Ligand-exchange assisted formation of Au/TiO2 Schottky contact for visible-light photocatalysis.

Plasmonic noble metal nanoparticles have emerged as a promising material in sensitizing wide-bandgap semiconductors for visible-light photocatalysis. Conventional methods in constructing such heterocatalysts suffer from either poor control over the size of the metal nanoparticles or inefficient charge transfer through the metal/semiconductor interface, which limit their photocatalytic activity. To solve this problem, in this work we construct Au/TiO2 photocatalysts by depositing presynthesized colloidal Au nanoparticles with well-controlled sizes to TiO2 nanocrystals and then removing capping ligands on the Au surface through a delicately designed ligand-exchange method, which leads to close Au/TiO2 Schottky contact after a mild annealing process. Benefiting from this unique synthesis strategy, the obtained photocatalysts show superior activity to conventionally prepared photocatalysts in dye decomposition and water-reduction hydrogen production under visible-light illumination. This study not only opens up new opportunities in designing photoactive materials with high stability and enhanced performance for solar energy conversion but also provides a potential solution for the well-recognized challenge in cleaning capping ligands from the surface of colloidal catalyst nanoparticles.

[1]  Benxia Li,et al.  Metal/Semiconductor Hybrid Nanostructures for Plasmon‐Enhanced Applications , 2014, Advanced materials.

[2]  M. Engelhard,et al.  Surface plasmon-driven water reduction: gold nanoparticle size matters. , 2014, Journal of the American Chemical Society.

[3]  Xiaobo Chen,et al.  Vacuum-treated titanium dioxide nanocrystals: Optical properties, surface disorder, oxygen vacancy, and photocatalytic activities , 2014 .

[4]  Yadong Yin,et al.  One-step growth of triangular silver nanoplates with predictable sizes on a large scale. , 2014, Nanoscale.

[5]  R. T. Tung The physics and chemistry of the Schottky barrier height , 2014 .

[6]  T. Tachikawa,et al.  Au/TiO2 superstructure-based plasmonic photocatalysts exhibiting efficient charge separation and unprecedented activity. , 2014, Journal of the American Chemical Society.

[7]  Zhenda Lu,et al.  Photocatalytic synthesis and photovoltaic application of Ag-TiO2 nanorod composites. , 2013, Nano letters.

[8]  D. Sun-Waterhouse,et al.  Effect of gold loading and TiO2 support composition on the activity of Au/TiO2 photocatalysts for H2 production from ethanol–water mixtures , 2013 .

[9]  Yadong Yin,et al.  Size-tailored synthesis of silver quasi-nanospheres by kinetically controlled seeded growth. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[10]  Y. Tong,et al.  Au nanostructure-decorated TiO2 nanowires exhibiting photoactivity across entire UV-visible region for photoelectrochemical water splitting. , 2013, Nano letters.

[11]  Shuxin Ouyang,et al.  Gold-nanorod-photosensitized titanium dioxide with wide-range visible-light harvesting based on localized surface plasmon resonance. , 2013, Angewandte Chemie.

[12]  Martin Moskovits,et al.  An autonomous photosynthetic device in which all charge carriers derive from surface plasmons. , 2013, Nature nanotechnology.

[13]  L. Rossi,et al.  Synthesis of supported metal nanoparticle catalysts using ligand assisted methods. , 2012, Nanoscale.

[14]  Zhi Wei Seh,et al.  Janus Au‐TiO2 Photocatalysts with Strong Localization of Plasmonic Near‐Fields for Efficient Visible‐Light Hydrogen Generation , 2012, Advanced materials.

[15]  Yiding Liu,et al.  One-step seeded growth of Au nanoparticles with widely tunable sizes. , 2012, Nanoscale.

[16]  Yasuhiro Shiraishi,et al.  Gold nanoparticles located at the interface of anatase/rutile TiO2 particles as active plasmonic photocatalysts for aerobic oxidation. , 2012, Journal of the American Chemical Society.

[17]  E. Thimsen,et al.  Plasmonic solar water splitting , 2012 .

[18]  S. Linic,et al.  Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. , 2011, Nature materials.

[19]  Christopher J. Kiely,et al.  Facile removal of stabilizer-ligands from supported gold nanoparticles. , 2011, Nature chemistry.

[20]  Claire M. Cobley,et al.  Controlling the synthesis and assembly of silver nanostructures for plasmonic applications. , 2011, Chemical reviews.

[21]  R. F. Howe,et al.  The effect of gold loading and particle size on photocatalytic hydrogen production from ethanol over Au/TiO₂ nanoparticles. , 2011, Nature chemistry.

[22]  Suljo Linic,et al.  Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface. , 2011, Journal of the American Chemical Society.

[23]  Plasmon enhanced solar-to-fuel energy conversion. , 2011, Nano letters.

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

[25]  H. García,et al.  Influence of excitation wavelength (UV or visible light) on the photocatalytic activity of titania containing gold nanoparticles for the generation of hydrogen or oxygen from water. , 2011, Journal of the American Chemical Society.

[26]  Hui Yang,et al.  An orthophosphate semiconductor with photooxidation properties under visible-light irradiation. , 2010, Nature materials.

[27]  Younan Xia,et al.  Chemical synthesis of novel plasmonic nanoparticles. , 2009, Annual review of physical chemistry.

[28]  Chad A Mirkin,et al.  Colloidal gold and silver triangular nanoprisms. , 2009, Small.

[29]  Tsuyoshi Takata,et al.  Self-Templated Synthesis of Nanoporous CdS Nanostructures for Highly Efficient Photocatalytic Hydrogen Production under Visible Light , 2008 .

[30]  Xiaobo Chen,et al.  Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications. , 2007, Chemical reviews.

[31]  R. Nuzzo,et al.  Preparation of TiO2-supported Au nanoparticle catalysts from a Au13 cluster precursor: Ligand removal using ozone exposure versus a rapid thermal treatment , 2006 .

[32]  H. Zeng,et al.  Preparation of Monodisperse Au/TiO 2 Nanocatalysts via Self-Assembly , 2006 .

[33]  Ferdi Schüth,et al.  Support effect in high activity gold catalysts for CO oxidation. , 2006, Journal of the American Chemical Society.

[34]  J. Moulijn,et al.  XPS and Mssbauer Characterization of Au/TiO 2 Propene Epoxidation Catalysts , 2002 .

[35]  R. Asahi,et al.  Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides , 2001, Science.