Enhancing the Catalytic Properties of Ruthenium Nanoparticle-SILP Catalysts by Dilution with Iron

The partial replacement of ruthenium by iron (“dilution”) provided enhanced catalytic activities and selectivities for bimetallic iron–ruthenium nanoparticles immobilized on a supported ionic liquid phase (FeRuNPs@SILP). An organometallic synthetic approach to the preparation of FeRuNPs@SILP allowed for a controlled and flexible incorporation of Fe into bimetallic FeRu NPs. The hydrogenation of substituted aromatic substrates using bimetallic FeRuNPs@SILP showed high catalytic activities and selectivities for the reduction of a variety of unsaturated moieties without saturation of the aromatic ring. The formation of a bimetallic phase not only leads to an enhanced differentiation of the hydrogenation selectivity, but even reversed the order of functional group hydrogenation in certain cases. In particular, bimetallic FeRuNPs@SILP (Fe:Ru = 25:75) were found to exhibit accelerated reaction rates for C═O hydrogenation within furan-based substrates which were >4 times faster than monometallic RuNPs@SILP. Thus...

[1]  Christian Gärtner,et al.  Carbon–carbon bond formation for biomass-derived furfurals and ketones by aldol condensation in a biphasic system , 2008 .

[2]  Uttam Chakraborty,et al.  Iron-catalyzed olefin hydrogenation at 1 bar H2 with a FeCl3–LiAlH4 catalyst , 2015 .

[3]  Haichao Liu,et al.  Cellulose conversion into polyols catalyzed by reversibly formed acids and supported ruthenium clusters in hot water. , 2007, Angewandte Chemie.

[4]  G. Huber,et al.  Aqueous-phase hydrogenation and hydrodeoxygenation of biomass-derived oxygenates with bimetallic catalysts , 2014 .

[5]  R. P. Swatloski,et al.  Efficient, halide free synthesis of new, low cost ionic liquids: 1,3-dialkylimidazolium salts containing methyl- and ethyl-sulfate anions , 2002 .

[6]  P. Domaille,et al.  Comparison of metal-hydrogen, -oxygen, -nitrogen and -carbon bond strengths and evaluation of functional group additivity principles for organoruthenium and organoplatinum compounds , 1988 .

[7]  Bing-Joe Hwang,et al.  Structural models and atomic distribution of bimetallic nanoparticles as investigated by X-ray absorption spectroscopy. , 2005, Journal of the American Chemical Society.

[8]  A. Beale,et al.  High performing and stable supported nano-alloys for the catalytic hydrogenation of levulinic acid to γ-valerolactone , 2015, Nature Communications.

[9]  R. Palkovits,et al.  Hydrogenolysis goes bio: from carbohydrates and sugar alcohols to platform chemicals. , 2012, Angewandte Chemie.

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

[11]  D. M. Alonso,et al.  Catalytic conversion of biomass to biofuels , 2010 .

[12]  Kylie L. Luska,et al.  Bifunctional nanoparticle–SILP catalysts (NPs@SILP) for the selective deoxygenation of biomass substrates , 2014 .

[13]  Rolf Mülhaupt,et al.  Iron Nanoparticles Supported on Chemically‐Derived Graphene: Catalytic Hydrogenation with Magnetic Catalyst Separation , 2011 .

[14]  Raymond A. Cook,et al.  Supported ionic liquid catalysis--a new concept for homogeneous hydroformylation catalysis. , 2002, Journal of the American Chemical Society.

[15]  A. Jacobi von Wangelin,et al.  Stereoselective iron-catalyzed alkyne hydrogenation in ionic liquids. , 2014, Chemical communications.

[16]  Yuriy Román‐Leshkov,et al.  Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates , 2007, Nature.

[17]  Chen Zhao,et al.  One-step conversion of cellobiose to C6-alcohols using a ruthenium nanocluster catalyst. , 2006, Journal of the American Chemical Society.

[18]  Kylie L. Luska,et al.  Iron-iron oxide core-shell nanoparticles are active and magnetically recyclable olefin and alkyne hydrogenation catalysts in protic and aqueous media. , 2012, Chemical communications.

[19]  Peter Wasserscheid,et al.  Propene and 1-Octene Hydroformylation with Silica-Supported, Ionic Liquid-Phase (SILP) Rh-Phosphine Catalysts in Continuous Fixed-Bed Mode , 2003 .

[20]  A. Guerrero-Ruíz,et al.  Hydrogenation of citral on activated carbon and high-surface-area graphite-supported ruthenium catalysts modified with iron , 2001 .

[21]  C. Claver,et al.  Colloidal Ru, Co and Fe-nanoparticles. Synthesis and application as nanocatalysts in the Fischer–Tropsch process , 2012 .

[22]  W. Leitner,et al.  A fully integrated continuous-flow system for asymmetric catalysis: enantioselective hydrogenation with supported ionic liquid phase catalysts using supercritical CO(2) as the mobile phase. , 2013, Chemistry.

[23]  A. Riisager,et al.  Continuous fixed-bed gas-phase hydroformylation using supported ionic liquid-phase (SILP) Rh catalysts , 2003 .

[24]  M. Beller,et al.  The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds. , 2013, Chemical communications.

[25]  M. Beller,et al.  Hydrogenation using iron oxide–based nanocatalysts for the synthesis of amines , 2015, Nature Protocols.

[26]  Haitao Wang,et al.  Microwave irradiation assisted rapid synthesis of Fe–Ru bimetallic nanoparticles and their catalytic properties in water-gas shift reaction , 2009 .

[27]  K. Philippot,et al.  Organometallic Ruthenium Nanoparticles: A Comparative Study of the Influence of the Stabilizer on their Characteristics and Reactivity , 2013 .

