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Effect of NO pressure on the reaction of NO and CO over Rh(111)

Journal Article · · Journal of Physical Chemistry
;  [1];  [2]; ;  [3]
  1. Wayne State Univ., Detroit, MI (United States)
  2. Pacific Northwest Lab., Richland, WA (United States)
  3. G.M. NAO R&D Center, Warren, MI (United States)

We have examined the reaction of NO and CO over a Rh(III) catalyst under conditions of both low (0.8 Torr) and high (9 Torr) NO pressures. Our results show that the same three products are formed (CO{sub 2}, N{sub 2}O, and N{sub 2}) regardless of the NO pressure employed. However the selectivity of the reaction and the E{sub a} for product formation are profoundly affected when the NO pressure is lowered by tenfold. For high NO pressures the selectivity is insensitive to either NO pressure (1 Torr < P{sub NO} < 40 Torr) or reaction temperature (T < 673 K). In sharp contrast to this high-pressure behavior, when the NO pressure is lowered to 0.8 Torr, then the selectivity is a strong function of reaction temperature, with N{sub 2}O being the major product below 635 K and N{sub 2} the major product above 635 K. It is exactly this switch over in selectivity at elevated temperature that has always been seen over low-loaded Rh/Al{sub 2}O{sub 3} catalysts but until this time not reported for single-crystal catalysts. On the basis of our new results we can say that Rh(III) has the characteristic selectivity behavior of practical Rh/Al{sub 2}O{sub 3} catalysts. These results are encouraging because they show that the mechanistic insight we gain over Rh(III) is more broadly applicable to supported catalysts than was previously thought. 20 refs., 4 figs., 1 tab.

Sponsoring Organization:
USDOE
OSTI ID:
171491
Journal Information:
Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 44 Vol. 99; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English

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