Silica‐Supported Au–Ag Catalysts for the Selective Hydrogenation of Butadiene

Gold and silver are miscible over the entire composition range, and form an attractive combination for fundamental studies on bimetallic catalysts. Au–Ag catalysts have shown synergistic effects for different oxidation and liquid‐phase hydrogenation reactions, but have rarely been studied for gas‐phase hydrogenation. In this study 3 nm particles of Au, Ag and Au–Ag supported on silica (SBA‐15) were investigated as catalysts for selective hydrogenation of butadiene in an excess of propene. The Au catalyst was over an order of magnitude more active than the Ag catalyst at 120 °C. The initial activity of the Au–Ag catalysts scaled linearly with the Au‐content, suggesting a direct correlation between the surface and overall compositions of the nanoparticles and the absence of synergistic effects. All Au‐containing catalysts were highly selective to butenes (>99.9 %). The Au catalysts were stable, whereas the Au–Ag catalysts lost about half of their activity during 20 h run time at 200 °C, but the initial activity was restored by a consecutive oxidation‐reduction treatment. Near ambient pressure x‐ray photoelectron spectroscopy showed that exposure to H2 at elevated temperatures led to a gradual enrichment of the surface of the Au–Ag nanoparticles by Ag. These observations highlight the importance of considering progressive atomic rearrangements in bimetallic nanocatalysts under reaction conditions.

[1]  P. D. de Jongh,et al.  Fully alloyed metal nanorods with highly tunable properties. , 2017, Nanoscale.

[2]  C. W. Han,et al.  Selective hydrogenation of 1,3-butadiene over bimetallic Au-Ni/TiO 2 catalysts prepared by deposition-precipitation with urea , 2016 .

[3]  Yanhui Yang,et al.  Surface Composition Control of the Binary Au–Ag Catalyst for Enhanced Oxidant-Free Dehydrogenation , 2016 .

[4]  J. K. Das,et al.  Extremely fast Au–Ag alloy–dealloy associated reversible plasmonic modifications in SiO2 films , 2016 .

[5]  B. Viswanathan,et al.  Studies on Ni–M (M = Cu, Ag, Au) bimetallic catalysts for selective hydrogenation of cinnamaldehyde , 2016 .

[6]  L. Kiwi-Minsker,et al.  Carbon supported gold and silver: Application in the gas phase hydrogenation of m-dinitrobenzene , 2015 .

[7]  M. Flytzani-Stephanopoulos,et al.  Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit , 2015, Nature Communications.

[8]  Yanhui Yang,et al.  Improved chemoselective hydrogenation of crotonaldehyde over bimetallic AuAg/SBA-15 catalyst , 2015 .

[9]  C. Louis,et al.  Synergetic effect in bimetallic Au–Ag/TiO2 catalysts for CO oxidation: New insights from in situ characterization , 2015 .

[10]  A. Beck,et al.  Bimetallic Au–Ag/SiO2 catalysts: comparison in glucose, benzyl alcohol and CO oxidation reactions , 2015, Reaction Kinetics, Mechanisms and Catalysis.

[11]  C. Louis,et al.  Selective hydrogenation of butadiene over TiO2 supported copper, gold and gold-copper catalysts prepared by deposition-precipitation. , 2014, Physical chemistry chemical physics : PCCP.

[12]  J. Pérez‐Ramírez,et al.  Beyond the use of modifiers in selective alkyne hydrogenation: silver and gold nanocatalysts in flow mode for sustainable alkene production. , 2014, Nanoscale.

[13]  Xiaoliang Yan,et al.  Stable Au catalysts for selective hydrogenation of acetylene in ethylene , 2014 .

[14]  Hieu A. Doan,et al.  The critical role of water at the gold-titania interface in catalytic CO oxidation , 2014, Science.

[15]  Andrew J. Logsdail,et al.  Segregation effects on the properties of (AuAg)₁₄₇. , 2014, Physical chemistry chemical physics : PCCP.

[16]  Michael Bender An Overview of Industrial Processes for the Production of Olefins – C4 Hydrocarbons , 2014 .

