Ethene Hydroformylation Catalyzed by Rhodium Dispersed with Zinc or Cobalt in Silanol Nests of Dealuminated Zeolite Beta

Catalysts for hydroformylation of ethene were prepared by grafting Rh into nests of ≡SiOZn-OH or ≡SiOCo-OH species prepared in dealuminated BEA zeolite. X-ray absorption spectra and infrared spectra of adsorbed CO were used to characterize the dispersion of Rh. The Rh dispersion was found to increase markedly with increasing M/Rh (M = Zn or Co) ratio; further increases in Rh dispersion occurred upon use for ethene hydroformylation catalysis. The turnover frequency for ethene hydroformylation measured for a fixed set of reaction conditions increased with the fraction of atomically dispersed Rh. The ethene hydroformylation activity is 15.5-fold higher for M = Co than for M = Zn, whereas the propanal selectivity is slightly greater for the latter catalyst. The activity of the Co-containing catalyst exceeds that of all previously reported Rh-containing bimetallic catalysts. The rates of ethene hydroformylation and ethene hydrogenation exhibit positive reaction orders in ethene and hydrogen but negative orders in carbon monoxide. <i>In situ</i> IR spectroscopy and the kinetics of the catalytic reactions suggest that ethene hydroformylation is mainly catalyzed by atomically dispersed Rh that is influenced by Rh-M interactions, whereas ethene hydrogenation is mainly catalyzed by Rh nanoclusters. <i>In situ</i> IR spectroscopy also indicates that the ethene hydroformylation is rate limited by formation of propionyl groups and by their hydrogenation, a conclusion supported by the measured H/D kinetic isotope effect. This study presents a novel method for creating highly active Rh-containing bimetallic sites for ethene hydroformylation and provides new insights into the mechanism and kinetics of this process.