Structural Construction of Au-Pd Nanocomposite for Alkali-Free Oxidation of Benzyl Alcohol.

A bimetallic Au-Pd system is an alternative candidate to catalyze primary alcohol oxidation and is of crucial importance for the sustainable chemical industry. However, understanding the bimetallic system in terms of the nanostructure is still challenging. Herein, we adopt the in situ colloid immobilization to obtain a series of bimetallic AuxPdy/CNT samples supported by carbon nanotubes (CNTs). Elaborate characterizations confirmed the bimetallic structure of AuPd alloy particles with randomly dispersed Pd2+ on the surface, forming the AuPd@PdO structure on CNTs. Unlike the monometallic samples, bimetallic ones, particularly Au1Pd1/CNT, efficiently transformed benzyl alcohol in an alkali-free mild condition. The DFT simulation confirmed the electron-rich gold atoms as a steric and electronic regulator to confine the electron-deficient Pd atoms in alloy particles. The interacted metal sites in the alloy system activated the alcohol with optimized adsorption configuration. Surface Pd2+ transported active oxygen to capture the abstracted H on alcohol. The collaboration between metal sites facilitated the transformation of benzyl alcohol to benzaldehyde with the selectivity of 91.8% by a fast TOF of 1274 h-1 at only 80 °C.

[1]  A. Villa,et al.  A Career in Catalysis: Laura Prati , 2023, ACS Catalysis.

[2]  Zhe Wang,et al.  Dual Pd2+ and Pd0 sites on CeO2 for benzyl alcohol selective oxidation , 2022, Journal of Catalysis.

[3]  Changhai Liang,et al.  Au Nanoparticles Anchored on Sulfonated Carbon Nanotubes for Benzyl Alcohol Oxidation , 2022, ACS Applied Nano Materials.

[4]  Peter J. Miedziak,et al.  Au–Pd separation enhances bimetallic catalysis of alcohol oxidation , 2022, Nature.

[5]  Ying Dai,et al.  TiO2/Ti3C2 as an efficient photocatalyst for selective oxidation of benzyl alcohol to benzaldehyde , 2021, Applied Catalysis B: Environmental.

[6]  G. Hutchings,et al.  Enhanced Selective Oxidation of Benzyl Alcohol via In Situ H2O2 Production over Supported Pd-Based Catalysts , 2021 .

[7]  Zifeng Yan,et al.  High-performance benzyl alcohol oxidation catalyst: Au-Pd alloy with ZrO2 as promoter , 2021 .

[8]  Wenzhong Shen,et al.  Atomically dispersed Feδ+ anchored on nitrogen-rich carbon for enhancing benzyl alcohol oxidation through Mott-Schottky effect , 2021 .

[9]  Linjiang Wang,et al.  Facile synthesis of AuPd nanowires anchored on the hybrid of layered double hydroxide and carbon black for enhancing catalytic performance towards ethanol electro-oxidation , 2019, International Journal of Hydrogen Energy.

[10]  D. Su,et al.  Atomic-scale observation of bimetallic Au-CuOx nanoparticles and their interfaces for activation of CO molecules. , 2019, ACS applied materials & interfaces.

[11]  Hefang Wang,et al.  Pd nanoparticles confined within triazine-based carbon nitride NTs: An efficient catalyst for Knoevenagel condensation-reduction cascade reactions , 2019, Catalysis Today.

[12]  De Chen,et al.  Optimising surface d charge of AuPd nanoalloy catalysts for enhanced catalytic activity , 2019, Nature Communications.

[13]  B. Puértolas,et al.  Enhanced Base-Free Formic Acid Production from CO2 on Pd/g-C3 N4 by Tuning of the Carrier Defects. , 2018, ChemSusChem.

[14]  W. Xu,et al.  Engineering Cobalt Defects in Cobalt Oxide for Highly Efficient Electrocatalytic Oxygen Evolution , 2018 .

[15]  Stuart H. Taylor,et al.  Aqueous Au-Pd colloids catalyze selective CH4 oxidation to CH3OH with O2 under mild conditions , 2017, Science.

[16]  Yongxin Li,et al.  Palladium Nanoparticles Supported on Mesoporous Carbon Nitride for Efficiently Selective Oxidation of Benzyl Alcohol with Molecular Oxygen , 2017 .

[17]  H. Hirata,et al.  Synergistic Promotion of NO-CO Reaction Cycle by Gold and Nickel Elucidated using a Well-Defined Model Bimetallic Catalyst Surface , 2017 .

[18]  A. Villa,et al.  Influence of pretreatment atmospheres on the performance of bimetallic Au-Pd supported on ceria-zirconia mixed oxide catalysts for benzyl alcohol oxidation , 2016 .

[19]  M. Szynkowska,et al.  Bimetallic Au–Cu, Au–Ni catalysts supported on MWCNTs for oxy-steam reforming of methanol , 2016 .

[20]  Xiaojun Wu,et al.  Integration of Kinetic Control and Lattice Mismatch To Synthesize Pd@AuCu Core-Shell Planar Tetrapods with Size-Dependent Optical Properties. , 2016, Nano letters.

[21]  Tao Zhang,et al.  Strong Metal-Support Interactions between Gold Nanoparticles and Nonoxides. , 2016, Journal of the American Chemical Society.

[22]  G. Hutchings,et al.  Glycerol oxidation using gold-containing catalysts. , 2015, Accounts of chemical research.

[23]  Changying Zhao,et al.  Dehydration/hydration of MgO/H2O chemical thermal storage system , 2015 .

[24]  N. Long,et al.  Highly selective oxidation of benzyl alcohol to benzaldehyde catalyzed by nano Au/γ-Al2O3 under environment-friendly conditions , 2015, Reaction Kinetics, Mechanisms and Catalysis.

[25]  Li Wang,et al.  Undoped ZnO abundant with metal vacancies , 2014 .

[26]  S. Stahl,et al.  Practical aerobic oxidations of alcohols and amines with homogeneous copper/TEMPO and related catalyst systems. , 2014, Angewandte Chemie.

[27]  Jiale Huang,et al.  Biosynthesized Bimetallic Au–Pd Nanoparticles Supported on TiO2 for Solvent-Free Oxidation of Benzyl Alcohol , 2014 .

[28]  I. Melián-Cabrera,et al.  An efficient one pot conversion of glycerol to lactic acid using bimetallic gold-platinum catalysts on a nanocrystalline CeO2 support , 2014 .

[29]  O. O. James,et al.  Aerobic oxidation of benzyl alcohol over mesoporous Mn-doped ceria supported Au nanoparticle catalyst , 2013 .

[30]  G. Hutchings,et al.  Aberration corrected analytical electron microscopy studies of sol-immobilized Au + Pd, Au{Pd} and Pd{Au} catalysts used for benzyl alcohol oxidation and hydrogen peroxide production. , 2011, Faraday discussions.

[31]  Peter J. Miedziak,et al.  Selective Oxidation of Glycerol by Highly Active Bimetallic Catalysts at Ambient Temperature under Base-Free Conditions , 2011, Angewandte Chemie.

[32]  G. Hutchings,et al.  Solvent-Free Oxidation of Primary Carbon-Hydrogen Bonds in Toluene Using Au-Pd Alloy Nanoparticles , 2011, Science.

[33]  Matthew Neurock,et al.  Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis , 2010, Science.

[34]  M. Rossi,et al.  Highly selective oxidation of benzyl alcohol to benzaldehyde catalyzed by bimetallic gold–copper catalyst , 2008 .

[35]  G. Hutchings,et al.  Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO2 Catalysts , 2006, Science.