CuNi Nanoparticles Assembled on Graphene for Catalytic Methanolysis of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds

We report a solution-phase synthesis of 16 nm CuNi nanoparticles (NPs) with the Cu/Ni composition control. These NPs are assembled on graphene (G) and show Cu/Ni composition-dependent catalysis for methanolysis of ammonia borane (AB) and hydrogenation of aromatic nitro (nitrile) compounds to primary amines in methanol at room temperature. Among five different CuNi NPs studied, the G-Cu36Ni64 NPs are the best catalyst for both AB methanolysis (turnover frequency (TOF) of 49.1 molH2 molCuNi–1 min–1 and an activation energy (Ea) of 24.4 kJ/mol) and hydrogenation reactions (conversion yield of >97%). The G-CuNi compound represents a unique noble-metal-free catalyst for hydrogenation reactions in a green environment without using pure hydrogen.

[1]  Mingsheng Wang,et al.  Magnetically Responsive Nanostructures with Tunable Optical Properties , 2016 .

[2]  Shouheng Sun,et al.  FePd alloy nanoparticles assembled on reduced graphene oxide as a catalyst for selective transfer hydrogenation of nitroarenes to anilines using ammonia borane as a hydrogen source , 2016 .

[3]  E. Pop,et al.  Role of Pressure in the Growth of Hexagonal Boron Nitride Thin Films from Ammonia-Borane , 2016, 1605.06861.

[4]  Yadong Li,et al.  Modulating fcc and hcp Ruthenium on the Surface of Palladium-Copper Alloy through Tunable Lattice Mismatch. , 2016, Angewandte Chemie.

[5]  M. Peruzzini,et al.  Ammonia-Borane and Amine-Borane Dehydrogenation Mediated by Complex Metal Hydrides. , 2016, Chemical reviews.

[6]  E. Waclawik,et al.  Alloying Gold with Copper Makes for a Highly Selective Visible-Light Photocatalyst for the Reduction of Nitroaromatics to Anilines , 2016 .

[7]  Yuen Wu,et al.  Ultrathin Icosahedral Pt-Enriched Nanocage with Excellent Oxygen Reduction Reaction Activity. , 2016, Journal of the American Chemical Society.

[8]  J. M. Kikkawa,et al.  Synthesis and Size-Selective Precipitation of Monodisperse Nonstoichiometric MxFe3–xO4 (M = Mn, Co) Nanocrystals and Their DC and AC Magnetic Properties , 2016 .

[9]  Shuang Cao,et al.  Nanostructured Ni2 P as a Robust Catalyst for the Hydrolytic Dehydrogenation of Ammonia-Borane. , 2015, Angewandte Chemie.

[10]  F. Alonso,et al.  Copper Nanoparticles in Click Chemistry , 2015 .

[11]  Xiangshu Chen,et al.  Ruthenium nanoparticles confined in SBA-15 as highly efficient catalyst for hydrolytic dehydrogenation of ammonia borane and hydrazine borane , 2015, Scientific Reports.

[12]  Younan Xia,et al.  Shape-Controlled Synthesis of Colloidal Metal Nanocrystals: Thermodynamic versus Kinetic Products. , 2015, Journal of the American Chemical Society.

[13]  T. Pal,et al.  Nitroarene reduction: a trusted model reaction to test nanoparticle catalysts. , 2015, Chemical communications.

[14]  Ö. Metin,et al.  Reduced graphene oxide-supported CuPd alloy nanoparticles as efficient catalysts for the Sonogashira cross-coupling reactions. , 2015, ACS applied materials & interfaces.

[15]  Yuxin Zhang,et al.  Methanolysis of ammonia borane by shape-controlled mesoporous copper nanostructures for hydrogen generation. , 2015, Dalton transactions.

[16]  Jiale Huang,et al.  Highly efficient hydrogen generation from methanolysis of ammonia borane on CuPd alloy nanoparticles , 2015, Nanotechnology.

[17]  D. Farrusseng,et al.  Transition-Metal Nanoparticles in Hollow Zeolite Single Crystals as Bifunctional and Size-Selective Hydrogenation Catalysts , 2015 .

[18]  Shuhong Yu,et al.  Tiny Pd@Co core-shell nanoparticles confined inside a metal-organic framework for highly efficient catalysis. , 2015, Small.

