| Thermodynamics of glycerol hydrogenolysis to propanediols over supported copper clusters: Insights from first-principles study | |
| Guan Jing; Wang XiCheng; Wang XiaoYan; Mu XinDong | |
| 2013-06-01 | |
| 发表期刊 | SCIENCE CHINA-CHEMISTRY
 |
| 卷号 | 56期号:6页码:763-772 |
| 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. ; 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. |
| 文章类型 | Article |
| 关键词 | Density Functional Calculations Glycerol Hydrogenolysis Propanediols Copper-based Catalysts Mechanism |
| 学科领域 | 绿色化学催化 |
| WOS标题词 | Science & Technology ; Physical Sciences |
| DOI | 10.1007/s11426-012-4828-y |
| 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研究方向 | Chemistry |
| WOS类目 | Chemistry, Multidisciplinary |
| WOS记录号 | WOS:000319775900009 |
| 引用统计 | |
| 文献类型 | 期刊论文 |
| 条目标识符 | http://ir.qibebt.ac.cn/handle/337004/1655 |
| 专题 | 绿色化学催化研究组 |
| 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. |
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