Glycerol Hydrogenolysis to Propylene Glycol and Ethylene Glycol on   Zirconia Supported Noble Metal Catalysts

doi:10.1021/cs400486z

CORC > 北京大学 > 化学与分子工程学院

	Glycerol Hydrogenolysis to Propylene Glycol and Ethylene Glycol on Zirconia Supported Noble Metal Catalysts
	Wang, Shuai ; Yin, Kehua ; Zhang, Yichi ; Liu, Haichao
刊名	acs catalysis
	2013
关键词	glycerol selective hydrogenolysis propylene glycol ethylene glycol noble metal size effect ION-EXCHANGE-RESIN SELECTIVE HYDROGENOLYSIS BIMETALLIC CATALYSTS REACTION-MECHANISM AQUEOUS-SOLUTION 1,2-PROPANEDIOL NANOPARTICLES CHEMICALS CONVERSION RUTHENIUM
DOI	10.1021/cs400486z
英文摘要	Monoclinic zirconia (m-ZrO2) supported Ru, Rh, Pt, and Pd nanoparticles with controlled sizes were prepared and examined in glycerol hydrogenolysis to propylene glycol and ethylene glycol at similar conversions in the kinetic regime. Their activity (normalized per exposed surface metal atom, i.e., turnover rate) and selectivity depend sensitively on the nature of the noble metals and their particle size. At a similar size (ca. 2 nm), Ru exhibited a greater turnover rate than Rh, Pt, and Pd, and the rate decreased in the sequence Ru >> Rh > Pt > Pd by a factor of about 25 (from 0.035 to 0.0014 mol glycerol (mol surface metal.s)(-1)) at 473 K and 6.0 MPa H-2. Following such activity sequence, Ru was more prone to catalyze excessive cleavage of C-C bonds, leading to the formation of ethylene glycol and methane, while Pd exhibited the highest selectivity to cleavage of C-O bonds to propylene glycol. Similarly, larger Ru particles possessed higher glycerol hydrogenolysis activity concurrently with higher selectivities to ethylene glycol and especially methane at the expense of propylene glycol in the range of 1.8-4.5 nm. Analysis of kinetics and thermodynamics for the proposed elementary steps involving kinetically relevant glycerol dehydrogenation to glyceraldehyde leads to expressions of glycerol hydrogenolysis rate and selectivity to cleavage of C-O bonds relative to C-C bonds. Together with different effects of reaction temperature and atmosphere of H-2 and N-2 on the activity and selectivity for Ru/m-ZrO2 and Pt/m-ZrO2, these results suggest that the observed difference for different noble metals and particle sizes can be attributed to the difference in the strength of adsorption of glycerol and glyceraldehyde, derived from their different availability of unoccupied d orbitals.; Chemistry, Physical; SCI(E); EI; 9; ARTICLE; 9; 2112-2121; 3
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/150728]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Wang, Shuai,Yin, Kehua,Zhang, Yichi,et al. Glycerol Hydrogenolysis to Propylene Glycol and Ethylene Glycol on Zirconia Supported Noble Metal Catalysts[J]. acs catalysis,2013.
APA	Wang, Shuai,Yin, Kehua,Zhang, Yichi,&Liu, Haichao.(2013).Glycerol Hydrogenolysis to Propylene Glycol and Ethylene Glycol on Zirconia Supported Noble Metal Catalysts.acs catalysis.
MLA	Wang, Shuai,et al."Glycerol Hydrogenolysis to Propylene Glycol and Ethylene Glycol on Zirconia Supported Noble Metal Catalysts".acs catalysis (2013).