Embedded Ru@ZrO2 Catalysts for H2 Production by Ammonia Decomposition

Ammonia can be used as fuel in internal combustion engines (ICEs). In this case, a flame accelerator, such as hydrogen, is needed. H2 can be produced on‐board by partial decomposition of ammonia. In this work, ruthenium nanoparticles were embedded into a lanthanum‐stabilized zirconia (LSZ) support to obtain active and stable heterogeneous catalysts for NH3 decomposition. The effects of the preparation of both Ru nanoparticles and LSZ support were investigated. The embedded catalysts present high metal dispersion and good metal accessibility. Despite the relatively low metal loading (3 wt %), activity was very high in the temperature range 400–600 °C. The activity of the reference catalysts prepared by using classical impregnation was significantly lower under the same working conditions. Although many factors contribute to the final catalyst performances, the data reported confirm that the embedding strategy minimizes the undesirable sintering of the Ru nanoparticles, leading to promising and stable catalytic activity.

[1]  V. Specchia,et al.  Effect of the Catalyst Load on Syngas Production in Short Contact Time Catalytic Partial Oxidation Reactors , 2010 .

[2]  P. Fornasiero,et al.  Embedded phases: a way to active and stable catalysts. , 2010, ChemSusChem.

[3]  L. Cornaglia,et al.  Surface properties and catalytic behavior of Ru supported on composite La2O3–SiO2 oxides , 2009 .

[4]  Hyun-Yong Lee,et al.  Selective CO removal in a H2-rich stream over supported Ru catalysts for the polymer electrolyte membrane fuel cell (PEMFC) , 2009 .

[5]  J. S. Lee,et al.  Ruthenium‐Catalyzed, One‐Pot Alcohol Oxidation–Wittig Reaction Producing α,β‐Unsaturated Esters , 2009 .

[6]  Ibrahim Dincer,et al.  Using ammonia as a sustainable fuel , 2008 .

[7]  Gustaaf Van Tendeloo,et al.  Ruthenium nanoparticles inside porous [Zn4O(bdc)3] by hydrogenolysis of adsorbed [Ru(cod)(cot)]: a solid-state reference system for surfactant-stabilized ruthenium colloids. , 2008, Journal of the American Chemical Society.

[8]  Paolo Fornasiero,et al.  Design of Rh@Ce0.2Zr0.8O2–Al2O3 nanocomposite for ethanol steam reforming , 2008 .

[9]  Jens Oluf Jensen,et al.  The energy efficiency of onboard hydrogen storage , 2007 .

[10]  A. Roucoux,et al.  Nanoheterogeneous Catalytic Hydrogenation of Arenes: Evaluation of the Surfactant‐Stabilized Aqueous Ruthenium(0) Colloidal Suspension , 2007 .

[11]  Hanfan Liu,et al.  Synthesis of PVP-stabilized ruthenium colloids with low boiling point alcohols. , 2007, Journal of colloid and interface science.

[12]  Hengyong Xu,et al.  NH3 Decomposition Kinetics on Supported Ru Clusters: Morphology and Particle Size Effect , 2007 .

[13]  W. Raróg-Pilecka,et al.  Ammonia synthesis over barium-promoted cobalt catalysts supported on graphitised carbon , 2007 .

[14]  P. Fornasiero,et al.  Embedded Rh(1wt %)@Al2O3: Effects of high temperature and prolonged aging under methane partial oxidation conditions , 2007 .

[15]  A. Roucoux,et al.  Competitive hydrogenation/dehalogenation of halogenoarenes with surfactant-stabilized aqueous suspensions of rhodium and palladium colloids: A major effect of the metal nature , 2007 .

[16]  Zhonghua Zhu,et al.  Catalytic ammonia decomposition over Ru/carbon catalysts: The importance of the structure of carbon support , 2007 .

[17]  M. Zawadzki,et al.  The use of hydrogen chemisorption for the determination of Ru dispersion in Ru/γ-alumina catalysts , 2007 .

[18]  P. Fornasiero,et al.  Rh(1%)@CexZr1−xO2–Al2O3 nanocomposites: Active and stable catalysts for ethanol steam reforming , 2007 .

[19]  Y. Chu,et al.  Surfactant-assisted synthesis, characterization and catalytic properties of nanostructure porous WO3/ZrO2 solid acid , 2006 .

[20]  Hengyong Xu,et al.  Highly efficient Ru/MgO catalysts for NH3 decomposition: Synthesis, characterization and promoter effect , 2006 .

[21]  S. Yin,et al.  Nanosized Ru on high-surface-area superbasic ZrO2-KOH for efficient generation of hydrogen via ammonia decomposition , 2006 .

[22]  P. Kooyman,et al.  Synthesis of well-dispersed ruthenium nanoparticles inside mesostructured porous silica under mild conditions , 2005 .

