Stoichiometric and catalytic CO2 reductions involving TiFe-containing intermetallic hydrides

Tsodikov, M. V.; Kugel, V. Ya.; Yandieva, F. A.; Mordovin, V. P.; Gekhman, A. E.; Moiseev, I. I.

doi:10.1351/pac200476091769

Pure Appl. Chem., 2004, Vol. 76, No. 9, pp. 1769-1779

http://dx.doi.org/10.1351/pac200476091769

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 [TiFe_0.95Zr_0.03Mo_0.02]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 [TiFe_0.95Zr_0.03Mo_0.02]H_x (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 [TiFe_0.95Zr_0.03Mo_0.02]H_0.36. 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.