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CO isotopic exchange reaction over Rh/Al/sub 2/O/sub 3/: nondissociative exchange on metallic Rh sites

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100332a044· OSTI ID:6255262
The isotopic exchange reaction /sup 12/C/sup 18/O + /sup 13/C/sup 16/O ..-->.. /sup 12/C/sup 16/O + /sup 13/C/sup 18/O has been studied over alumina-supported rhodium catalysts between 300 and 470 K. For a 2.2 wt % Rh/Al/sub 2/O/sub 3/ catalyst containing both metallic Rh/sub x//sup 0/ sites and Rh/sup I/ sites, the onset of the CO isotopic exchange reaction is observed at 373 K, and an activation energy of 10.8 kcal/times/mol/sup /minus/1/ is estimated. In the same temperature range, no CO disproportionation/dissociation reactions are observed. The rate of isotopic exchange per Rh site over 0.2% Rh/Al/sub 2/O/sub 3/ is found to be slower by a factor of 7 than that over 2.2% Rh/Al/sub 2/O/sub 3/, due to the low relative population of metallic Rh sites compared to Rh/sup I/ sites on the 0.2% Rh/Al/sub 2/O/sub 3/ surfaces. It is proposed that the CO isotopic exchange proceeds via a nondissociative mechanism on the metallic Rh sites of the Rh catalysts and that the exchange reaction will not occur on Rh/sup I/ sites. Mass spectrometric, chemisorption, and IR spectroscopic measurements have been employed.
Research Organization:
Univ. of Pittsburgh, PA (USA)
OSTI ID:
6255262
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:21; ISSN JPCHA
Country of Publication:
United States
Language:
English