Abstract
Iron-containing bimetallic catalysts were prepared from carbonyl clusters as precursors deposited on SiO 2. FeRh 4 and Fe 2Rh 4 cluster-derived catalysts showed high activity and selectivity for formation of ethanol and methanol in CO hydrogenation. Fe 3Pt 3, Fe 6Pd 6 and FeIr 4 cluster catalysts gave methanol in high selectivity, while Fe-rich Fe 4Pt and Fe 4Pd were not selective catalysts. The RhFe cluster catalysts showed improved activity in hydroformylation of olefins; C 4-alcohols were substantially obtained from C 3 + CO + H 2. Mössbauer and EXAFS studies on the Fe 2Rh 4/SiO 2 catalyst show that highly dispersed RhFe bimetallic particles are located on the SiO 2 surface, where Fe atoms exist preferentially in the state of Fe 3+ even after H 2 reduction. FTIR spectra of CO chemisorbed on Fe 2Rh 4/SiO 2 exhibit a low-frequency band possibly due to the G and O-bonded CO on Rh-Fe 3+ sites. Bimetallic promotion of alcohol production in CO hydrogenation and olefin hydroformylation is proposed to originate from the two-site interaction of Rh-Fe 3+ (or Pt-Fe 3+, Pd-Fe 3+, IrFe 3+) sites with CO to enhance migratory CO insertion.
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