.org/10.1088/2043-6262/5/1/015004
Ma X, Li M, Meng F, Wang L, Feng C, Chen N, Liu X (2018) Efficient nano titanium electrode via a two-step electrochemical anodization with reconstructed nanotubes: electrochemical activity and stability. Chemosphere 202:177–183. https://doi.org/10.1016/j.chemosphere.2018.03.063
Manovah David T, Wilson P, Mahesh R, Dhanavel S, Hussain S, Jacob Melvin Boby S, Stephen A, Ramesh C, Sagayaraj P (2018) Investigating the photocatalytic degradation property of Pt, Pd and Ni nanoparticles-loaded TiO2 nanotubes powder prepared via rapid breakdown anodization. Environ Technol 39:2994–3005. https://doi.org/10.1080/09593330.2017.1371248
Manovah David T, Wilson P, Ramesh C, Sagayaraj P (2014) A comparative study on the morphological features of highly ordered titania nanotube arrays prepared via galvanostatic and potentiostatic modes. Curr Appl Phys 14:868–875. https://doi.org/10.1016/j.cap.2014.04.002
Mohammadpour F, Moradi M (2015) Double-layer TiO2 nanotube arrays by two-step anodization: used in back and front-side illuminated dye-sensitized solar cells. Mater Sci Semicond Process 39:255–264. https://doi.org/10.1016/j.mssp.2015.04.048
Nasirpouri F, Peighambardoust N-S, Samardak A et al (2017) Structural defect-induced bandgap narrowing in dopant-free anodic TiO2 nanotubes. Chem Electro Chem 4:1227–1235. https://doi.org/10.1002/celc.201700038
Noothongkaew S, Jung HK, Thumtan O, An K-S (2018) Synthesis of free-standing anatase TiO2 membrane by using two-step anodization. Mater Lett 233:153–157. https://doi.org/10.1016/j.matlet.2018.08.116
Raut SS, Patil GP, Chavan PG, Sankapal BR (2016) Vertically aligned TiO2 nanotubes: highly stable electrochemical supercapacitor. J Electroanal Chem 780:197–200. https://doi.org/10.1016/j.jelechem.2016.09.024
Ruan C, Paulose M, Varghese OK et al (2005) Fabrication of highly ordered TiO2 nanotube arrays using an organic electrolyte. J Phys Chem B 109:15754–15759. https://doi.org/10.1021/jp052736u
Sacco A, Garino N, Lamberti A et al (2017) Anodically-grown TiO2 nanotubes: effect of the crystallization on the catalytic activity toward the oxygen reduction reaction. Appl Surf Sci 412:447–454. https://doi.org/10.1016/j.apsusc.2017.03.224
Shah UH, Rahman Z, Deen KM, Asgar H, Shabib I, Haider W (2017) Investigation of the formation mechanism of titanium oxide nanotubes and its electrochemical evaluation. J Appl Electrochem 47:1147–1159. https://doi.org/10.1007/s10800-017-1102-1
Smith YR, Sarma B, Mohanty SK, Misra M (2012) Light-assisted anodized TiO2 nanotube arrays. ACS Appl Mater Interfaces 4:5883–5890. https://doi.org/10.1021/am301527g
Sreekantan S, Wei LC, Lockman Z (2011) Extremely fast growth rate of TiO2 nanotube arrays in electrochemical Bath containing H2O2. J Electrochem Soc 158:C397. https://doi.org/10.1149/2.020112jes
Sun L, Zhang S, Sun X, He X (2010) Effect of the geometry of the anodized titania nanotube array on the performance of dye-sensitized solar cells. J Nanosci Nanotechnol 10:4551–4561. https://doi.org/10.1166/jnn.2010.1695
Tao J, Zhao J, Tang C et al (2008) Mechanism study of self-organized TiO2 nanotube arrays by anodization. New J Chem 32:2164. https://doi.org/10.1039/b808719a
Viet PV, Huy TH, You S-J et al (2018) Hydrothermal synthesis, characterization, and photocatalytic activity of silicon doped TiO2 nanotubes. Superlattice Microst 123:447–455. https://doi.org/10.1016/j.spmi.2018.09.035
Wang K, Liu G, Hoivik N, Johannessen E, Jakobsen H (2014) Electrochemical engineering of hollow nanoarchitectures: pulse/step anodization (Si, Al, Ti) and their applications. Chem Soc Rev 43:1476–1500. https://doi.org/10.1039/C3CS60150A
Xiao P, Zhang Y, Cao G (2011) Effect of surface defects on biosensing properties of TiO2 nanotube arrays. Sensors Actuators B Chem 155:159–164. https://doi.org/10.1016/j.snb.2010.11.041
Xie ZB, Blackwood DJ (2010) Effects of anodization parameters on the formation of titania nanotubes in ethylene glycol. Electrochim Acta 56:905–912. https://doi.org/10.1016/j.electacta.2010.10.004
Yang P, Liu Y, Chen S et al (2016) Influence of H2O2 and H2O content on anodizing current and morphology evolution of anodic TiO 2 nanotubes. Mater Res Bull 83:581–589. https://doi.org/10.1016/j.materresbull.2016.07.006
Yasuda K, Macak JM, Berger S et al (2007) Mechanistic aspects of the self-organization process for oxide nanotube formation on valve metals. J Electrochem Soc 154:C472. https://doi.org/10.1149/1.2749091
Yazıcı EY (2017) Improvement of stability of hydrogen peroxide using ethylene glycol. Deu Muhendislik Fakultesi Fen ve Muhendislik 19:938–949. https://doi.org/10.21205/deufmd.2017195782
Zhu K, Neale NR, Miedaner A, Frank AJ (2007a) Enhanced charge-collection efficiencies and light scattering in dye-sensitized solar cells using oriented TiO2 nanotubes arrays. Nano Lett 7:69–74. https://doi.org/10.1021/nl062000o
Zhu K, Vinzant TB, Neale NR, Frank AJ (2007b) Removing structural disorder from oriented TiO2 nanotube arrays: reducing the dimensionality of transport and recombination in dye-sensitized solar cells. Nano Lett 7:3739–3746. https://doi.org/10.1021/nl072145a
Zwilling V, Aucouturier M, Darque-Ceretti E (1999) Anodic oxidation of titanium and TA6V alloy in chromic media. An electrochemical approach. Electrochim Acta 45:921–929. https://doi.org/10.1016/S0013-4686(99)00283-2
Acknowledgments
Special thanks to the members of Dr. P. Wilson’s research group, Department of Chemistry, Madras Christian College for their valuable discussion and insights. The authors also thank Mr. Raju, EEC Division, CECRI and the Central Instrumentation Facility (CIF) at CSIR-CECRI, Karaikudi, India for providing the analytical instrumentation. We acknowledge Nanotechnology Research Centre (NRC), SRMIST for providing the research facilities.
Funding
Financial support was received through the Science and Engineering Research Board (SERB) under the Department of Science and Technology (DST) (Grant No: EMR/2015/001406) and DST-FIST, Ministry of Science and Technology, India.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Dev, P.R., David, T.M., Samuel Justin, S. et al. A plausible impact on the role of pulses in anodized TiO2 nanotube arrays enhancing Ti3+ defects. J Nanopart Res 22, 56 (2020). https://doi.org/10.1007/s11051-020-4780-2
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-020-4780-2