Stoichiometric and catalytic CO2 reductions involving TiFe-containing intermetallic hydrides
M. V. Tsodikov, V. Ya. Kugel, F. A. Yandieva, V. P. Mordovin, A. E. Gekhman,
and I. I. Moiseev
A.V. Topchiev Institute of Petrochemical Synthesis,
Russian Academy of Sciences, 29 Leninsky Prospect, Moscow 119991, Russia;
A.A. Baikov Institute of Metallurgy and Material Sciences, Russian Academy
of Sciences, 49 Leninsky Prospect, Moscow 119991, Russia; N.S. Kurnakov
Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky Prospect, Moscow 119991, Russia; I.M. Gubkin Russian State
University of Oil and Gas, 65 Leninsky Prospect, Moscow 119991, Russia
Abstract: Thermoprogrammed desorption of H2 from
[TiFe0.95Zr0.03Mo0.02]H2
showed two forms of absorbed hydrogen. The first one is evolved from
the intermetallic hydride under heating up to 185 �C under Ar (loosely
bound hydrogen, LBH). The second portion of H2 (strongly
bound hydrogen, SBH) remains in the intermetallic hydride up to 700�920
�C. SBH reacts with CO2 to give CO rather selectively (80�99
%) at CO2 conversion of 50�70 % at 350 �430 �C and 10 �12
atm. Dehydrogenation of cyclohexane coupled with CO2 hydrogenation
into CO predominantly proceeds efficiently in the presence of the intermetallic
hydride [TiFe0.95Zr0.03Mo0.02]Hx
(where x = 0.1) in a combination with industrial Pt/Al2O3
catalyst. Aliphatic primary alcohols undergo oxidation by CO2
forming aldehydes in the presence of [TiFe0.95Zr0.03Mo0.02]H0.36.
Conversion of the alcohols into alkanes with carbon skeleton counting
at least doubled carbon number in comparison with parent alcohol was
found to be catalyzed by the mixture of the last intermetallic hydride
and Pt/Al2O3 catalyst.
*Plenary lecture presented at the XVII Mendeleev Congress on General and Applied Chemistry, Kazan, Tatarstan, Russia, 21 -26 September 2003. Other presentations are published in this issue, pp. 1605-1798.
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