[23]  S. Yin,et al.  A mini-review on ammonia decomposition catalysts for on-site generation of hydrogen for fuel cell applications , 2004 .

[24]  S. Yin,et al.  Investigation on modification of Ru/CNTs catalyst for the generation of COx-free hydrogen from ammonia , 2004 .

[25]  A. Roucoux,et al.  Enantioselective hydrogenation of ethyl pyruvate in biphasic liquid-liquid media by reusable surfactant-stabilized aqueous suspensions of platinum nanoparticles , 2004 .

[26]  E. Seebauer,et al.  A Priori Catalytic Activity Correlations: The Difficult Case of Hydrogen Production from Ammonia , 2004 .

[27]  S. Yin,et al.  Investigation on the catalysis of COx-free hydrogen generation from ammonia , 2004 .

[28]  S. Yin,et al.  Nano Ru/CNTs: a highly active and stable catalyst for the generation of COx-free hydrogen in ammonia decomposition , 2004 .

[29]  V. Pârvulescu,et al.  Hydrogenolysis of 1,1a,6,10b-tetrahydro-1,6-methanodibenzo[a,e]cyclopropa[c]-cycloheptene over silica- and zirconia-embedded Ru-colloids , 2002 .

[30]  T. Ressler,et al.  Sulfated Zirconia with Ordered Mesopores as an Active Catalyst for n-Butane Isomerization , 2002 .

[31]  D. Duprez,et al.  An optimized route for the preparation of well dispersed supported ruthenium catalysts , 2002 .

[32]  William J. Thomson,et al.  Ammonia decomposition kinetics over Ni-Pt/Al2O3 for PEM fuel cell applications , 2002 .

[33]  J. Nørskov,et al.  Electronic factors in catalysis: the volcano curve and the effect of promotion in catalytic ammonia synthesis , 2001 .

[34]  D. Goodman,et al.  Catalytic ammonia decomposition: COx-free hydrogen production for fuel cell applications , 2001 .

[35]  S. Dahl,et al.  Structure sensitivity of supported ruthenium catalysts for ammonia synthesis , 2000 .

[36]  A. Roucoux,et al.  Stabilized rhodium(0) nanoparticles: a reusable hydrogenation catalyst for arene derivatives in a biphasic water-liquid system. , 2000, Chemistry.

[37]  A. Rives,et al.  A study of the ruthenium–alumina system , 1998 .

[38]  M. Muhler,et al.  Effect of Potassium on the Kinetics of Ammonia Synthesis and Decomposition over Fused Iron Catalyst at Atmospheric Pressure , 1997 .

[39]  P. Canton,et al.  Rietveld analysis of the cubic crystal structure of Na-stabilized zirconia , 1997 .

[40]  Dae‐Joon Kim,et al.  Lattice Parameters, Ionic Conductivities, and Solubility Limits in Fluorite‐Structure MO2 Oxide [M = Hf4+, Zr4+, Ce4+, Th4+, U4+] Solid Solutions , 1989 .

[41]  S. L. Jones,et al.  Dehydration of Hydrous Zirconia with Methanol , 1988 .

[42]  K. Sing Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984) , 1985 .

[43]  R. Schloegl,et al.  Surface characterization of ammonia synthesis catalysts , 1983 .

[44]  G. Ertl,et al.  The role of potassium in the catalytic synthesis of ammonia , 1979 .

[45]  C. A. Bunton,et al.  Hydrolysis of di- and trisubstituted phosphate esters catalyzed by nucleophilic surfactants , 1973 .

[46]  R. D. Shannon,et al.  Effective ionic radii in oxides and fluorides , 1969 .

[47]  A. B. Scott,et al.  Electrolytic Properties of Solutions of Paraffin-chain Quaternary Ammonium Salts , 1943 .

[48]  J. Okal Oxygen Adsorption and H2-O2 Titration Method for Measurement of Ru Dispersion in Ru/gamma-Al2O3 Catalysts , 2007 .

[49]  K. Philippot,et al.  Surfactant-Stabilized Aqueous Iridium(0) Colloidal Suspension: An Efficient Reusable Catalyst for Hydrogenation of Arenes in Biphasic Media , 2004 .

[50]  A. Roucoux,et al.  Arene Hydrogenation with a Stabilised Aqueous Rhodium(0) Suspension: A Major Effect of the Surfactant Counter‐Anion , 2003 .

[51]  M. Muhler,et al.  The Kinetics of Ammonia Synthesis over Ruthenium-Based Catalysts: The Role of Barium and Cesium , 2002 .

[52]  D. Segal Chemical synthesis of ceramic materials , 1997 .

[53]  G. Ertl,et al.  The Kinetics of Ammonia Synthesis over Ru-Based Catalysts: 1. The Dissociative Chemisorption and Associative Desorption of N2 , 1997 .