Ultrastable 3V-PPh<inf>3</inf> polymers supported single Rh sites for fixed-bed hydroformylation of olefins

Miao Jiang, Li Yan, Yunjie Ding, Qi Sun, Jia Liu, Hejun Zhu, Ronghe Lin, Fengshou Xiao, Zheng Jiang, Jingyue Liu

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The heterogenization of homogeneous catalysts is of critical importance for both fundamental research and practical applications. The key obstacle to industrial applications of heterogenized homogeneous catalysts is the long-term stability of the immobilized molecular complexes. We unambiguously demonstrate in this report that the vinyl-functionalized PPh<inf>3</inf> polymers supported single Rh sites (Rh/POL-PPh<inf>3</inf>) catalyst provided not only excellent catalytic activity but also ultrahigh stability for fixed-bed olefins hydroformylation, which is one of the most important industrial homogeneous catalytic processes for the synthesis of aldehydes and alcohols. HAADF-STEM and EXAFS results indicated that the Rh atoms were present in single Rh sites which were strongly coordinated with the exposed phosphorous atoms of the POL-PPh<inf>3</inf> support. The Rh/POL-PPh<inf>3</inf> catalyst provided high activity and selectivity because it maintained the catalytic functionalities similar to the homogeneous HRh(CO)(PPh<inf>3</inf>)<inf>3</inf> complex, as demonstrated both by <sup>31</sup>P MAS NMR and in situ FT-IR experiments. Thus a reaction mechanism, similar to that over the homogeneous HRh(CO)(PPh<inf>3</inf>)<inf>3</inf> complex, was proposed for olefin hydroformylation over the novel Rh/POL-PPh<inf>3</inf> catalyst.

Original languageEnglish (US)
Pages (from-to)211-217
Number of pages7
JournalJournal of Molecular Catalysis A: Chemical
Volume404-405
DOIs
StatePublished - May 30 2015

Fingerprint

Hydroformylation
Alkenes
alkenes
Olefins
beds
Polymers
catalysts
Catalysts
polymers
Carbon Monoxide
Catalyst activity
Atoms
Catalyst selectivity
Aldehydes
aldehydes
Catalyst supports
Industrial applications
atoms
catalytic activity
alcohols

Keywords

  • Heterogenized catalysts
  • Hydroformylation
  • Porous organic ligands
  • Rhodium
  • Stability

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Process Chemistry and Technology

Cite this

Ultrastable 3V-PPh<inf>3</inf> polymers supported single Rh sites for fixed-bed hydroformylation of olefins. / Jiang, Miao; Yan, Li; Ding, Yunjie; Sun, Qi; Liu, Jia; Zhu, Hejun; Lin, Ronghe; Xiao, Fengshou; Jiang, Zheng; Liu, Jingyue.

In: Journal of Molecular Catalysis A: Chemical, Vol. 404-405, 30.05.2015, p. 211-217.

Research output: Contribution to journalArticle

Jiang, Miao ; Yan, Li ; Ding, Yunjie ; Sun, Qi ; Liu, Jia ; Zhu, Hejun ; Lin, Ronghe ; Xiao, Fengshou ; Jiang, Zheng ; Liu, Jingyue. / Ultrastable 3V-PPh<inf>3</inf> polymers supported single Rh sites for fixed-bed hydroformylation of olefins. In: Journal of Molecular Catalysis A: Chemical. 2015 ; Vol. 404-405. pp. 211-217.
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AU - Yan, Li

AU - Ding, Yunjie

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AU - Liu, Jia

AU - Zhu, Hejun

AU - Lin, Ronghe

AU - Xiao, Fengshou

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AB - The heterogenization of homogeneous catalysts is of critical importance for both fundamental research and practical applications. The key obstacle to industrial applications of heterogenized homogeneous catalysts is the long-term stability of the immobilized molecular complexes. We unambiguously demonstrate in this report that the vinyl-functionalized PPh3 polymers supported single Rh sites (Rh/POL-PPh3) catalyst provided not only excellent catalytic activity but also ultrahigh stability for fixed-bed olefins hydroformylation, which is one of the most important industrial homogeneous catalytic processes for the synthesis of aldehydes and alcohols. HAADF-STEM and EXAFS results indicated that the Rh atoms were present in single Rh sites which were strongly coordinated with the exposed phosphorous atoms of the POL-PPh3 support. The Rh/POL-PPh3 catalyst provided high activity and selectivity because it maintained the catalytic functionalities similar to the homogeneous HRh(CO)(PPh3)3 complex, as demonstrated both by 31P MAS NMR and in situ FT-IR experiments. Thus a reaction mechanism, similar to that over the homogeneous HRh(CO)(PPh3)3 complex, was proposed for olefin hydroformylation over the novel Rh/POL-PPh3 catalyst.

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