Xantphos doped Rh/POPs-PPh3 catalyst for highly selective long-chain olefins hydroformylation: Chemical and DFT insights into Rh location and the roles of Xantphos and PPh3

	Xantphos doped Rh/POPs-PPh3 catalyst for highly selective long-chain olefins hydroformylation: Chemical and DFT insights into Rh location and the roles of Xantphos and PPh3
	Jiang, Zheng 3; Li, Cunyao 4; Sun, Keju 5; Wang, Wenlong 4; Yan, Li 4; Sun, Xueping 3; Wang, Yuqing 4; Xiong, Kai 2; Zhan, Zhuangping 2; Ding, Yunjie 1,4
刊名	JOURNAL OF CATALYSIS
	2017-09-01
卷号	353 页码:123-132
关键词	Heterogeneous hydroformylation Long-chain olefins Porous organic polymers Linear-regioselectivity
英文摘要	Vinyl functionalized Xantphos ligand (denoted as 4v-Xantphos) was newly synthesized and successfully doped into the PPh3 based porous organic polymers (POPs) through the solvothermal synthesis technique. After proper coordination with Rh precursor, the resultant Xantphos doped Rh/POPs-PPh3 catalysts exhibited high activity (TOF: 300-500 h(-1)), chemoselectivity (87-91%) and regioselectivity (about 90:10) in the hydroformylation of long-chain olefins (C6-C12). As a representative substrate, hydroformylation of 1-octene could be easily realized in a fixed bed reactor for more than 400 h with high efficiency employing Xantphos doped Rh/POPs-PPh3 catalyst, which represented a rare successful example that realized heterogenization of homogeneous hydrofromylation catalysts as well as the regioselectivity-control at the same time without leaching of rhodium. Interestingly, the hydroformylation reaction data indicated that the Rh species tend to coordinate with the exposed P atom from Xantphos rather than that from PPh3 ligand in the Xantphos doped catalyst frame. More importantly, the HAADF-STEM and EXAFS characterizations indicated that Rh species demonstrated as single site dispersion in Xantphos doped Rh/POPs-PPh3 catalyst, thus endowed the catalyst with high activity. Detailed DFT calculations revealed that the unique location of single site dispersed Rh species (Rh species coordinated with both of Xantphos and PPh3 in the catalyst frame simultaneously) was responsible for the high linear regioselectivity and stability of the catalysts, the roles of Xantphos and PPh3 were further elucidated in details. (C) 2017 Elsevier Inc. All rights reserved.
WOS标题词	Science & Technology ; Physical Sciences ; Technology
类目[WOS]	Chemistry, Physical ; Engineering, Chemical
研究领域[WOS]	Chemistry ; Engineering
关键词[WOS]	SUPERCRITICAL CARBON-DIOXIDE ; GAS-PHASE HYDROFORMYLATION ; FIXED-BED HYDROFORMYLATION ; MODIFIED RH/SIO2 CATALYSTS ; IONIC LIQUID ; TETRAPHOSPHORUS LIGANDS ; RHODIUM CATALYST ; REGIOSELECTIVE HYDROFORMYLATION ; ASYMMETRIC HYDROFORMYLATION ; PROPYLENE CARBONATE
收录类别	SCI
语种	英语
WOS记录号	WOS:000410468300015
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/149924]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Peoples R China 2.Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China 3.Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China 4.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, Dalian 116023, Peoples R China 5.Yanshan Univ, Coll Environm & Chem Engn, Key Lab Appl Chem, Qinhuangdao 066004, Peoples R China
推荐引用方式 GB/T 7714	Jiang, Zheng,Li, Cunyao,Sun, Keju,et al. Xantphos doped Rh/POPs-PPh3 catalyst for highly selective long-chain olefins hydroformylation: Chemical and DFT insights into Rh location and the roles of Xantphos and PPh3[J]. JOURNAL OF CATALYSIS,2017,353:123-132.
APA	Jiang, Zheng.,Li, Cunyao.,Sun, Keju.,Wang, Wenlong.,Yan, Li.,...&Ding, Yunjie.(2017).Xantphos doped Rh/POPs-PPh3 catalyst for highly selective long-chain olefins hydroformylation: Chemical and DFT insights into Rh location and the roles of Xantphos and PPh3.JOURNAL OF CATALYSIS,353,123-132.
MLA	Jiang, Zheng,et al."Xantphos doped Rh/POPs-PPh3 catalyst for highly selective long-chain olefins hydroformylation: Chemical and DFT insights into Rh location and the roles of Xantphos and PPh3".JOURNAL OF CATALYSIS 353(2017):123-132.