DFT Studies of the Selective C-O Hydrogenolysis and Ring-Opening of Biomass-Derived Tetrahydrofurfuryl Alcohol over Rh(111) surfaces

doi:10.1021/acs.jpcc.6b05026

QIBEBT-IR > 绿色化学催化研究组

	DFT Studies of the Selective C-O Hydrogenolysis and Ring-Opening of Biomass-Derived Tetrahydrofurfuryl Alcohol over Rh(111) surfaces
	Guan, Jing1 ; Li, Jing2 ; Yu, Yifeng 2; Mu, Xindong 1; Chen, Aibing 2
	2016-09-01
发表期刊	JOURNAL OF PHYSICAL CHEMISTRY C
卷号	120 期号:34 页码:19124-19134
摘要	Tetrahydrofurfuryl alcohol (THFA) has been identified as a platform chemical of interest because of its production from biomass. It can be converted into valuable alcohols and ethers by selective hydrogenation/hydrogenolysis reaction over Rh-based metal catalysts. To better understand the chemistry of THFA, the reaction energies and the corresponding energy barriers of selective C-O bond hydrogenolysis and ring-opening of THFA on Rh(111) for the formation of 2-methyltetrahydrofuran (2-MeTHF), 1,5-pentanediol (1,5-PeD), and 1,2-pentanediol (1,2-PeD) were studied using density functional theory (DFT) calculations. The results indicate that starting from THFA to produce 2-MeTHF, the direct C-O bond cleavage of the CH2OH group is not favored. Alternatively and more preferentially, the reaction occurs through the initial activation of C-H bond on the side chain, followed by dehydroxylation and hydrogenation. On the other hand, in the metal catalyzed ring-opening process of THFA to 1,5-PeD and 1,2-PeD, the first dehydrogenation of secondary CH-O or primary CH2-O moiety in the ring decreases the barriers of the subsequent C-O bond dissociation. Moreover, the energy span theory shows that the ring-opening at the sterically less-hindered primary C-O bond exhibits a lower effective barrier than that for ring-opening at the more sterically hindered secondary C-O bond, as well as hydrogenolysis at the side CH2OH chain, suggesting that the formation of 1,2-PeD is much kinetically favored than the formation of 1,5-PeD and 2-MeTHF. Our theoretical results give a good explanation for the experimental fact that 1,2-PeD was the dominant product observed on unprompted Rh/SiO2.
文章类型	Article
WOS标题词	Science & Technology ; Physical Sciences ; Technology
DOI	10.1021/acs.jpcc.6b05026
关键词[WOS]	TOTAL-ENERGY CALCULATIONS ; AUGMENTED-WAVE METHOD ; FURFURYL ALCOHOL ; CHEMOSELECTIVE HYDROGENOLYSIS ; CATALYTIC CYCLES ; BASIS-SET ; CONVERSION ; 1,5-PENTANEDIOL ; HYDROGENATION ; CHEMICALS
收录类别	SCI
语种	英语
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science
项目资助者	National Natural Science Foundation of China(21303238 ; Qingdao Applied Basic Research Program(14-2-4-74-jch) ; Shandong Provincial Natural Science Foundation for Distinguished Young Scholar, China(JQ201305) ; 21273260 ; 21433001)
WOS类目	Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
WOS记录号	WOS:000382596900021
引用统计
文献类型	期刊论文
条目标识符	http://ir.qibebt.ac.cn/handle/337004/8493
专题	绿色化学催化研究组
作者单位	1.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, CAS Key Lab Biobased Mat, Qingdao 266101, Peoples R China 2.Hebei Univ Sci & Technol, Coll Chem & Pharmaceut Engn, Shijiazhuang 050018, Peoples R China
推荐引用方式 GB/T 7714	Guan, Jing,Li, Jing,Yu, Yifeng,et al. DFT Studies of the Selective C-O Hydrogenolysis and Ring-Opening of Biomass-Derived Tetrahydrofurfuryl Alcohol over Rh(111) surfaces[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2016,120(34):19124-19134.
APA	Guan, Jing,Li, Jing,Yu, Yifeng,Mu, Xindong,&Chen, Aibing.(2016).DFT Studies of the Selective C-O Hydrogenolysis and Ring-Opening of Biomass-Derived Tetrahydrofurfuryl Alcohol over Rh(111) surfaces.JOURNAL OF PHYSICAL CHEMISTRY C,120(34),19124-19134.
MLA	Guan, Jing,et al."DFT Studies of the Selective C-O Hydrogenolysis and Ring-Opening of Biomass-Derived Tetrahydrofurfuryl Alcohol over Rh(111) surfaces".JOURNAL OF PHYSICAL CHEMISTRY C 120.34(2016):19124-19134.