Fibrous Nano-Silica Supported Ruthenium (KCC-1/Ru): A Sustainable Catalyst for the Hydrogenolysis of Alkanes with Good Catalytic Activity and Lifetime

We have shown that fibrous nanosilica (KCC-1) can serve as a suitable support for the synthesis of highly dispersed ruthenium (Ru) nanoparticles. The resulting KCC-1/Ru catalyst displayed superior activity for the hydrogenolysis of propane and ethane at atmospheric pressure and at low temperature. The high catalytic activity was due to the formation of Ru-nanoparticles with an active size range (1–4 nm) and the presence of hexagonal-shaped particles with several corners and sharp edges possessing reactive atoms with lowest coordination numbers. The catalyst was stable with an excellent lifetime and no sign of deactivation, even after eight days. This enhanced stability may be due to the fibrous nature of KCC-1 which restricts Ostwald ripening of Ru nanoparticles.

[1]  R. Varma,et al.  The synthesis and applications of a micro-pine-structured nanocatalyst. , 2008, Chemical communications.

[2]  R. Varma,et al.  Nanoparticle-supported and magnetically recoverable nickel catalyst: a robust and economic hydrogenation and transfer hydrogenation protocol , 2009 .

[3]  R. Larsson,et al.  Hydrogenolysis of ethane on silica-supported cobalt catalysts , 2002 .

[4]  K. Komvopoulos,et al.  Carbon monoxide adsorption and oxidation on monolayer films of cubic platinum nanoparticles investigated by infrared-visible sum frequency generation vibrational spectroscopy. , 2006, The journal of physical chemistry. B.

[5]  G. Bond,et al.  The origin of particle size effects in supported metal catalysts: Propane hydrogenolysis on Ru/Al2O3 catalysts , 1996 .

[6]  Dongkyu Cha,et al.  High-surface-area silica nanospheres (KCC-1) with a fibrous morphology. , 2010, Angewandte Chemie.

[7]  V. Polshettiwar,et al.  Fibrous nano-silica (KCC-1)-supported palladium catalyst: Suzuki coupling reactions under sustainable conditions. , 2012, ChemSusChem.

[8]  R. W. Rice,et al.  The effect of bimetallic catalyst preparation and treatment on behavior for propane hydrogenolysis , 2004 .

[9]  W. H. Weinberg,et al.  Hydrogenolysis of ethane, propane, n-butane, and neopentane on the (111) and (110)-(1 times 2) surfaces of iridium , 1988 .

[10]  J. Sinfelt Catalytic Hydrogenolysis over Supported Metals , 1970 .

[11]  H. Taylor,et al.  The Hydrogenation of Ethane on Cobalt Catalysts , 1939 .

[12]  R. Varma,et al.  Nanoparticle-supported and magnetically recoverable ruthenium hydroxide catalyst: efficient hydration of nitriles to amides in aqueous medium. , 2009, Chemistry.

[13]  G. Bond,et al.  Hydrogenolysis of Propane and ofn-Butane on Pt/KL Zeolite , 1997 .

[14]  Wenjie Shen,et al.  Low-temperature oxidation of CO catalysed by Co3O4 nanorods , 2009, Nature.

[15]  C. Copéret,et al.  Homogeneous and heterogeneous catalysis: bridging the gap through surface organometallic chemistry. , 2003, Angewandte Chemie.

[16]  I. Beletskaya,et al.  Efficient and Recyclable Catalyst of Palladium Nanoparticles Stabilized by Polymer Micelles Soluble in Water for Suzuki-Miyaura Reaction, Ostwald Ripening Process with Palladium Nanoparticles , 2008 .

[17]  G. Somorjai Active sites for hydrocarbon catalysis on metal surfaces , 1977 .

[18]  K. Morikawa,et al.  The Activation of Specific Bonds in Complex Molecules at Catalytic Surfaces. II. The Carbon-Hydrogen and Carbon-Carbon Bonds in Ethane and Ethane-d , 1936 .

[19]  G. Webb,et al.  Supported Metal Catalysts; Preparation, Characterisation, and Function: Part VI. Hydrogenolysis of Ethane, Propane, n-Butane and iso-Butane over Supported Platinum Catalysts , 1998 .

[20]  J. Sinfelt CATALYSIS BY METALS: THE R H. EMMETT AWARD ADDRESS , 1974 .

[21]  C. Copéret,et al.  Low-Temperature Hydrogenolysis of Alkanes Catalyzed by a Silica-Supported Tantalum Hydride Complex, and Evidence for a Mechanistic Switch from Group IV to Group V Metal Surface Hydride Complexes , 2000 .

[22]  G. Bond,et al.  Modification of ruthenium catalysts for alkane hydrogenolysis , 2000 .

[23]  J. Rostrup-Nielsen,et al.  Innovation and science in the process industry: Steam reforming and hydrogenolysis , 1999 .

[24]  G. Somorjai,et al.  The dehydrogenation and hydrogenolysis of cyclohexane and cyclohexene on stepped (high miller index) platinum surfaces , 1976 .

[25]  Rafael Luque,et al.  Magnetically recoverable nanocatalysts. , 2011, Chemical reviews.

[26]  C. Mirodatos,et al.  Applicability and Limits of the Ensemble Model in Catalysis by Metals: The Kinetics of Ethane Hydrogenolysis over Pt/SiO2☆ , 1998 .

[27]  T. C. Green,et al.  Shape-Controlled Synthesis of Colloidal Platinum Nanoparticles , 1996, Science.

[28]  G. Somorjai,et al.  The hydrogenolysis of cyclopropane on a platinum stepped single crystal at atmospheric pressure , 1974 .

[29]  M. Hävecker,et al.  Stabilization of 200-atom platinum nanoparticles by organosilane fragments. , 2011, Angewandte Chemie.

[30]  G. Bond,et al.  Catalytic and structural properties of ruthenium bimetallic catalysts: hydrogenolysis of propane and n-butane on RuAl2O3 catalysts modified by a Group 14 element , 1996 .

[31]  S. Norsic,et al.  "Hydro-metathesis" of olefins: a catalytic reaction using a bifunctional single-site tantalum hydride catalyst supported on fibrous silica (KCC-1) Nanospheres. , 2011, Angewandte Chemie.

[32]  R. Varma,et al.  Self-assembly of palladium nanoparticles: synthesis of nanobelts, nanoplates and nanotrees using vitamin B1, and their application in carbon–carbon coupling reactions , 2009 .

[33]  J. Sinfelt Catalytic hydrogenolysis on metals , 1991 .

[34]  R. Varma,et al.  Magnetic nanoparticle-supported glutathione: a conceptually sustainable organocatalyst. , 2009, Chemical communications.

[35]  K. Morikawa,et al.  The Activation of Specific Bonds in Complex Molecules at Catalytic Surfaces. I. The Carbon—Hydrogen Bond in Methane and Methane-d4 , 1936 .

[36]  Rajender S Varma,et al.  Self-assembly of metal oxides into three-dimensional nanostructures: synthesis and application in catalysis. , 2009, ACS nano.

[37]  V. Polshettiwar,et al.  Nanocatalysts for Suzuki cross-coupling reactions. , 2011, Chemical Society reviews.

[38]  J. F. Creemer,et al.  Nanoscale chemical imaging of a working catalyst by scanning transmission X-ray microscopy , 2008, Nature.

[39]  P. Sermon,et al.  Products and intermediates in propane hydrogenolysis on supported Pt , 2000 .