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Title: An in-situ infrared study of the formation of n- and iso-butyraldehyde from propylene hydroformylation on Rh/SiO[sub 2] and sulfided Rh/SiO[sub 2]

Abstract

In situ infrared (IR) technique has been employed to study the reaction of adsorbed CO on Rh/SiO[sub 2] and S-Rh/SiO[sub 2] with C[sub 3]H[sub 6] and H[sub 2], and to investigate the effect of sulfur on the n- and iso-butyraldehyde selectivities during steady-state propylene hydroformylation. CO adsorption on Rh/SiO[sub 2] results in the formation of linear CO and bridged CO adsorbed on Rh[sup 0] sites, and the gemdicarbonyl on Rh[sup +] sites. CO adsorption on S-Rh/SiO[sub 2] results in a high wavenumber Rh[sup +](CO) species in addition to linear CO adsorbed on Rh[sup 0] and the gem-dicarbonyl adsorbed on Rh[sup +]. Sulfur decreases the rate of CO adsorption and inhibits the formation of bridged CO on Rh/SiO[sub 2]. Pulse CO chemisorption on Rh/SiO[sub 2] and S-Rh/SiO[sub 2] reveals that equilibrium constant for CO adsorption on S-Rh/SiO[sub 2] is smaller than that on Rh/SiO[sub 2] at 303 K. The analogy between homogeneous and heterogeneous hydroformylation suggests that enhancement of the isobutryaldehyde formation by adsorbed sulfur could be due to the spacious environment of the protruding Rh[sup +] ion sites ion the S-Rh/SiO[sub 2] allowing isomerization of n-propyl groups before CO insertion. 56 refs., 11 figs., 3 tabs.

Authors:
;  [1]
  1. Univ. of Akron, OH (United States)
Publication Date:
OSTI Identifier:
5088274
Resource Type:
Journal Article
Journal Name:
Journal of Catalysis; (United States)
Additional Journal Information:
Journal Volume: 144:1; Journal ID: ISSN 0021-9517
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 10 SYNTHETIC FUELS; PROPYLENE; CARBONYLATION; RHODIUM COMPLEXES; CATALYTIC EFFECTS; ABSORPTION SPECTROSCOPY; CATALYST SUPPORTS; HETEROGENEOUS CATALYSIS; SILICA; SORPTIVE PROPERTIES; ALKENES; CATALYSIS; CHALCOGENIDES; CHEMICAL REACTIONS; COMPLEXES; HYDROCARBONS; MINERALS; ORGANIC COMPOUNDS; OXIDE MINERALS; OXIDES; OXYGEN COMPOUNDS; SILICON COMPOUNDS; SILICON OXIDES; SPECTROSCOPY; SURFACE PROPERTIES; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 100200 - Synthetic Fuels- Production- (1990-)

Citation Formats

Srinivas, G, and Chuang, S S. An in-situ infrared study of the formation of n- and iso-butyraldehyde from propylene hydroformylation on Rh/SiO[sub 2] and sulfided Rh/SiO[sub 2]. United States: N. p., 1993. Web. doi:10.1006/jcat.1993.1319.
Srinivas, G, & Chuang, S S. An in-situ infrared study of the formation of n- and iso-butyraldehyde from propylene hydroformylation on Rh/SiO[sub 2] and sulfided Rh/SiO[sub 2]. United States. doi:10.1006/jcat.1993.1319.
Srinivas, G, and Chuang, S S. Mon . "An in-situ infrared study of the formation of n- and iso-butyraldehyde from propylene hydroformylation on Rh/SiO[sub 2] and sulfided Rh/SiO[sub 2]". United States. doi:10.1006/jcat.1993.1319.
@article{osti_5088274,
title = {An in-situ infrared study of the formation of n- and iso-butyraldehyde from propylene hydroformylation on Rh/SiO[sub 2] and sulfided Rh/SiO[sub 2]},
author = {Srinivas, G and Chuang, S S},
abstractNote = {In situ infrared (IR) technique has been employed to study the reaction of adsorbed CO on Rh/SiO[sub 2] and S-Rh/SiO[sub 2] with C[sub 3]H[sub 6] and H[sub 2], and to investigate the effect of sulfur on the n- and iso-butyraldehyde selectivities during steady-state propylene hydroformylation. CO adsorption on Rh/SiO[sub 2] results in the formation of linear CO and bridged CO adsorbed on Rh[sup 0] sites, and the gemdicarbonyl on Rh[sup +] sites. CO adsorption on S-Rh/SiO[sub 2] results in a high wavenumber Rh[sup +](CO) species in addition to linear CO adsorbed on Rh[sup 0] and the gem-dicarbonyl adsorbed on Rh[sup +]. Sulfur decreases the rate of CO adsorption and inhibits the formation of bridged CO on Rh/SiO[sub 2]. Pulse CO chemisorption on Rh/SiO[sub 2] and S-Rh/SiO[sub 2] reveals that equilibrium constant for CO adsorption on S-Rh/SiO[sub 2] is smaller than that on Rh/SiO[sub 2] at 303 K. The analogy between homogeneous and heterogeneous hydroformylation suggests that enhancement of the isobutryaldehyde formation by adsorbed sulfur could be due to the spacious environment of the protruding Rh[sup +] ion sites ion the S-Rh/SiO[sub 2] allowing isomerization of n-propyl groups before CO insertion. 56 refs., 11 figs., 3 tabs.},
doi = {10.1006/jcat.1993.1319},
journal = {Journal of Catalysis; (United States)},
issn = {0021-9517},
number = ,
volume = 144:1,
place = {United States},
year = {1993},
month = {11}
}