A simple, rapid, one-step approach for preparation of Ag@TiO2 nanospheres with multiple cores as effective catalyst

Novel Ag@TiO2 nanostructures with multiple Ag nanoparticles as cores and a crystalline TiO2 as the outer shell have been successfully achieved via a facile and one-step solvothermal route. The synthetic approach is simple, rapid, and environmentally friendly, in which no any sacrificial template, toxic reagent or surfactant is emploited. Moreover, the as-prepared Ag@TiO2 products show an uniform and spherical morphology as well as a large specific surface area (225.9 m2 g−1). The time-dependent experiments reveal that the formation of Ag@TiO2 nanospheres includes a nucleation, aggregation and self-assembly process. Apart form this, the rattle-type Ag@TiO2 nanoparticles can be also obtained by only tuning the amount of tetrabutyl titanate (TBOT) added in the precursor. When employed as catalyst for reduction of 4-nitrophenol (4-NP), the Ag@TiO2 nanospheres prepared exhibit a superior catalytic activity and a good cycle stability, benefiting from their unique multiple-cored nanostructure and the effective synergistic effect between Ag nanoparticles and TiO2 shell. The present method also provides a great possibility for preparation of other metal@TiO2 nanocomposites and their promising applications in catalysis, electrochemistry, and purification, and so on.

[1]  N. Yan,et al.  Recent advances in the synthesis and catalytic applications of ligand-protected, atomically precise metal nanoclusters , 2016 .

[2]  Haijiao Zhang,et al.  Dual-templating synthesis of multi-shelled mesoporous silica nanoparticles as catalyst and drug carrier , 2016 .

[3]  I. Piwoński,et al.  Examination of Ostwald ripening in the photocatalytic growth of silver nanoparticles on titanium dioxide coatings , 2016 .

[4]  Jiangtian Li,et al.  Controlling Plasmon-Induced Resonance Energy Transfer and Hot Electron Injection Processes in Metal@TiO2 Core–Shell Nanoparticles , 2015 .

[5]  Younghun Kim,et al.  Au nanoparticle-embedded SiO2–Au@SiO2 catalysts with improved catalytic activity, enhanced stability to metal sintering and excellent recyclability , 2015 .

[6]  Ib Chorkendorff,et al.  Crystalline TiO2: A Generic and Effective Electron-Conducting Protection Layer for Photoanodes and -cathodes , 2015 .

[7]  S. Hikichi,et al.  Effects of Re addition upon aqueous phase reforming of ethanol over TiO2 supported Rh and Ir catalysts , 2015 .

[8]  Yanyan Zhang,et al.  Catalytic performance of TiO2@Ag composites prepared by modified photodeposition method , 2014 .

[9]  Luhong Zhang,et al.  One-step synthesis of metal@titania core-shell materials for visible-light photocatalysis and catalytic reduction reaction. , 2014, Chemistry.

[10]  D. Leong,et al.  Toward understanding the growth mechanism: tracing all stable intermediate species from reduction of Au(I)-thiolate complexes to evolution of Au₂₅ nanoclusters. , 2014, Journal of the American Chemical Society.

[11]  A. Selloni,et al.  Theoretical studies on anatase and less common TiO2 phases: bulk, surfaces, and nanomaterials. , 2014, Chemical reviews.

[12]  Hua Chun Zeng,et al.  Synthesis of complex nanomaterials via Ostwald ripening , 2014 .

[13]  Arne Thomas,et al.  Polymeric carbon nitride/mesoporous silica composites as catalyst support for Au and Pt nanoparticles. , 2014, Chemistry.

[14]  T. Kanda,et al.  Preparation of gold/silver/titania trilayered nanorods and their photocatalytic activities. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[15]  Rodney D. Priestley,et al.  Au@carbon yolk-shell nanostructures via one-step core-shell-shell template. , 2014, Chemical communications.

[16]  D. Zhao,et al.  A Perspective on Mesoporous TiO2 Materials , 2014 .

[17]  Canhui Lu,et al.  Nanofibrillated cellulose as the support and reductant for the facile synthesis of Fe3O4/Ag nanocomposites with catalytic and antibacterial activity , 2013 .

[18]  H. Fu,et al.  A facile and green synthesis route towards two-dimensional TiO2@Ag heterojunction structure with enhanced visible light photocatalytic activity , 2013 .

