Ethylene hydrogenation catalysis on Pt(111) single-crystal surfaces studied by using mass spectrometry and in situ infrared absorption spectroscopy
| Autor: | Aashani Tillekaratne, Francisco Zaera, Juan Pablo Simonovis |
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| Rok vydání: | 2016 |
| Předmět: |
Ethylene
Hydrogen Chemistry Analytical chemistry chemistry.chemical_element Infrared spectroscopy 02 engineering and technology Surfaces and Interfaces 010402 general chemistry 021001 nanoscience & nanotechnology Condensed Matter Physics 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films Catalysis chemistry.chemical_compound Adsorption Deuterium Materials Chemistry Molecule 0210 nano-technology Stoichiometry |
| Zdroj: | Surface Science. 652:134-141 |
| ISSN: | 0039-6028 |
| DOI: | 10.1016/j.susc.2015.11.005 |
| Popis: | The catalytic hydrogenation of ethylene promoted by a Pt(111) single crystal was studied by using a ultrahigh-vacuum surface-science instrument equipped with a so-called high-pressure cell. Kinetic data were acquired continuously during the catalytic conversion of atmospheric-pressure mixtures of ethylene and hydrogen by using mass spectrometry while simultaneously characterizing the surface species in operando mode by reflection–absorption infrared spectroscopy (RAIRS). Many observations reported in previous studies of this system were corroborated, including the presence of adsorbed alkylidyne intermediates during the reaction and the zero-order dependence of the rate of hydrogenation on the pressure of ethylene. In addition, the high quality of the kinetic data, which could be recorded continuously versus time and processed to calculate time-dependent turnover frequencies (TOFs), afforded a more detailed analysis of the mechanism. Specifically, deuterium labeling could be used to estimate the extent of isotope scrambling reached with mixed-isotope-substituted reactants (C 2 H 4 + D 2 and C 2 D 4 + H 2 ). Perhaps the most important new observation from this work is that, although extensive H-D exchange takes place on ethylene before being fully converted to ethane, the average stoichiometry of the final product retains the expected stoichiometry of the gas mixture, that is, four regular hydrogen atoms and two deuteriums per ethane molecule in the case of the experiments with C 2 H 4 + D 2 . This means that no hydrogen atoms are removed from the surface via their inter-recombination to produce X 2 (X = H or D). It is concluded that, under catalytic conditions, hydrogen surface recombination is much slower than ethylene hydrogenation and H-D exchange. |
| Databáze: | OpenAIRE |
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