[17]  N. Kruse,et al.  Higher Alcohols through CO Hydrogenation over CoCu Catalysts: Influence of Precursor Activation , 2014 .

[18]  A. Beck,et al.  Bimetallic Ag–Au/SiO2 catalysts: Formation, structure and synergistic activity in glucose oxidation , 2014 .

[19]  V. Papaefthimiou,et al.  Mixing Patterns and Redox Properties of Iron-Based Alloy Nanoparticles under Oxidation and Reduction Conditions , 2014 .

[20]  Tao Zhang,et al.  Understanding the synergistic effects of gold bimetallic catalysts , 2013 .

[21]  K. Kaneda,et al.  Gold nanoparticle catalysts for selective hydrogenations , 2013 .

[22]  Qihua Wang,et al.  Fabrication of thermally stable and active bimetallic Au-Ag nanoparticles stabilized on inner wall of mesoporous silica shell. , 2013, Dalton transactions.

[23]  C. Louis,et al.  Improved activity and stability in CO oxidation of bimetallic Au-Cu/TiO2 catalysts prepared by deposition-precipitation with urea , 2013 .

[24]  G. Somorjai,et al.  Exploring surface science and restructuring in reactive atmospheres of colloidally prepared bimetallic CuNi and CuCo nanoparticles on SiO2 in situ using ambient pressure X-ray photoelectron spectroscopy. , 2013, Faraday discussions.

[25]  Tianpin Wu,et al.  Selective hydrogenation of acrolein on supported silver catalysts: A kinetics study of particle size effects , 2013 .

[26]  C. Louis,et al.  Bimetallic Au-Pd catalysts for selective hydrogenation of butadiene: Influence of the preparation method on catalytic properties , 2013 .

[27]  Jianwei Zheng,et al.  Efficient low-temperature selective hydrogenation of esters on bimetallic Au-Ag/SBA-15 catalyst , 2013 .

[28]  Yanan Li,et al.  Selective hydrogenation of acetylene in excess ethylene over SiO2 supported Au–Ag bimetallic catalyst , 2012 .

[29]  Kenta Yoshida,et al.  On the Effect of Atomic Structure on the Activity and Deactivation of Catalytic Gold Nanoparticles , 2012 .

[30]  Jingguang G. Chen,et al.  Review of Pt-based bimetallic catalysis: from model surfaces to supported catalysts. , 2012, Chemical reviews.

[31]  C. Louis,et al.  Bimetallic Au-Ag/TiO2 catalyst prepared by deposition-precipitation: High activity and stability in CO oxidation , 2011 .

[32]  M. Cortie,et al.  Synthesis and optical properties of hybrid and alloy plasmonic nanoparticles. , 2011, Chemical reviews.

[33]  T. Akita,et al.  Synergistic catalysis of Au@Ag core-shell nanoparticles stabilized on metal-organic framework. , 2011, Journal of the American Chemical Society.

[34]  Santiago Gómez-Quero,et al.  Tunable gas phase hydrogenation of m-dinitrobenzene over alumina supported Au and Au–Ni , 2010 .

[35]  N. López,et al.  Molecular understanding of alkyne hydrogenation for the design of selective catalysts. , 2010, Dalton transactions.

[36]  C. Louis,et al.  Selective Hydrogenation of 1,3-Butadiene in the Presence of an Excess of Alkenes over Supported Bimetallic Gold−Palladium Catalysts , 2010 .

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

[38]  Tao Zhang,et al.  Unusual Selectivity of Gold Catalysts for Hydrogenation of 1,3-Butadiene toward cis-2-Butene: A Joint Experimental and Theoretical Investigation , 2010 .

[39]  R. Schlögl,et al.  Activation of dihydrogen on supported and unsupported silver catalysts , 2010 .

[40]  C. Louis,et al.  Influence of the reactant concentration in selective hydrogenation of 1,3-butadiene over supported gold catalysts under alkene rich conditions: A consideration of reaction mechanism , 2009 .