[19]  Jianfang Wang,et al.  Metal Nanocrystal‐Embedded Hollow Mesoporous TiO2 and ZrO2 Microspheres Prepared with Polystyrene Nanospheres as Carriers and Templates , 2013 .

[20]  Zhenyu Liu,et al.  Synthesis of thermally stable Ag@TiO2 core–shell nanoprisms and plasmon–enhanced optical properties for a P3HT thin film , 2013 .

[21]  P. Camargo,et al.  A facile approach to TiO2 colloidal spheres decorated with Au nanoparticles displaying well-defined sizes and uniform dispersion. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[22]  Yaqi Cai,et al.  A novel Fe3O4–graphene–Au multifunctional nanocomposite: green synthesis and catalytic application , 2012 .

[23]  J. Yates,et al.  Localized partial oxidation of acetic acid at the dual perimeter sites of the Au/TiO2 catalyst-formation of gold ketenylidene. , 2012, Journal of the American Chemical Society.

[24]  O. Ersen,et al.  Experimental assessment of the phonon confinement in TiO2 anatase nanocrystallites by Raman spectroscopy , 2012 .

[25]  F. Besenbacher,et al.  Promotion of phenol photodecomposition over TiO2 using Au, Pd, and Au-Pd nanoparticles. , 2012, ACS nano.

[26]  P. Kamat.  TiO2 Nanostructures: Recent Physical Chemistry Advances , 2012 .

[27]  A. Ismail,et al.  Mesostructure Au/TiO2 nanocomposites for highly efficient catalytic reduction of p-nitrophenol , 2012 .

[28]  Z. Tang,et al.  Facile synthesis of Au@TiO2 core–shell hollow spheres for dye-sensitized solar cells with remarkably improved efficiency , 2012 .

[29]  Weidong Ruan,et al.  Raman Investigation of Nanosized TiO2: Effect of Crystallite Size and Quantum Confinement , 2012 .

[30]  Chun-yan Liu,et al.  Au/graphene hydrogel: synthesis, characterization and its use for catalytic reduction of 4-nitrophenol , 2012 .

[31]  W. Cai,et al.  Rattle-type Au@TiO2 hollow microspheres with multiple nanocores and porous shells and their structurally enhanced catalysis , 2010 .

[32]  K. Shimizu,et al.  Size- and support-dependent silver cluster catalysis for chemoselective hydrogenation of nitroaromatics , 2010 .

[33]  Shuhong Yu,et al.  Large scale photochemical synthesis of M@TiO2 nanocomposites (M = Ag, Pd, Au, Pt) and their optical properties, CO oxidation performance, and antibacterial effect , 2010 .

[34]  B. Popov,et al.  Development of a titanium dioxide-supported platinum catalyst with ultrahigh stability for polymer electrolyte membrane fuel cell applications. , 2009, Journal of the American Chemical Society.

[35]  Yeon-Tae Yu,et al.  Synthesis of core-shell Au@TiO2 nanoparticles with truncated wedge-shaped morphology and their photocatalytic properties. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[36]  Da Chen,et al.  Tuning Photoelectrochemical Performances of Ag−TiO2 Nanocomposites via Reduction/Oxidation of Ag , 2008 .

[37]  Hyunjoon Song,et al.  A Nanoreactor Framework of a Au@SiO2 Yolk/Shell Structure for Catalytic Reduction of p‐Nitrophenol , 2008 .

[38]  Zhichuan J. Xu,et al.  Magnetic core/shell Fe3O4/Au and Fe3O4/Au/Ag nanoparticles with tunable plasmonic properties. , 2007, Journal of the American Chemical Society.

[39]  A. Corma,et al.  Gold Catalysts Open a New General Chemoselective Route to Synthesize Oximes by Hydrogenation of α,β-Unsaturated Nitrocompounds with H2 , 2007 .

[40]  L. Archer,et al.  Encapsulation and Ostwald Ripening of Au and Au–Cl Complex Nanostructures in Silica Shells , 2006 .

[41]  Reji Philip,et al.  Freely Dispersible Au@TiO2, Au@ZrO2, Ag@TiO2, and Ag@ZrO2 Core−Shell Nanoparticles: One-Step Synthesis, Characterization, Spectroscopy, and Optical Limiting Properties , 2003 .

[42]  A. Corma,et al.  Catalyst parameters determining activity and selectivity of supported gold nanoparticles for the aerobic oxidation of alcohols: the molecular reaction mechanism. , 2008, Chemistry.