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

氢甲酰化 化学 催化作用 双金属片 红外光谱学 沸石 一氧化碳 无机化学 光化学 有机化学
作者
Liang Qi,Sonali Das,Yanfei Zhang,Danna Nozik,Bruce C. Gates,Alexis T. Bell
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:145 (5): 2911-2929 被引量:41
标识
DOI:10.1021/jacs.2c11075
摘要

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. In situ 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. In situ 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.
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