[28]  D. Weibel,et al.  Sputtering-deposition of Ru nanoparticles onto Al2O3 modified with imidazolium ionic liquids: synthesis, characterisation and catalysis. , 2015, Dalton transactions.

[29]  J. Dumesic,et al.  Liquid alkanes with targeted molecular weights from biomass-derived carbohydrates. , 2008, ChemSusChem.

[30]  Raymond A. Cook,et al.  Supported ionic liquid catalysis investigated for hydrogenation reactions. , 2002, Chemical communications.

[31]  A. Baiker,et al.  Selective hydrogenation of cyclohexenone on iron–ruthenium nano-particles suspended in ionic liquids and CO2-expanded ionic liquids , 2012 .

[32]  J. D. de Vries,et al.  Soluble iron nanoparticles as cheap and environmentally benign alkene and alkyne hydrogenation catalysts. , 2009, Chemical communications.

[33]  W. Leitner,et al.  Selective hydrogenation of biomass derived substrates using ionic liquid-stabilized ruthenium nanoparticles , 2010 .

[34]  Stephanie G. Wettstein,et al.  Bimetallic catalysts for upgrading of biomass to fuels and chemicals. , 2012, Chemical Society reviews.

[35]  Walter Leitner,et al.  Synthesis of 1-octanol and 1,1-dioctyl ether from biomass-derived platform chemicals. , 2012, Angewandte Chemie.

[36]  Weize Wu,et al.  Pd nanoparticles immobilized on molecular sieves by ionic liquids: heterogeneous catalysts for solvent-free hydrogenation. , 2004, Angewandte Chemie.

[37]  Yoichi M. A. Yamada,et al.  Highly efficient iron(0) nanoparticle-catalyzed hydrogenation in water in flow , 2013 .

[38]  F. Tao,et al.  Synthesis and catalysis of chemically reduced metal-metalloid amorphous alloys. , 2012, Chemical Society reviews.

[39]  S. Miao,et al.  Ru nanoparticles immobilized on montmorillonite by ionic liquids: a highly efficient heterogeneous catalyst for the hydrogenation of benzene. , 2005, Angewandte Chemie.

[40]  Wolfgang Marquardt,et al.  Selective and flexible transformation of biomass-derived platform chemicals by a multifunctional catalytic system. , 2010, Angewandte Chemie.

[41]  M. Beller,et al.  Nitrogen-Doped Graphene-Activated Iron-Oxide-Based Nanocatalysts for Selective Transfer Hydrogenation of Nitroarenes , 2015 .

[42]  Juan Wang,et al.  Carbon Nanotube-Supported RuFe Bimetallic Nanoparticles as Efficient and Robust Catalysts for Aqueous-Phase Selective Hydrogenolysis of Glycerol to Glycols , 2011 .

[43]  Kylie L. Luska,et al.  Ionic liquid-stabilized nanoparticles as catalysts for the conversion of biomass , 2015 .

[44]  B. Hwang,et al.  Chemical transformation from FePt to Fe1-xPtMx (M = Ru, Ni, Sn) nanocrystals by a cation redox reaction: X-ray absorption spectroscopic studies. , 2007, Journal of the American Chemical Society.

[45]  J. Dupont,et al.  “Imprinting” Catalytically Active Pd Nanoparticles onto Ionic‐Liquid‐Modified Al2O3 Supports , 2013 .

[46]  M. Bauer,et al.  Iron(0) Particles: Catalytic Hydrogenations and Spectroscopic Studies , 2012 .

[47]  J. Dupont,et al.  Supported ionic liquid phase rhodium nanoparticle hydrogenation catalysts. , 2007, Dalton transactions.

[48]  J. Clark,et al.  Efficient aqueous hydrogenation of biomass platform molecules using supported metal nanoparticles on Starbons. , 2009, Chemical communications.

[49]  Avelino Corma,et al.  Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels , 2014 .

[50]  Robert J. Davis,et al.  X‐ray Absorption Spectroscopy of an Fe‐Promoted Rh/TiO2 Catalyst for Synthesis of Ethanol from Synthesis Gas , 2009 .

[51]  G. Huber,et al.  Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates , 2005, Science.

[52]  N. Coombs,et al.  Iron nanoparticles catalyzing the asymmetric transfer hydrogenation of ketones. , 2012, Journal of the American Chemical Society.

[53]  A. Datye,et al.  Fe-Ru small particle bimetallic catalysts supported on carbon nanotubes for use in Fischer-Tropsch synthesis , 2007 .

[54]  W. Delgass,et al.  Fischer-Tropsch synthesis over freshly reduced iron-ruthenium alloys , 1979 .

[55]  P. Fazzini,et al.  How to Modulate Catalytic Properties in Nanosystems: The Case of Iron–Ruthenium Nanoparticles , 2014 .

[56]  Viktória Fábos,et al.  Integration of Homogeneous and Heterogeneous Catalytic Processes for a Multi-step Conversion of Biomass: From Sucrose to Levulinic Acid, γ-Valerolactone, 1,4-Pentanediol, 2-Methyl-tetrahydrofuran, and Alkanes , 2008 .

[57]  Wei Qi,et al.  Production of jet and diesel fuel range alkanes from waste hemicellulose-derived aqueous solutions , 2010 .

[58]  W. Delgass,et al.  Carbon deposition and activity changes over FeRu alloys during Fischer-Tropsch synthesis , 1980 .

[59]  R. Palkovits,et al.  Heteropoly acids as efficient acid catalysts in the one-step conversion of cellulose to sugar alcohols. , 2011, Chemical communications.

[60]  Nikolaos Dimitratos,et al.  Designing bimetallic catalysts for a green and sustainable future. , 2012, Chemical Society reviews.