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Title: Final Technical Report for DOE Grant, number DE-FG02-05ER15701; Probing Surface Chemistry Under Catalytic Conditions: Olefin Hydrogenation,Cyclization and Functionalization.

Abstract

The specific goal of this work was to understanding the catalytic reactions pathways for the synthesis of vinyl acetate over Pd, Au and PdAu alloys. A combination of both experimental methods (X-ray and Auger spectroscopies, low-energy ion scattering (LEIS), low-energy electron diffraction (LEED) and theory (Density Functional Theory (DFT) calculations and Monte Carlo methods under various different reactions) were used to track the surface chemistry and the influence of alloying. The surface intermediates involved in the various reactions were characterized using reflection-absorption infrared spectroscopy and LEED to identify the nature of the surface species and temperature-programmed desorption (TPD) to follow the decomposition pathways and measure heats of adsorption. These results along with those from density functional theoretical calculations were used determine the kinetics for elementary steps. The results from this work showed that the reaction proceeds via the Samanos mechanism over Pd surfaces whereby the ethylene directly couples with acetate to form an acetoxyethyl intermediate that subsequently undergoes a beta-hydride elimination to form the vinyl acetate monomer. The presence of Au was found to modify the adsorption energies and surface coverages of important surface intermediates including acetate, ethylidyne and ethylene which ultimately influences the critical C-H activation and coupling steps.more » By controlling the surface alloy composition or structure one can begin to control the steps that control the rate and even the mechanism.« less

Authors:
Publication Date:
Research Org.:
University of Virginia, Charlottesville, VA
Sponsoring Org.:
USDOE SC Basic Energy Sciences (SC-22)
OSTI Identifier:
1014870
Report Number(s):
DOE/ER15701-3 Final Report
Final_Report; TRN: US201113%%176
DOE Contract Number:
FG02-05ER15701
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETATES; ADSORPTION; ALKENES; ALLOYS; CHEMISTRY; DESORPTION; ELECTRON DIFFRACTION; ETHYLENE; FUNCTIONALS; KINETICS; MONTE CARLO METHOD; SCATTERING; SPECTROSCOPY; SYNTHESIS; VINYL ACETATE; Vinyl acetate; VAM; DFT; catalysis; kinetics, PdAu; alloys

Citation Formats

Neurock, Matthew. Final Technical Report for DOE Grant, number DE-FG02-05ER15701; Probing Surface Chemistry Under Catalytic Conditions: Olefin Hydrogenation,Cyclization and Functionalization.. United States: N. p., 2011. Web. doi:10.2172/1014870.
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Neurock, Matthew. Final Technical Report for DOE Grant, number DE-FG02-05ER15701; Probing Surface Chemistry Under Catalytic Conditions: Olefin Hydrogenation,Cyclization and Functionalization.. United States. doi:10.2172/1014870.
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Neurock, Matthew. Thu . "Final Technical Report for DOE Grant, number DE-FG02-05ER15701; Probing Surface Chemistry Under Catalytic Conditions: Olefin Hydrogenation,Cyclization and Functionalization.". United States. doi:10.2172/1014870. https://www.osti.gov/servlets/purl/1014870.
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@article{osti_1014870,
title = {Final Technical Report for DOE Grant, number DE-FG02-05ER15701; Probing Surface Chemistry Under Catalytic Conditions: Olefin Hydrogenation,Cyclization and Functionalization.},
author = {Neurock, Matthew},
abstractNote = {The specific goal of this work was to understanding the catalytic reactions pathways for the synthesis of vinyl acetate over Pd, Au and PdAu alloys. A combination of both experimental methods (X-ray and Auger spectroscopies, low-energy ion scattering (LEIS), low-energy electron diffraction (LEED) and theory (Density Functional Theory (DFT) calculations and Monte Carlo methods under various different reactions) were used to track the surface chemistry and the influence of alloying. The surface intermediates involved in the various reactions were characterized using reflection-absorption infrared spectroscopy and LEED to identify the nature of the surface species and temperature-programmed desorption (TPD) to follow the decomposition pathways and measure heats of adsorption. These results along with those from density functional theoretical calculations were used determine the kinetics for elementary steps. The results from this work showed that the reaction proceeds via the Samanos mechanism over Pd surfaces whereby the ethylene directly couples with acetate to form an acetoxyethyl intermediate that subsequently undergoes a beta-hydride elimination to form the vinyl acetate monomer. The presence of Au was found to modify the adsorption energies and surface coverages of important surface intermediates including acetate, ethylidyne and ethylene which ultimately influences the critical C-H activation and coupling steps. By controlling the surface alloy composition or structure one can begin to control the steps that control the rate and even the mechanism.},
doi = {10.2172/1014870},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu May 26 00:00:00 EDT 2011},
month = {Thu May 26 00:00:00 EDT 2011}
}
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Technical Report:
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DOI:  10.2172/1014870
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