Blue TiO2 Nanotube Array as an Oxidant Generating Novel Anode Material Fabricated by Simple Cathodic Polarization

Great interest in anode materials has dramatically emerged with increasing demand for electrochemically generated oxidants in industrial electrochemistry. For the last five decades, these needs have been mostly achieved by the introduction of two well-known anode materials, the dimensional stable anode (DSA®) and boron-doped diamond (BDD) electrodes. Nevertheless, the high cost and complicated process in fabricating these electrodes remains as a big obstacle for further development. Here, we report a novel anode material for the production of oxidants, the dark blue colored TiO2 nanotube array (NTA) (denoted as Blue TiO2 NTA) which has never been successfully achieved with titania-based materials. This titania-based electrocatalyst with irreversible electrochromism and high conductivity was successfully fabricated with simple cathodic polarization of anatase TiO2 NTA and exhibits the excellent electrocatalytic activity in generating chlorine (Cl2) and hydroxyl radical (•OH) which is comparable to the commercial DSA® and BDD electrodes, respectively. Thus, this Blue TiO2 NTA is suggested as a potential cost effective anodic material in industrial electrochemistry. In addition, even in other metal oxides other than titania, the cathodic polarization (accompanied with irreversible electrochromism) method may be applied to explore a new route for low-cost and novel anodic materials.

[1]  M. Rodrigo,et al.  Electrogeneration of Hydroxyl Radicals on Boron-Doped Diamond Electrodes , 2003 .

[2]  Xiaobo Chen,et al.  Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals , 2011, Science.

[3]  David R. Rosseinsky,et al.  Electrochromic Systems and the Prospects for Devices , 2001 .

[4]  Anne C. Dillon,et al.  Metal-oxide films for electrochromic applications: present technology and future directions , 2010 .

[5]  Guohua Chen,et al.  Electrochemistry for the Environment , 2010 .

[6]  M. Miyauchi,et al.  Electrochromism of titanate-based nanotubes. , 2005, Angewandte Chemie.

[7]  Kouji Yasuda,et al.  TiO2 nanotubes: Self-organized electrochemical formation, properties and applications , 2007 .

[8]  Álvaro Somoza,et al.  Synthesis and surface modification of uniform MFe2O4 (M = Fe, Mn, and Co) nanoparticles with tunable sizes and functionalities , 2012, Journal of Nanoparticle Research.

[9]  Han Gao,et al.  Transparent, well-aligned TiO(2) nanotube arrays with controllable dimensions on glass substrates for photocatalytic applications. , 2010, ACS applied materials & interfaces.

[10]  A. Fujishima,et al.  Highly Hydrophilic Surfaces of Cathodically Polarized Amorphous TiO2 Electrodes , 2001 .

[11]  C. Grimes,et al.  Fabrication of PbS nanoparticle-sensitized TiO₂ nanotube arrays and their photoelectrochemical properties. , 2011, ACS applied materials & interfaces.

[12]  Marc Doyle,et al.  Report on the electrolytic industries for the year 1999 , 2000 .

[13]  M. Panizza,et al.  Electrochemical oxidation of phenol at boron-doped diamond electrode. Application to electro-organic synthesis and wastewater treatment. , 2001, Annali di chimica.

[14]  Sergio Trasatti,et al.  Electrocatalysis: understanding the success of DSA® , 2000 .

[15]  Jan M. Macak,et al.  TiO2 nanotubes: H+insertion and strong electrochromic effects , 2006 .

[16]  Krishnan Rajeshwar,et al.  Environmental Electrochemistry: Fundamentals and Applications in Pollution Abatement , 1997 .

[17]  Hui Wu,et al.  High-performance and renewable supercapacitors based on TiO2 nanotube array electrodes treated by an electrochemical doping approach , 2014 .

[18]  Satyen K. Deb,et al.  Opportunities and challenges in science and technology of WO3 for electrochromic and related applications , 2008 .

[19]  Choonsoo Kim,et al.  The effect of electrode material on the generation of oxidants and microbial inactivation in the electrochemical disinfection processes. , 2009, Water research.

[20]  M. Grätzel,et al.  A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films , 1991, Nature.

[21]  Brinkmann Thomas,et al.  CORRIGENDUM Best Available Techniques (BAT) Reference Document for the Production of Chlor-alkali. Industrial Emissions Directive 2010/75/EU (Integrated Pollution Prevention and Control) , 2014 .

