Cluster Size Selectivity in the Product Distribution of Ethene Dehydrogenation on Niobium Clusters
Department of Chemistry, Trent University, Питерборо, Ontario, CanadaThe Journal of Physical Chemistry A (Impact Factor: 2.69). 09/2005; 109(32):7046-56. DOI: 10.1021/jp0506944
Ethene reactions with niobium atoms and clusters containing up to 25 constituent atoms have been studied in a fast-flow metal cluster reactor. The clusters react with ethene at about the gas-kinetic collision rate, indicating a barrierless association process as the cluster removal step. Exceptions are Nb8 and Nb10, for which a significantly diminished rate is observed, reflecting some cluster size selectivity. Analysis of the experimental primary product masses indicates dehydrogenation of ethene for all clusters save Nb10, yielding either Nb(n)C2H2 or Nb(n)C2. Over the range Nb-Nb6, the extent of dehydrogenation increases with cluster size, then decreases for larger clusters. For many clusters, secondary and tertiary product masses are also observed, showing varying degrees of dehydrogenation corresponding to net addition of C2H4, C2H2, or C2. With Nb atoms and several small clusters, formal addition of at least six ethene molecules is observed, suggesting a polymerization process may be active. Kinetic analysis of the Nb atom and several Nb(n) cluster reactions with ethene shows that the process is consistent with sequential addition of ethene units at rates corresponding approximately to the gas-kinetic collision frequency for several consecutive reacting ethene molecules. Some variation in the rate of ethene pick up is found, which likely reflects small energy barriers or steric constraints associated with individual mechanistic steps. Density functional calculations of structures of Nb clusters up to Nb(6), and the reaction products Nb(n)C2H2 and Nb(n)C2 (n = 1...6) are presented. Investigation of the thermochemistry for the dehydrogenation of ethene to form molecular hydrogen, for the Nb atom and clusters up to Nb6, demonstrates that the exergonicity of the formation of Nb(n)C2 species increases with cluster size over this range, which supports the proposal that the extent of dehydrogenation is determined primarily by thermodynamic constraints. Analysis of the structural variations present in the cluster species studied shows an increase in C-H bond lengths with cluster size that closely correlates with the increased thermodynamic drive to full dehydrogenation. This correlation strongly suggests that all steps in the reaction are barrierless, and that weakening of the C-H bonds is directly reflected in the thermodynamics of the overall dehydrogenation process. It is also demonstrated that reaction exergonicity in the initial partial dehydrogenation step must be carried through as excess internal energy into the second dehydrogenation step.
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ABSTRACT: The reactions of matrix-isolated Ti, V, or Nb atoms with ethene (C(2)H(4)) have been studied by FTIR absorption spectroscopy. Under conditions where the ethene dimer forms, metal atoms react with the ethene dimer to yield matrix-isolated ethane (C(2)H(6)) and methane. Under lower ethene concentration conditions ( approximately 1:70 ethene/Ar), hydridic intermediates of the types HMC(2)H(3) and H(2)MC(2)H(2) are also observed, and the relative yield of hydrocarbons is diminished. Reactions of these metals with perdeuterioethene, and equimolar mixtures of C(2)H(4) and C(2)D(4), yield products that are consistent with the production of ethane via a metal atom reaction involving at least two C(2)H(4) molecules. The absence of any other observed products suggests the mechanism also involves production of small, highly symmetric species such as molecular hydrogen and metal carbides. Evidence is presented suggesting that ethane production from the ethene dimer is a general photochemical process for the reaction of excited-state transition-metal atoms with ethene at high concentrations of ethene.The Journal of Physical Chemistry A 11/2005; 109(42):9465-70. DOI:10.1021/jp0447542 · 2.69 Impact Factor
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ABSTRACT: Neutral niobium and tantalum clusters (Nbn and Tan) are generated by laser ablation and supersonic expansion into a vacuum and are reacted in a pickup cell with various low pressure (approximately 1 mTorr) unsaturated hydrocarbons (acetylene, ethylene, propylene, 1-butene, 1,3-butadiene, benzene, and toluene) under nearly single collision conditions. The bare metal clusters and their reaction products are ionized by a 193 nm laser and detected by a time of flight mass spectrometer. Partially and fully dehydrogenated products are observed for small (n<or=m) and large (n>or=m) neutral metal clusters, respectively, with m ranging from 2 to 5 depending on the particular hydrocarbon. In addition to primary, single collision products, sequential addition products that are usually fully dehydrogenated are also observed. With toluene used as the reactant gas, carbon loss products are observed, among which Nb8C12 and Ta8C12 are particularly abundant, indicating that the Met-Car molecule M8C12 can be formed from the neutral metal cluster upon two collisions with toluene molecules. The dehydrogenation results for low pressure reactions are compared with those available from previous studies employing flow tube (high pressure) reactors. Low pressure and high pressure cluster ion reactions are also compared with the present neutral metal cluster reactions. Reactions of unsaturated hydrocarbons and metal surfaces are discussed in terms of the present neutral cluster results.The Journal of Chemical Physics 11/2006; 125(16):164306. DOI:10.1063/1.2360278 · 2.95 Impact Factor
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ABSTRACT: The main purpose of this work is to study metal−molecule interactions that can lead to the production of molecular hydrogen. Two systems were chosen for this analysis: yttrium atom and clusters interacting with the simple electron donor ammonia (NH3) and copper atoms and ions with imidazole. For yttrium with ammonia as well as for copper with imidazole there is a charge-transfer process from the metal to the molecule that promotes the dissociation of the hydrogen atoms.Journal of Chemical Theory and Computation 02/2007; 3(3). DOI:10.1021/ct6003615 · 5.50 Impact Factor
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