[19]  Ö. Metin,et al.  CoPd alloy nanoparticles catalyzed tandem ammonia borane dehydrogenation and reduction of aromatic nitro, nitrile and carbonyl compounds , 2014 .

[20]  M. Zahmakiran,et al.  Carbon supported trimetallic PdNiAg nanoparticles as highly active, selective and reusable catalyst in the formic acid decomposition , 2014 .

[21]  Steven L. Suib,et al.  Mesoporous Co3O4 with Controlled Porosity: Inverse Micelle Synthesis and High-Performance Catalytic CO Oxidation at −60 °C , 2014 .

[22]  Armando J. Marenco,et al.  Nickel/Iron Oxide Nanocrystals with a Nonequilibrium Phase: Controlling Size, Shape, and Composition , 2014 .

[23]  Dong Su,et al.  Tuning nanoparticle structure and surface strain for catalysis optimization. , 2014, Journal of the American Chemical Society.

[24]  M. Beller Nanoscale Fe2O3‐Based Catalysts for Selective Hydrogenation of Nitroarenes to Anilines. , 2014 .

[25]  Shouheng Sun,et al.  Tandem Dehydrogenation of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds Catalyzed by Graphene-Supported NiPd Alloy Nanoparticles , 2014 .

[26]  Jun Chen,et al.  Ni nanoparticles supported on carbon as efficient catalysts for the hydrolysis of ammonia borane , 2014, Nano Research.

[27]  Tsunehiro Tanaka,et al.  A Series of NiM (M = Ru, Rh, and Pd) Bimetallic Catalysts for Effective Lignin Hydrogenolysis in Water , 2014 .

[28]  Hsing-Yu Tuan,et al.  Scalable Solution-Grown High-Germanium-Nanoparticle-Loading Graphene Nanocomposites as High-Performance Lithium-Ion Battery Electrodes: An Example of a Graphene-Based Platform toward Practical Full-Cell Applications , 2014 .

[29]  Hsin‐Lung Chen,et al.  Monodisperse Copper Nanocubes: Synthesis, Self-Assembly, and Large-Area Dense-Packed Films , 2014 .

[30]  Catherine Pinel,et al.  Conversion of biomass into chemicals over metal catalysts. , 2014, Chemical reviews.

[31]  Detlef-M. Smilgies,et al.  Solvent-mediated self-assembly of nanocube superlattices. , 2014, Journal of the American Chemical Society.

[32]  Yadong Li,et al.  Removal and Utilization of Capping Agents in Nanocatalysis , 2014 .

[33]  C. Tung,et al.  Graphene-supported ultrafine metal nanoparticles encapsulated by mesoporous silica: robust catalysts for oxidation and reduction reactions. , 2014, Angewandte Chemie.

[34]  Z. Ren,et al.  Efficient solar water-splitting using a nanocrystalline CoO photocatalyst. , 2014, Nature nanotechnology.

[35]  M. Beller,et al.  Nanoscale Fe2O3-Based Catalysts for Selective Hydrogenation of Nitroarenes to Anilines , 2013, Science.

[36]  Charles C. L. McCrory,et al.  Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. , 2013, Journal of the American Chemical Society.

[37]  Qiang Xu,et al.  PdPt Nanocubes: A High‐Performance Catalyst for Hydrolytic Dehydrogenation of Ammonia Borane , 2013 .

[38]  S. Akbayrak,et al.  Hydroxyapatite supported ruthenium(0) nanoparticles catalyst in hydrolytic dehydrogenation of ammonia borane: Insight to the nanoparticles formation and hydrogen evolution kinetics , 2013 .

[39]  Younan Xia,et al.  Shape-controlled synthesis of Pd nanocrystals and their catalytic applications. , 2013, Accounts of chemical research.

[40]  Glenn Jones,et al.  Rationalization of interactions in precious metal/ceria catalysts using the d-band center model. , 2013, Angewandte Chemie.

[41]  V. Papaefthimiou,et al.  Fast Assembling of Magnetic Iron Oxide Nanoparticles by Microwave-Assisted Copper(I) Catalyzed Alkyne–Azide Cycloaddition (CuAAC) , 2013 .

[42]  B. Ladewig,et al.  Removal of surfactant and capping agent from Pd nanocubes (Pd-NCs) using tert-butylamine: its effect on electrochemical characteristics , 2013 .

