Vapor phase hydroformylation of ethene over Co/SiO2 promoted by noble metals: dynamic in situ diffuse reflectance FT-IR study of surface species

An in situ diffuse reflectance FT-IR technique was employed to investigate the active surface species and the reaction mechanism of the oxygenate formation in the vapor phase hydroformylation of ethene on Co/SiO₂ promoted with various noble metals such as Ir, Rh, Pt, Re, Ru, and Pd. Co(A)/SiO₂ and Ir(CO)/SiO₂ which were derived from cobalt(II) acetate and Ir₄(CO)₁₂, respectively, were quite inactive in the reaction, and showed only quite small peaks of adsorbed CO under the conditions of 1.1 MPa of C₂H₄/CO/H₂ at 298 K. In contrast, Co(A)-Ir(CO)/SiO₂, which were very active in the reaction, exhibited strong absorption bands of linear and bridged CO species. At 423–463 K, propanal adsorbed on the catalyst and acyl species which is suggested as the intermediate for the formation of propanal were also observed on this catalyst. By exposing CO preadsorbed on this catalyst to C₂H₄/H₂ at 289 K and 0.1 MPa, the intensity of the linear CO band decreased, and the bands of propanal and acyl species emerged simultaneously, whereas that of the bridged CO band remained constant after the initial drop. These results suggested that the oxygenates are formed via the CO insertion into adsorbed ethyl species, and linear CO species plays a major role in the CO insertion on these noble metal-promoted cobalt catalysts.