Selenium-doped hexarhodium carbonyl clusters on magnesia: structures and promoting effects in ethene hydroformylation

Yasuo Izumi, Yasuhiro Iwasawa
1992 The Journal of Physical Chemistry  
Selenium-modified Rh6(CO) 16/Mg0 catalysts were prepared by the reaction of Rh6(CO)16/Mg0 with (CH3)2Se in order to examine the promoting effect of an electronegative additive on Rh catalysis for ethene hydroformylation. The deposited Se (Se/Rh6 = 0.6) enhanced the rate of propanal formation 1.9 times as compared with the case of an undepited catalyst. The selectivity of the hydroformylation was improved from 20 to 50% by the Se addition. To the contrary, the monotonous suppression of ethane
more » ... ession of ethane formation by increasing the Se amount was observed. Further doping of Se reduced the hydroformylation activity. TPD, IR, and Se K-edge and Rh K-edge EXAFS revealed that (CH3)2Se reacted with the Rh atoms of partially-decarbonylated Rh, species on the MgO surface, forming Se-Rh bonds at a distance of 0.244 nm. XPS data suggested that the oxidation state of Se in the catalyst is Se-, while Rh is in a nearly metallic state. CO adsorbs on the rhodium atoms bonded to Se, which is contrasted to blocking of the neighboring Rh sites by Se atom observed with usual impregnated Rh catalysts. The structures of the Se-undoped and -doped Rh6 clusters on MgO are presented in relation to the active site of the cluster catalyst. The data indicate an advantage of molecular clusters over impregnated particles in adsorption capability and catalysis.
doi:10.1021/j100205a062 fatcat:w6roo2hmhrh3fgaw4xttpdjgpy