Thermodynamics of glycerol hydrogenolysis to propanediols over supported copper clusters: Insights from first-principles study

CORC > 青岛生物能源与过程研究所 > 中国科学院青岛生物能源与过程研究所 > 绿色化学催化团队

	Thermodynamics of glycerol hydrogenolysis to propanediols over supported copper clusters: Insights from first-principles study
	Guan Jing; Wang XiCheng; Wang XiaoYan; Mu XinDong
刊名	SCIENCE CHINA-CHEMISTRY
	2013-06-01
卷号	56 期号:6 页码:763-772
关键词	density functional calculations glycerol hydrogenolysis propanediols copper-based catalysts mechanism
中文摘要	Copper catalysts supported on metal oxides display unique efficiency and selectivity in catalyzing glycerol hydrogenolysis to propanediols. Understanding the reaction at the molecular level is the key to rational design of better catalysts for propanediol synthesis, which is one of the major challenges for glycerol application in energy. In this work, extensive calculations based on periodic density functional theory were carried out to study thermodynamics of glycerol hydrogenolysis over binary model catalysts, including Cu/ZrO2 and Cu/MgO, with the focus to elucidate the competitive reaction pathways to produce the 1,2-propanediol (1,2-PDO) and 1,3-propanediol (1,3-PDO). Our results suggest that the reaction starts with glycerol dehydration on the metal oxide, followed by sequential hydrogenation over metal centers. Based on our explorations on the stabilities of adsorbed reactants, dehydrated intermediates and hydrogenated species along the reaction channels, the DFT calculations show that the 1,2-PDO formation will dominate in comparison to the 1,3-PDO from thermodynamic viewpoint. This is consistent with our experiments where the Cu catalysts seem to give the 1,2-PDO as a main product. The calculations and experiments also indicate that the Cu/MgO exhibits superior activities than Cu/ZrO2 for the hydrogenolysis of glycerol molecules.
英文摘要	Copper catalysts supported on metal oxides display unique efficiency and selectivity in catalyzing glycerol hydrogenolysis to propanediols. Understanding the reaction at the molecular level is the key to rational design of better catalysts for propanediol synthesis, which is one of the major challenges for glycerol application in energy. In this work, extensive calculations based on periodic density functional theory were carried out to study thermodynamics of glycerol hydrogenolysis over binary model catalysts, including Cu/ZrO2 and Cu/MgO, with the focus to elucidate the competitive reaction pathways to produce the 1,2-propanediol (1,2-PDO) and 1,3-propanediol (1,3-PDO). Our results suggest that the reaction starts with glycerol dehydration on the metal oxide, followed by sequential hydrogenation over metal centers. Based on our explorations on the stabilities of adsorbed reactants, dehydrated intermediates and hydrogenated species along the reaction channels, the DFT calculations show that the 1,2-PDO formation will dominate in comparison to the 1,3-PDO from thermodynamic viewpoint. This is consistent with our experiments where the Cu catalysts seem to give the 1,2-PDO as a main product. The calculations and experiments also indicate that the Cu/MgO exhibits superior activities than Cu/ZrO2 for the hydrogenolysis of glycerol molecules.
学科主题	绿色化学催化
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Multidisciplinary
研究领域[WOS]	Chemistry
关键词[WOS]	DENSITY-FUNCTIONAL THEORY ; AUGMENTED-WAVE METHOD ; PROPYLENE-GLYCOL ; SELECTIVE HYDROGENOLYSIS ; SURFACE HYDROXYLS ; CO2 HYDROGENATION ; AQUEOUS-SOLUTION ; 1ST PRINCIPLES ; C-H ; O-H
收录类别	SCI
语种	英语
WOS记录号	WOS:000319775900009
公开日期	2014-03-21
内容类型	期刊论文
源URL	[http://ir.qibebt.ac.cn:8080/handle/337004/1655]
专题	青岛生物能源与过程研究所_绿色化学催化团队
作者单位	Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Key Lab Biofuels, Qingdao 266101, Peoples R China
推荐引用方式 GB/T 7714	Guan Jing,Wang XiCheng,Wang XiaoYan,et al. Thermodynamics of glycerol hydrogenolysis to propanediols over supported copper clusters: Insights from first-principles study[J]. SCIENCE CHINA-CHEMISTRY,2013,56(6):763-772.
APA	Guan Jing,Wang XiCheng,Wang XiaoYan,&Mu XinDong.(2013).Thermodynamics of glycerol hydrogenolysis to propanediols over supported copper clusters: Insights from first-principles study.SCIENCE CHINA-CHEMISTRY,56(6),763-772.
MLA	Guan Jing,et al."Thermodynamics of glycerol hydrogenolysis to propanediols over supported copper clusters: Insights from first-principles study".SCIENCE CHINA-CHEMISTRY 56.6(2013):763-772.