Site-Selective Growth of Crystalline Ceria with Oxygen Vacancies on Gold Nanocrystals for Near-Infrared Nitrogen Photofixation.

Site-selective growth of crystalline semiconductors on gold nanocrystals remains a great challenge because of the difficult control of both nucleation and growth dynamics as well as the easy agglomeration and deformation of gold nanocrystals at high temperatures of 400-1000 °C. Here we report a facile wet-chemistry route for the selective growth of crystalline ceria at the ends of gold nanorods (Au NRs) in the presence of a small amount of bifunctional K2PtCl4. Due to the smaller steric hindrance at the ends than at the side surface, K2PtCl4 may preferentially adsorb at the ends of Au NRs, triggering the autoredox reaction with the ceria precursor to obtain crystalline CeO2 at the ends. Notably, the surface of grown ceria is rich in oxygen vacancies (OVs) that facilitate the adsorption and activation of N2 molecules. The unique structure, the plasmon-induced hot carriers and the OVs make the obtained Au/end-CeO2 an excellent catalyst for nitrogen photofixation under near-infrared (NIR) illumination.

[1]  Hangqi Zhao,et al.  Quantifying hot carrier and thermal contributions in plasmonic photocatalysis , 2018, Science.

[2]  Jianfang Wang,et al.  Emerging Applications of Plasmons in Driving CO2 Reduction and N2 Fixation , 2018, Advanced materials.

[3]  J. Renner,et al.  The Use of Controls for Consistent and Accurate Measurements of Electrocatalytic Ammonia Synthesis from Dinitrogen , 2018, ACS Catalysis.

[4]  Jianfang Wang,et al.  High-Efficiency "Working-in-Tandem" Nitrogen Photofixation Achieved by Assembling Plasmonic Gold Nanocrystals on Ultrathin Titania Nanosheets. , 2018, Journal of the American Chemical Society.

[5]  H. Tada,et al.  Red-Light-Driven Water Splitting by Au(Core)-CdS(Shell) Half-Cut Nanoegg with Heteroepitaxial Junction. , 2018, Journal of the American Chemical Society.

[6]  Yasuhiro Shiraishi,et al.  Photocatalytic Conversion of Nitrogen to Ammonia with Water on Surface Oxygen Vacancies of Titanium Dioxide. , 2017, Journal of the American Chemical Society.

[7]  Shuyan Song,et al.  Achieving the Trade‐Off between Selectivity and Activity in Semihydrogenation of Alkynes by Fabrication of (Asymmetrical Pd@Ag Core)@(CeO2 Shell) Nanocatalysts via Autoredox Reaction , 2017, Advanced materials.

[8]  Lizhi Zhang,et al.  Solar Water Splitting and Nitrogen Fixation with Layered Bismuth Oxyhalides. , 2017, Accounts of chemical research.

[9]  Jianfang Wang,et al.  Aerosol-Sprayed Gold/Ceria Photocatalyst with Superior Plasmonic Hot Electron-Enabled Visible-Light Activity. , 2017, ACS applied materials & interfaces.

[10]  Xinchen Wang,et al.  Precise Formation of a Hollow Carbon Nitride Structure with a Janus Surface To Promote Water Splitting by Photoredox Catalysis , 2016, Angewandte Chemie.

[11]  G. Stucky,et al.  Anisotropic Growth of TiO2 onto Gold Nanorods for Plasmon-Enhanced Hydrogen Production from Water Reduction. , 2016, Journal of the American Chemical Society.

[12]  Peter Nordlander,et al.  Plasmon-induced hot carrier science and technology. , 2015, Nature nanotechnology.

[13]  M. Ouyang,et al.  Hierarchical synthesis of non-centrosymmetric hybrid nanostructures and enabled plasmon-driven photocatalysis , 2014, Nature Communications.

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

[15]  Jianfang Wang,et al.  (Gold core)@(ceria shell) nanostructures for plasmon-enhanced catalytic reactions under visible light. , 2014, ACS nano.

[16]  Jian Pan,et al.  Titanium dioxide crystals with tailored facets. , 2014, Chemical reviews.

[17]  M. Ouyang,et al.  Controlling Structural Symmetry of a Hybrid Nanostructure and its Effect on Efficient Photocatalytic Hydrogen Evolution , 2014, Advanced materials.

[18]  C. Clavero,et al.  Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices , 2014, Nature Photonics.

[19]  Jianfang Wang,et al.  Anisotropic overgrowth of metal heterostructures induced by a site-selective silica coating. , 2013, Angewandte Chemie.

[20]  R. Hamers,et al.  Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction. , 2013, Nature materials.

[21]  J. Paier,et al.  Oxygen defects and surface chemistry of ceria: quantum chemical studies compared to experiment. , 2013, Chemical reviews.

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

[23]  A. Heller,et al.  Mixed-valence metal oxide nanoparticles as electrochemical half-cells: substituting the Ag/AgCl of reference electrodes by CeO(2-x) nanoparticles. , 2012, Journal of the American Chemical Society.

[24]  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.

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

[26]  H. Ramanarayan,et al.  Anisotropic growth of titania onto various gold nanostructures: synthesis, theoretical understanding, and optimization for catalysis. , 2011, Angewandte Chemie.

[27]  F. Zhang,et al.  Cerium oxidation state in ceria nanoparticles studied with X-ray photoelectron spectroscopy and absorption near edge spectroscopy , 2004 .