Mechanism of formation oxygenated compounds from CO + H[sub 2] reaction over SiO[sub 2]-supported Ru-Co bimetallic carbonyl cluster-derived catalysts

Journal Article · Sun Nov 01 00:00:00 EST 1992 · Journal of Catalysis; (United States)

DOI:https://doi.org/10.1016/0021-9517(92)90018-D· OSTI ID:5518303

Xiao, Feng-Shou ^[1]; Fukuoka, A; Ichikawa, M ^[2]

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1. Hokkaido Univ., Sapporo (Japan) Jilin Univ., Changchun (China)
2. Hokkaido Univ., Sapporo (Japan)

The catalytic performance in CO hydrogenation over Ru, Ru-Co, and Co carbonyl cluster-derived catalysts has been investigated, and it was found that the activity and selectivity for oxygenated products on a series of Ru-Co/SiO[sub 2] catalysts are much higher than those on Ru[sub 3]/SiO[sub 2] and Co[sub 4]/SiO[sub 2] catalysts. The mechanism of oxygenated formation on these Ru-Co/SiO[sub 2] catalysts has been investigated by in situ infrared, mass, and X-ray photoelectron spectroscopies. The IR spectra of reaction of CO + H[sub 2] with Ru-Co/SiO[sub 2] catalysts show a band appearing at 1584 cm[sup [minus]1], which has a good relationship to the activity and selectivity for oxygenates in CO hydrogenation. The adsorption of CO on reduced Ru-Co/SiO[sub 2] catalysts prepared from Ru-Co bimetallic carbonyl clusters exhibits a band at 1680 cm[sup [minus]1] shifting to 1640 cm[sup [minus]1] with [sup 13]CO, which is assigned to the C- and O-ended CO chemisorbed on Ru-Co/SiO[sub 2] catalysts. The chemical trapping of 1584 cm[sup [minus]1] adspecies shows that the 1584 cm[sup [minus]1] species reacts with H[sub 2] to produce CH[sub 4] and CH[sub 3]OH, and the addition of D[sub 2] to 1584 cm[sup [minus]1] species results in the formation of CHD[sub 3] and CHD[sub 2]OD. With the increase of reaction time and temperature, the author finds the bands at 1555 and 1440-1470 cm[sup [minus]1], while the 1584 cm[sup [minus]1] band gradually decreases on Ru-Co/SiO[sub 2] catalysts. XPS spectra demonstrate that the Ru and Co sites on the surface of Ru-Co/SiO[sub 2] catalysts are in the chemical state of Ru[sup 0] and Co[sup 2[minus]], respectively, and it is suggested that the bimetallic Ru[sup 0]-Co[sup 2+] sites are very active centers for the formation of oxygenates in CO hydrogenation. 62 refs., 19 figs., 5 tabs.

• OSTI ID: 5518303
• Journal Information: Journal of Catalysis; (United States), Vol. 138:1; ISSN 0021-9517
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
01 COAL, LIGNITE, AND PEAT
CARBON MONOXIDE
HYDROGENATION
COBALT COMPLEXES
CATALYTIC EFFECTS
RUTHENIUM COMPLEXES
SILICON OXIDES
ABSORPTION SPECTROSCOPY
ADSORPTION
CATALYST SUPPORTS
CATALYSTS
CHEMISORPTION
DEUTERIUM
ETHANOL
HETEROGENEOUS CATALYSIS
MASS SPECTROSCOPY
PHOTOELECTRON SPECTROSCOPY
X-RAY SPECTROSCOPY
ALCOHOLS
CARBON COMPOUNDS
CARBON OXIDES
CATALYSIS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
ELECTRON SPECTROSCOPY
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
ISOTOPES
LIGHT NUCLEI
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
SEPARATION PROCESSES
SILICON COMPOUNDS
SORPTION
SPECTROSCOPY
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400102* - Chemical & Spectral Procedures
010408 - Coal
Lignite
& Peat- C1 Processes- (1987-)