[43]  S. Tsang,et al.  Hydrogenolysis of ethylene glycol to methanol over modified RANEY® catalysts. , 2013, Physical chemistry chemical physics : PCCP.

[44]  M. Beller,et al.  Heterogenized cobalt oxide catalysts for nitroarene reduction by pyrolysis of molecularly defined complexes , 2013, Nature Chemistry.

[45]  Jiajun Li,et al.  Carbon-encapsulated Fe3O4 nanoparticles as a high-rate lithium ion battery anode material. , 2013, ACS nano.

[46]  Shouheng Sun,et al.  Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions. , 2013, Nanoscale.

[47]  Shouheng Sun,et al.  Co/CoO nanoparticles assembled on graphene for electrochemical reduction of oxygen. , 2012, Angewandte Chemie.

[48]  Daohua Sun,et al.  Methanolysis of Ammonia Borane by CoPd Nanoparticles , 2012 .

[49]  Ping Liu,et al.  A new type of strong metal-support interaction and the production of H2 through the transformation of water on Pt/CeO2(111) and Pt/CeO(x)/TiO2(110) catalysts. , 2012, Journal of the American Chemical Society.

[50]  F. Viñes,et al.  Bonding Mechanisms of Graphene on Metal Surfaces , 2012 .

[51]  Miaofang Chi,et al.  Ni/Pd core/shell nanoparticles supported on graphene as a highly active and reusable catalyst for Suzuki-Miyaura cross-coupling reaction , 2012, Nano Research.

[52]  Ö. Metin,et al.  Oleylamine-Stabilized Palladium(0) Nanoclusters As Highly Active Heterogeneous Catalyst for the Dehydrogenation of Ammonia Borane , 2011 .

[53]  Yong Wang,et al.  Stabilization of electrocatalytic metal nanoparticles at metal-metal oxide-graphene triple junction points. , 2011, Journal of the American Chemical Society.

[54]  Ping Wang,et al.  Ruthenium nanoparticles immobilized in montmorillonite used as catalyst for methanolysis of ammonia borane , 2010 .

[55]  F. Tezcan,et al.  Metal-directed protein self-assembly. , 2010, Accounts of chemical research.

[56]  Junliang Zhang,et al.  Truncated octahedral Pt(3)Ni oxygen reduction reaction electrocatalysts. , 2010, Journal of the American Chemical Society.

[57]  Shouheng Sun,et al.  Monodisperse nickel nanoparticles and their catalysis in hydrolytic dehydrogenation of ammonia borane. , 2010, Journal of the American Chemical Society.

[58]  Huriye Erdoğan,et al.  In situ-generated PVP-stabilized palladium(0) nanocluster catalyst in hydrogen generation from the methanolysis of ammonia-borane. , 2009, Physical chemistry chemical physics : PCCP.

[59]  J. J. Gracio,et al.  Surface Modification of Graphene Nanosheets with Gold Nanoparticles: The Role of Oxygen Moieties at Graphene Surface on Gold Nucleation and Growth , 2009 .

[60]  Feng Tao,et al.  Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles , 2008, Science.

[61]  Thomas Bligaard,et al.  Identification of Non-Precious Metal Alloy Catalysts for Selective Hydrogenation of Acetylene , 2008, Science.

[62]  J. Nørskov,et al.  Chemical bonding at surfaces and interfaces , 2008 .

[63]  Snigdhamayee Praharaj,et al.  Synthesis and size-selective catalysis by supported gold nanoparticles: Study on heterogeneous and homogeneous catalytic process , 2007 .

[64]  B. D. Kay,et al.  Nanoscaffold mediates hydrogen release and the reactivity of ammonia borane. , 2005, Angewandte Chemie.

[65]  J. Baumann,et al.  Calorimetric process monitoring of thermal decomposition of B–N–H compounds , 2000 .

[66]  H. Brown,et al.  Mechanism of hydroboration of alkenes with borane-Lewis base complexes. Evidence that the mechanism of the hydroboration reaction proceeds through a prior dissociation of such complexes , 1984 .

[67]  W. Wendlandt,et al.  The thermal decomposition of ammonia borane , 1978 .

[68]  G. E. Ryschkewitsch Amine Boranes. I. Kinetics of Acid Hydrolysis of Trimethylamine Borane , 1960 .