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Role of ReOx in Re-modified Rh/ZrO2 and Ir/ZrO2 catalysts in glycerol hydrogenolysis: Insights from first-principles study
Guan, Jing1; Chen, Xiufang1; Peng, Gongming1; Wang, Xicheng1; Cao, Quan1; Lan, Zhenggang1,2; Mu, Xindong1
2013-09-01
发表期刊CHINESE JOURNAL OF CATALYSIS
卷号34期号:9页码:1656-1666
摘要 The thermodynamics of glycerol hydrogenolysis to produce 1,2‐propanediol (1,2‐PDO) and 1,3‐propanediol (1,3‐PDO) over Ru/ZrO2, Rh/ZrO2, ReOx‐Rh/ZrO2, and ReOx‐Ir/ZrO2 were studied using density functional theory calculations, with a special focus on the mechanism controlling the activity and selectivity of the reactions. It is found that the decomposition of glycerol on Ru/ZrO2 and Rh/ZrO2 proceeds through a dehydration‐hydrogenation mechanism. The formation of 1,2‐PDO is thermodynamically favored, and the activity of the Ru‐based catalyst is higher than that of the Rh‐based one. In contrast, a direct hydrogenolysis mechanism is proposed for the Re‐modified Rh and Ir catalysts, in which a dissociated H atom on the Rh(Ir) metal surface attacks the C–O bond neighboring the alkoxide species on the ReOx cluster. In the presence of ReOx‐Rh/ZrO2, the modified catalyst favors the production of 1,2‐PDO, and 1,3‐PDO production becomes competitive. However, the ReOx‐Ir/ZrO2 catalyst significantly improves 1,3‐PDO selectivity. The direct hydrogenolysis pathway, as opposed to the indirect hydrogenolysis mechanism for monometallic catalysts, may be the key to the high 1,3‐PDO selectivity on the modified catalysts, where the hydroxylated Re group facilitates the formation of terminal alkoxide species rather than secondary alkoxides. Steric effects are important in preferential terminal alkoxide formation on the ReOx‐Ir/ZrO2 catalysts because of the growth of large Ir‐Re clusters, resulting in high selectivity for 1,3‐PDO.
 
; The thermodynamics of glycerol hydrogenolysis to produce 1,2-propanediol (1,2-PDO) and 1,3-propanediol (1,3-PDO) over Ru/ZrO2, Rh/ZrO2, ReOx-Rh/ZrO2, and ReOx-Ir/ZrO2 were studied using density functional theory calculations, with a special focus on the mechanism controlling the activity and selectivity of the reactions. It is found that the decomposition of glycerol on Ru/ZrO2 and Rh/ZrO2 proceeds through a dehydration-hydrogenation mechanism. The formation of 1,2-PDO is thermodynamically favored, and the activity of the Ru-based catalyst is higher than that of the Rh-based one. In contrast, a direct hydrogenolysis mechanism is proposed for the Re-modified Rh and Ir catalysts, in which a dissociated H atom on the Rh(Ir) metal surface attacks the C-O bond neighboring the alkoxide species on the ReOx cluster. In the presence of ReOx-Rh/ZrO2, the modified catalyst favors the production of 1,2-PDO, and 1,3-PDO production becomes competitive. However, the ReOx-Ir/ZrO2 catalyst significantly improves 1,3-PDO selectivity. The direct hydrogenolysis pathway, as opposed to the indirect hydrogenolysis mechanism for monometallic catalysts, may be the key to the high 1,3-PDO selectivity on the modified catalysts, where the hydroxylated Re group facilitates the formation of terminal alkoxide species rather than secondary alkoxides. Steric effects are important in preferential terminal alkoxide formation on the ReOx-Ir/ZrO2 catalysts because of the growth of large Ir-Re clusters, resulting in high selectivity for 1,3-PDO. 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
文章类型Article
关键词Density Functional Theory Glycerol Hydrogenolysis Propanediol Re-modified Metal Catalyst Thermodynamics
学科领域绿色化学催化
WOS标题词Science & Technology ; Physical Sciences ; Technology
DOI10.1016/S1872-2067(12)60626-3
关键词[WOS]AUGMENTED-WAVE METHOD ; ION-EXCHANGE-RESIN ; SELECTIVE HYDROGENOLYSIS ; MECHANISM ; SURFACE ; RUTHENIUM ; 1,3-PROPANEDIOL ; TEMPERATURE ; TRANSITION ; EFFICIENT
收录类别SCI
语种英语
WOS研究方向Chemistry ; Engineering
WOS类目Chemistry, Applied ; Chemistry, Physical ; Engineering, Chemical
WOS记录号WOS:000324664900004
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文献类型期刊论文
条目标识符http://ir.qibebt.ac.cn/handle/337004/1668
专题绿色化学催化研究组
作者单位1.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Key Lab Biobased Mat, Qingdao 266101, Shandong, Peoples R China
2.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Qingdao Key Lab Solar Energy Utilizat & Energy St, Qingdao 266101, Shandong, Peoples R China
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Guan, Jing,Chen, Xiufang,Peng, Gongming,et al. Role of ReOx in Re-modified Rh/ZrO2 and Ir/ZrO2 catalysts in glycerol hydrogenolysis: Insights from first-principles study[J]. CHINESE JOURNAL OF CATALYSIS,2013,34(9):1656-1666.
APA Guan, Jing.,Chen, Xiufang.,Peng, Gongming.,Wang, Xicheng.,Cao, Quan.,...&Mu, Xindong.(2013).Role of ReOx in Re-modified Rh/ZrO2 and Ir/ZrO2 catalysts in glycerol hydrogenolysis: Insights from first-principles study.CHINESE JOURNAL OF CATALYSIS,34(9),1656-1666.
MLA Guan, Jing,et al."Role of ReOx in Re-modified Rh/ZrO2 and Ir/ZrO2 catalysts in glycerol hydrogenolysis: Insights from first-principles study".CHINESE JOURNAL OF CATALYSIS 34.9(2013):1656-1666.
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