Surface and catalytic elucidation of Rh/gamma-Al2O3 catalysts during NO reduction by C3H8 in the presence of excess O2, H2O, and SO2.
The present study aims at exploring the surface and catalytic behavior of Rh/gamma-Al(2)O(3) catalysts during the selective reduction of NO by C(3)H(8) in the presence of excess oxygen, H(2)O, and SO(2) with particular emphasis on identifying the elementary steps that describe the reaction mechanism. To this end, detailed activity and stability tests were employed and a precise kinetic analysis was carried out at differential conditions to elucidate the effect of each reactant, including H(2)O and SO(2), on the total reaction rate. At the same time, temperature programmed desorption (TPD) studies in combination with in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy were carried out under various reaction conditions to correlate the catalytic performance of Rh/gamma-Al(2)O(3) catalyst with its corresponding surface chemistry. The results reveal that in the absence of H(2)O and SO(2), the reaction follows a typical "reduction" type mechanism, where the active intermediates (NO(X), carboxylates, isocyanates) are interacting to yield the final products. In this reaction sequence the formation of carboxylate (C(x)H(y)O(z)) species is considered as the rate determining step. Water affects in a different way the NO and C(3)H(8) conversion performance of Rh/gamma-Al(2)O(3) catalyst; its effect is totally reversible in the case of C(3)H(8) oxidation, while the NO reduction was permanently affected mainly due to the oxidation of Rh active sites. In contrast, SO(2) poisons both reactions irreversibly via the formation of strongly adsorbed sulfate compounds, which hinder the adsorption and consequently the activation of reactants.
Pekridis
G
G
Department of Mechanical Engineering, University of Western Macedonia, Bakola & Sialvera, GR-50100 Kozani, Greece.
Kaklidis
N
N
Komvokis
V
V
Athanasiou
C
C
Konsolakis
M
M
Yentekakis
I V
IV
Marnellos
G E
GE
D000537:Aluminum Oxide / Q000737:chemistry*; D002384:Catalysis; D009569:Nitric Oxide / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D011407:Propane / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013458:Sulfur Dioxide / Q000737:chemistry*; D013499:Surface Properties; D014867:Water / Q000737:chemistry*
D014867:Water; D013458:Sulfur Dioxide; D009569:Nitric Oxide; D012238:Rhodium; D000537:Aluminum Oxide; D010100:Oxygen; D011407:Propane