TY - JOUR
T1 - Disentangling ensemble, electronic and coverage effects on alloy catalysts
T2 - Vinyl acetate synthesis on Au/Pd(1 1 1)
AU - Calaza, Florencia
AU - Mahapatra, Mausumi
AU - Neurock, Matthew
AU - Tysoe, Wilfred T.
N1 - Funding Information:
We gratefully acknowledge the support of this work by the National Science Foundation, under Grant Number CHE-1109377.
PY - 2014/4
Y1 - 2014/4
N2 - The activation energies for the reaction of gas-phase ethylene with adsorbed acetate species on Au/Pd(1 1 1) alloys are measured as a function of gold coverage in the alloy to probe the elementary steps in gold-palladium alloy catalyzed vinyl acetate monomer (VAM) synthesis. The activation energy decreases with increasing gold coverage in the alloy up to a gold coverage of ∼0.25 ML and then increases. The reaction exhibits a kinetic isotope effect when using C2D4 for gold coverages below ∼0.25 ML, and no isotope effect for alloys with larger gold coverages. This is ascribed to a change in rate-limiting step for the reaction, which is postulated to proceed via an initial coupling between ethylene and adsorbed acetate species to form an acetoxyethyl intermediate, which decomposes via a β-hydride elimination reaction to form VAM. For low gold coverages, the second step is rate limiting, while at higher coverage, the coupling step becomes rate limiting. This allows the reaction energies for each of the steps to be obtained as a function of gold coverage, where it is found that both energies decrease with increasing gold coverage, causing an increase in overall reaction rate. The activation energy for β-hydride elimination decreases more rapidly than that for the coupling step. The contributions to the energy change are estimated, and it is found that the effect of coverage on the reaction energies is comparable to the more commonly considered ensemble and electronic effects.
AB - The activation energies for the reaction of gas-phase ethylene with adsorbed acetate species on Au/Pd(1 1 1) alloys are measured as a function of gold coverage in the alloy to probe the elementary steps in gold-palladium alloy catalyzed vinyl acetate monomer (VAM) synthesis. The activation energy decreases with increasing gold coverage in the alloy up to a gold coverage of ∼0.25 ML and then increases. The reaction exhibits a kinetic isotope effect when using C2D4 for gold coverages below ∼0.25 ML, and no isotope effect for alloys with larger gold coverages. This is ascribed to a change in rate-limiting step for the reaction, which is postulated to proceed via an initial coupling between ethylene and adsorbed acetate species to form an acetoxyethyl intermediate, which decomposes via a β-hydride elimination reaction to form VAM. For low gold coverages, the second step is rate limiting, while at higher coverage, the coupling step becomes rate limiting. This allows the reaction energies for each of the steps to be obtained as a function of gold coverage, where it is found that both energies decrease with increasing gold coverage, causing an increase in overall reaction rate. The activation energy for β-hydride elimination decreases more rapidly than that for the coupling step. The contributions to the energy change are estimated, and it is found that the effect of coverage on the reaction energies is comparable to the more commonly considered ensemble and electronic effects.
KW - Infrared absorption spectroscopy
KW - Palladium gold alloy
KW - Vinyl acetate monomer
KW - Vinyl acetate synthesis
UR - http://www.scopus.com/inward/record.url?scp=84894202472&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84894202472&partnerID=8YFLogxK
U2 - 10.1016/j.jcat.2014.01.003
DO - 10.1016/j.jcat.2014.01.003
M3 - Article
AN - SCOPUS:84894202472
SN - 0021-9517
VL - 312
SP - 37
EP - 45
JO - Journal of Catalysis
JF - Journal of Catalysis
ER -