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On the reaction pathway for the hydrogenation of acetylene and vinylidene on Pd(111)

Journal Article · · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
DOI:https://doi.org/10.1021/jp993250e· OSTI ID:20034434

The pathways for the hydrogenation of adsorbed acetylene and vinylidene on Pd(111) are investigated using temperature-programmed desorption and infrared reflection-absorption spectroscopies. The chemistry of the vinyl intermediate formed by the hydrogenation of both species is investigated by adsorbing vinyl iodide on Pd(111) where it is found that vinyl species hydrogenate more rapidly than adsorbed acetylene, indicating that the rate-limiting step in acetylene hydrogenation is the addition of the first hydrogen to acetylene to form a vinyl species. Infrared spectroscopy also reveals that vinyl species convert to ethylidynes as Pd(111) is heated above {approximately}160 K. The hydrogenation of vinylidene by up to {approximately}0.2 Torr of hydrogen involves intermediate ethylidyne species in accord with this observation. Surprisingly, the rate constant for the conversion of vinylidene into ethylidyne is identical to that for the titration of ethylidyne from the surface by hydrogen, an effect that may be explained in terms of the different saturation coverages of the two species.

Research Organization:
Univ. of Wisconsin, Milwaukee, WI (US)
Sponsoring Organization:
US Department of Energy
DOE Contract Number:
FG02-92ER14289
OSTI ID:
20034434
Journal Information:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 14 Vol. 104; ISSN 1089-5647; ISSN JPCBFK
Country of Publication:
United States
Language:
English