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Adsorption and Reaction Mechanisms of Thiophene over Sulfided Ruthenium Catalysts

Published online by Cambridge University Press:  28 February 2011

Ray A. Cocco
Affiliation:
Department of Chemical Engineering, Auburn University, AL 36849
Bruce J. Tatarchuk
Affiliation:
Department of Chemical Engineering, Auburn University, AL 36849
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Abstract

Adjustable (hydrogenolysis/hydrogenation) ratios (i.e., selectivity) of thiophene over sulfided ruthenium catalysts have been observed to depend on the method of presulfidization. Sulfidization in 10% H2S/H2 at 300–800K yielded a selectivity greater than 100, whereas a ratio of ca. 1 was noted after presulfidization in 100% H2S. The transition from one selectivity regime to another is reversible and can be changed via subsequent annealing or resulfidization procedures. X-Ray photoelectron spectroscopy shows similar results where sulfidization in 100% H2S yields: (i) a higher sulfur uptake with a corresponding 0.5 eV shift of the S 2P1/2–3/2 peaks to higher binding energy; (ii) multilayer sulfur incorporation at lower temperatures; and (iii) similar reversible behavior following subsequent annealing or resulfidization. Secondary ion mass spectroscopy and temperature programmed desorption studies also reveal that sulfur coverages affect thiophene adsorption, orientation and cracking on ruthenium surfaces.

Type
Research Article
Copyright
Copyright © Materials Research Society 1988

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