The acidic properties of cobalt-and silicon-substituted AIPO-5, -11 and -44 have been characterized by adsorption calorimetry and IR measurements. Adsorption calorimetric measurements indicate that the adsorption potential of the samples for acetonitrile is enhanced upon cobalt incorporation. The calorimetrically measured heats of adsorption indicate the formation of strong acid sites, due to this cobalt incorporation, as well as the presence of weaker acid sites, probably terminal P-OH groups. IR measurements of adsorbed ammonia and acetonitrile indicate that some Brsnsted-bonded ammonia and acetonitrile are present, in combination with Lewis-bonded species. The Brsnsted-bonded species presumably originate from interaction of the base with the weakly acidic P-OH groups. The Lewis-bonded species are due to the coordinative interaction of the lone pair of the base with framework cobalt ions,

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R. (1987). Hydrogenation of carbon monoxide over rhodium/silica catalysts promoted with molybdenum oxide and thorium oxide. Applied Catalysis, 35(1), 109-139. DOI: 10.1016/S0166-9834(00) General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. ABSTRACTThe promotion of silica-supported rhodium catalysts in the hydrogenation of carbon monoxide by molybdenum oxide and thorium oxide has been examined. Temperature programmed reduction studies indicated the formation of rhodium molybdates, while no evidence was found for the formation of such mixed oxides in the thorium oxide-promoted catalysts. Hydrogen and carbon monoxide chemisorption were suppressed by the presence of molybdenum oxide, pointing to a coverage of the rhodium particles by this promoter oxide. The catalysts with MO: Rh ratios exceeding one even exhibited an almost complete suppression of the rhodium chemisorption capacity. In the thorium oxide-promoted catalysts the chemisorption of hydrogen and carbon monoxide were not suppressed. Infrared spectroscopy of adsorbed carbon monoxide showed that molybdenum oxide completely suppressed bridge-bonded and linearly bonded carbon monoxide, as well as the gemdicarbonyl species. Thorium oxide addition resulted in a minor decrease of the linearly bonded carbon monoxide, while the bridge-bonded carbon monoxide was suppressed to a greater extent. The IR spectra of the thorium oxide-promoted catalysts also exhibited a broad absorption band between 1300 and 1750 cm-', which is thought to be due to carbon monoxide bonded with the carbon atom to the metal and with the oxygen atom to the promoter ion.Carbon monoxide hydrogenation was greatly enhanced by the presence of both molybdenum oxide and thorium oxide. Thorium oxide-promoted catalysts had a high selectivity to C,-oxygenates, while the molybdenum oxide-promoted catalysts exhibited a high methanol selectivity. Ethylene addition to a working catalyst showed that the carbon monoxide insertion reaction, which is thought to be responsible for the formation of oxygenates, was not enhanced by molybdenum oxide, nor by thorium oxide. The ethylene addition experiments indicated that the role of the promoter is to enhance carbon monoxide dissociation. The results can be understood by assuming that side-bonded carbon monoxide, with its weakened C-O...

Instead, a reaction model is proposed, which is based upon the involvement of I thiyl-and a superoxoactivati Cu(II) complex, respectively. These two types of complexes are operative in a chainlike propagation cycle _

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