[22]  John R. Owen,et al.  Electrochemistry of novel materials , 1997 .

[23]  Y. Lai,et al.  Effects of the Structure of TiO2 Nanotube Array on Ti Substrate on Its Photocatalytic Activity , 2006 .

[24]  W. Stickle,et al.  Handbook of X-Ray Photoelectron Spectroscopy , 1992 .

[25]  Craig A. Grimes,et al.  Transparent Highly Ordered TiO2 Nanotube Arrays via Anodization of Titanium Thin Films , 2005 .

[26]  T. Yamase,et al.  Photo- and Electrochromism of Polyoxometalates and Related Materials. , 1998, Chemical reviews.

[27]  Patrik Schmuki,et al.  TiO2 nanotubes: synthesis and applications. , 2011, Angewandte Chemie.

[28]  Choonsoo Kim,et al.  Facile detection of photogenerated reactive oxygen species in TiO2 nanoparticles suspension using colorimetric probe-assisted spectrometric method. , 2013, Chemosphere.

[29]  G. Frey,et al.  Enhanced reversible electrochromism via in situ phase transformation in tungstate monohydrate. , 2009, Chemical communications.

[30]  R. Mortimer,et al.  New Electrochromic Materials , 2002, Science progress.

[31]  Y. Sung,et al.  Enhanced Photovoltaic Properties of a Cobalt Bipyridyl Redox Electrolyte in Dye-Sensitized Solar Cells Employing Vertically Aligned TiO2 Nanotube Electrodes , 2011 .

[32]  Craig A. Grimes,et al.  TiO2 Nanotube Arrays: Synthesis, Properties, and Applications , 2009 .

[33]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[34]  Wonyong Choi,et al.  Linear correlation between inactivation of E. coli and OH radical concentration in TiO2 photocatalytic disinfection. , 2004, Water research.

[35]  J. Macák,et al.  Filling of TiO2 Nanotubes by Self‐Doping and Electrodeposition , 2007 .

[36]  Juan Bisquert,et al.  High carrier density and capacitance in TiO2 nanotube arrays induced by electrochemical doping. , 2008, Journal of the American Chemical Society.

[37]  C. Martínez-Huitle,et al.  Electrochemical alternatives for drinking water disinfection. , 2008, Angewandte Chemie.

[38]  C. N. Trumbore,et al.  p-Nitrosodimethylaniline as an OH Radical Scavenger in Radiation Chemistry1 , 1965 .

[39]  Teng Zhai,et al.  Hydrogenated TiO2 nanotube arrays for supercapacitors. , 2012, Nano letters.

[40]  K. Kowalski,et al.  Photocatalytic bleaching of p-nitrosodimethylaniline and a comparison to the performance of other AOP technologies , 2010 .

[41]  J. Yi,et al.  Influence of Aspect Ratio of TiO2 Nanorods on the Photocatalytic Decomposition of Formic Acid , 2009 .

[42]  Premanand Ramadass,et al.  Report on the Electrolytic Industries for the Year 2004 , 2006 .

[43]  H. Over Atomic scale insights into electrochemical versus gas phase oxidation of HCl over RuO2-based catalysts: A comparative review , 2013 .

[44]  N. Lewis,et al.  Electrochemical production of hydroxyl radical at polycrystalline Nb-doped TiO2 electrodes and estimation of the partitioning between hydroxyl radical and direct hole oxidation pathways , 1997 .

[45]  B. Mamba,et al.  Multiwalled carbon nanotubes decorated with nitrogen, palladium co-doped TiO2 (MWCNT/N, Pd co-doped TiO2) for visible light photocatalytic degradation of Eosin Yellow in water , 2012, Journal of Nanoparticle Research.

[46]  A. Fujishima,et al.  Electrochemical Photolysis of Water at a Semiconductor Electrode , 1972, Nature.

[47]  Giacomo Cerisola,et al.  Application of diamond electrodes to electrochemical processes , 2005 .

[48]  A. Kraft Doped Diamond: A Compact Review on a New, Versatile Electrode Material , 2007, International Journal of Electrochemical Science.

[49]  Claes G. Granqvist,et al.  Handbook of inorganic electrochromic materials , 1995 .