Facile Synthesis of Monodispersed In2O3 Hollow Spheres and Application in Photocatalysis and Gas Sensing

Monodispersed, agglomerate-free In2O3 hollow spheres have been prepared via a simple synthetic route involving permeation and anchoring of In3+ ions with carbonyl groups of swollen commercial polymer beads in tetrachloroethylene solvent followed by thermal removal of the template cores in ambient air. The as-synthesized hollow spheres exhibit a narrow size distribution with tunable particle size (0.5–1.2 μm) and shell thickness (62–230 nm) over the process variables examined, i.e., InCl3 precursor concentration (4.5 × 10−3–6.7 × 10−2 M), reaction temperature (55°C–95°C), and reaction time (1–6 h). Kinetics calculation reveals that the formation of permeating In3+-rich shell in the swollen template beads becomes energetically less favorable to proceed as the reaction time increases. This limits the maximum shell thickness attainable at the given process variables. The shell is nanoporous with a Horvath-Kawazoe (HK) pore size of ~3 nm, which remains essentially unchanged as the process variables alter. The In2O3 hollow spheres with an increased Brunauer-Emmett-Teller (BET) surface area (up to 329 m2/g) show an improved capability in photodegradation of aqueous methylene blue (MB) dye under UV exposure as well as an increased sensitivity for CO-gas detection. This metal-implantation scheme is general and can be extended to the synthesis of other hollow materials in various solvent liquids.

[1]  Deren Yang,et al.  InOOH hollow spheres synthesized by a simple hydrothermal reaction. , 2005, The journal of physical chemistry. B.

[2]  K. Nebesny,et al.  Characterization of Indium−Tin Oxide Interfaces Using X-ray Photoelectron Spectroscopy and Redox Processes of a Chemisorbed Probe Molecule: Effect of Surface Pretreatment Conditions , 2002 .

[3]  W. Tseng,et al.  A Novel Technique for Synthesizing Nanoshell Hollow Alumina Particles , 2009 .

[4]  Yuqiu Wang,et al.  Morphology Control of β-In2S3 from Chrysanthemum-Like Microspheres to Hollow Microspheres: Synthesis and Electrochemical Properties , 2009 .

[5]  Yun Chan Kang,et al.  Ultrasensitive and selective C2H5OH sensors using Rh-loaded In2O3 hollow spheres , 2011 .

[6]  K. Awaga,et al.  Preparation, photocatalytic activities, and dye-sensitized solar-cell performance of submicron-scale TiO2 hollow spheres. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[7]  J. H. Lee,et al.  Gas sensors using hierarchical and hollow oxide nanostructures: Overview , 2009 .

[8]  Ling Liu,et al.  Phase-controlled synthesis of monodispersed porous In2O3 nanospheres via an organic acid-assisted hydrothermal process , 2011 .

[9]  Kunio Furusawa,et al.  Assembly of Latex Particles by Using Emulsion Droplets as Templates. 1. Microstructured Hollow Spheres , 1996 .

[10]  W. Tseng,et al.  Synthesis, microstructure, and photocatalysis of In2O3 hollow particles , 2011 .

[11]  A. Pich,et al.  Tailored growth of In(OH)(3) shell on functionalized polystyrene beads. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[12]  A. Gurlo,et al.  Surfactant-free self-assembly route to hollow In2O3 microspheres. , 2009, Chemical communications.

[13]  R. Caruso,et al.  Template Synthesis and Photocatalytic Properties of Porous Metal Oxide Spheres Formed by Nanoparticle Infiltration , 2004 .

[14]  Nai-Ben Ming,et al.  Facile Methods to Coat Polystyrene and Silica Colloids with Metal , 2004 .

[15]  A. R. Bausch,et al.  Colloidosomes: Selectively Permeable Capsules Composed of Colloidal Particles , 2002, Science.

[16]  M. T. Colomer,et al.  Synthesis and Characterization of Anatase‐Structured Titania Hollow Spheres Doped with Erbium (III) , 2012 .

[17]  L. Archer,et al.  A General Route to Nonspherical Anatase TiO2 Hollow Colloids and Magnetic Multifunctional Particles , 2008 .

[18]  W. S. Choi,et al.  Templated Synthesis of Porous Capsules with a Controllable Surface Morphology and their Application as Gas Sensors , 2007 .

[19]  Caruso,et al.  Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating , 1998, Science.

[20]  Kaixun Huang,et al.  Fabrication of indium sulfide hollow spheres and their conversion to indium oxide hollow spheres consisting of multipore nanoflakes , 2007 .

[21]  Hua Zhao,et al.  Controlled synthesis and photocatalytic properties of porous hollow In2O3 microcubes with different sizes , 2011 .

[22]  Jiguang Liu,et al.  Template synthesis of tin-doped indium oxide (ITO)/polymer and the corresponding carbon composite hollow colloids , 2007 .

[23]  John Man-shun Ma,et al.  Synthesis of Spheres with Complex Structures Using Hollow Latex Cages as Templates , 2005 .

[24]  Yong Jia,et al.  Template synthesis, organic gas-sensing and optical properties of hollow and porous In2O3 nanospheres , 2008, Nanotechnology.

[25]  Yun Chan Kang,et al.  Enhanced C2H5OH sensing characteristics of nano-porous In2O3 hollow spheres prepared by sucrose-mediated hydrothermal reaction , 2011 .

[26]  Guangzhao Zhang,et al.  In2O3 hollow microspheres: synthesis from designed In(OH)3 precursors and applications in gas sensors and photocatalysis. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[27]  K. Choi,et al.  Enhanced CO sensing characteristics of hierarchical and hollow In2O3 microspheres , 2009 .

[28]  L. Archer,et al.  Hollow Micro‐/Nanostructures: Synthesis and Applications , 2008 .

[29]  Takeshi Hashishin,et al.  NO2 sensing properties of macroporous In2O3-based powders fabricated by utilizing ultrasonic spray pyrolysis employing polymethylmethacrylate microspheres as a template , 2010 .