[41]  Keli Han,et al.  Combined Experimental and Theoretical Investigation on the Selectivities of Ag, Au, and Pt Catalysts for Hydrogenation of Crotonaldehyde , 2009 .

[42]  Aiqin Wang,et al.  CO Oxidation Catalyzed by Au−Ag Bimetallic Nanoparticles Supported in Mesoporous Silica , 2009 .

[43]  D. Su,et al.  Synthesis of Thermally Stable and Highly Active Bimetallic Au−Ag Nanoparticles on Inert Supports , 2009 .

[44]  P. Claus,et al.  Silica supported silver nanoparticles from a silver(I) carboxylate: Highly active catalyst for regioselective hydrogenation , 2009 .

[45]  C. Louis,et al.  Supported gold catalysts for selective hydrogenation of 1,3-butadiene in the presence of an excess of alkenes , 2008 .

[46]  R. Schlögl,et al.  Silver as acrolein hydrogenation catalyst: intricate effects of catalyst nature and reactant partial pressures. , 2007, Physical chemistry chemical physics : PCCP.

[47]  A. Singh,et al.  Heterogenized vanadyl cations over modified silica surfaces: A comprehensive understanding toward the structural property and catalytic activity difference over mesoporous and amorphous silica supports , 2006 .

[48]  Bo-Qing Xu,et al.  Catalysis by gold: isolated surface Au3+ ions are active sites for selective hydrogenation of 1,3-butadiene over Au/ZrO2 catalysts. , 2005, Angewandte Chemie.

[49]  Aiqin Wang,et al.  Evolution of catalytic activity of Au-Ag bimetallic nanoparticles on mesoporous support for CO oxidation. , 2005, The journal of physical chemistry. B.

[50]  G. Fecher,et al.  Selective Hydrogenation of 1,3‐Butadiene to 1‐Butene by Pd(0) Nanoparticles Embedded in Imidazolium Ionic Liquids , 2005 .

[51]  Aiqin Wang,et al.  Synergistic effect in an Au-Ag alloy nanocatalyst: CO oxidation. , 2005, The journal of physical chemistry. B.

[52]  Bao-hang Han,et al.  Simple synthesis route to monodispersed SBA-15 silica rods. , 2004, Journal of the American Chemical Society.

[53]  C. Louis,et al.  Crotonaldehyde hydrogenation by gold supported on TiO2: structure sensitivity and mechanism , 2004 .

[54]  P. Claus,et al.  Structural Properties of Ag/TiO 2 Catalysts for Acrolein Hydrogenation , 2004 .

[55]  Z. Révay,et al.  Some features of acetylene and 1,3-butadiene hydrogenation on Ag/SiO2 and Ag/TiO2 catalysts , 2003 .

[56]  S. Pratsinis,et al.  OH Surface Density of SiO 2 and TiO 2 by Thermogravimetric Analysis , 2003 .

[57]  Catherine J. Murphy,et al.  Solution-Phase Synthesis of Sub-10 nm Au−Ag Alloy Nanoparticles , 2002 .

[58]  T. Akita,et al.  Hydrogenation of 1,3-butadiene and of crotonaldehyde over highly dispersed Au catalysts , 2002 .

[59]  Zhenyuan Zhang,et al.  Size-dependent melting of silica-encapsulated gold nanoparticles. , 2002, Journal of the American Chemical Society.

[60]  C. Powell,et al.  Evaluation of Calculated and Measured Electron Inelastic Mean Free Paths Near Solid Surfaces , 1999 .

[61]  J. Nørskov,et al.  Why gold is the noblest of all the metals , 1995, Nature.

[62]  L. Guczi,et al.  1,3-Butadiene selective hydrogenation over Pd/alumina and CuPd/alumina catalysts , 1994 .

[63]  M. Derrien Chapter 18 Selective Hydrogenation Applied to the Refining of Petrochemical Raw Materials Produced by Steam Cracking , 1986 .

[64]  P. Wells The influence on selectivity of the environment of catalyst sitesIII. The role of hydrogen occlusion in group VIII metals , 1978 .