Highly Efficient Activation, Regeneration, and Active Site Identification of Oxide-Based Olefin Metathesis Catalysts

Kunlun Ding, Ahmet Gulec, Alexis M. Johnson, Tasha L. Drake, Weiqiang Wu, Yuyuan Lin, Eric Weitz, Laurence D. Marks, Peter C Stair

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Supported metal oxide based olefin metathesis catalysts are widely used in the chemical industry. In comparison to their organometallic catalyst cousins, the oxide catalysts have much lower activity due to the very small fraction of active sites. We report that a simple pretreatment of MoO3/SiO2 and WO3/SiO2 under an olefin-containing atmosphere at elevated temperatures leads to a 100-1000-fold increase in the low-temperature propylene metathesis activity. The performance of these catalysts is comparable with those of the well-defined organometallic catalysts. Unprecedentedly, the catalyst can be easily regenerated by inert gas purging at elevated temperatures. Furthermore, using UV resonance Raman spectroscopy and electron microscopy, we provide strong evidence that the active sites for MoO3/SiO2 are derived from monomeric Mo(=O)2 dioxo species.

Original languageEnglish
Pages (from-to)5740-5746
Number of pages7
JournalACS Catalysis
Volume6
Issue number9
DOIs
Publication statusPublished - Sep 2 2016

Fingerprint

Alkenes
Oxides
Olefins
Chemical activation
Catalysts
Organometallics
Noble Gases
Purging
Chemical industry
Inert gases
Temperature
Electron microscopy
Propylene
Raman spectroscopy
Metals

Keywords

  • activation
  • active site
  • metal oxides
  • olefin metathesis
  • regeneration

ASJC Scopus subject areas

  • Catalysis

Cite this

Highly Efficient Activation, Regeneration, and Active Site Identification of Oxide-Based Olefin Metathesis Catalysts. / Ding, Kunlun; Gulec, Ahmet; Johnson, Alexis M.; Drake, Tasha L.; Wu, Weiqiang; Lin, Yuyuan; Weitz, Eric; Marks, Laurence D.; Stair, Peter C.

In: ACS Catalysis, Vol. 6, No. 9, 02.09.2016, p. 5740-5746.

Research output: Contribution to journalArticle

Ding, Kunlun ; Gulec, Ahmet ; Johnson, Alexis M. ; Drake, Tasha L. ; Wu, Weiqiang ; Lin, Yuyuan ; Weitz, Eric ; Marks, Laurence D. ; Stair, Peter C. / Highly Efficient Activation, Regeneration, and Active Site Identification of Oxide-Based Olefin Metathesis Catalysts. In: ACS Catalysis. 2016 ; Vol. 6, No. 9. pp. 5740-5746.
@article{a5d8ee1dcc4f4302a6cd1fffadbd0a67,
title = "Highly Efficient Activation, Regeneration, and Active Site Identification of Oxide-Based Olefin Metathesis Catalysts",
abstract = "Supported metal oxide based olefin metathesis catalysts are widely used in the chemical industry. In comparison to their organometallic catalyst cousins, the oxide catalysts have much lower activity due to the very small fraction of active sites. We report that a simple pretreatment of MoO3/SiO2 and WO3/SiO2 under an olefin-containing atmosphere at elevated temperatures leads to a 100-1000-fold increase in the low-temperature propylene metathesis activity. The performance of these catalysts is comparable with those of the well-defined organometallic catalysts. Unprecedentedly, the catalyst can be easily regenerated by inert gas purging at elevated temperatures. Furthermore, using UV resonance Raman spectroscopy and electron microscopy, we provide strong evidence that the active sites for MoO3/SiO2 are derived from monomeric Mo(=O)2 dioxo species.",
keywords = "activation, active site, metal oxides, olefin metathesis, regeneration",
author = "Kunlun Ding and Ahmet Gulec and Johnson, {Alexis M.} and Drake, {Tasha L.} and Weiqiang Wu and Yuyuan Lin and Eric Weitz and Marks, {Laurence D.} and Stair, {Peter C}",
year = "2016",
month = "9",
day = "2",
doi = "10.1021/acscatal.6b00098",
language = "English",
volume = "6",
pages = "5740--5746",
journal = "ACS Catalysis",
issn = "2155-5435",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

T1 - Highly Efficient Activation, Regeneration, and Active Site Identification of Oxide-Based Olefin Metathesis Catalysts

AU - Ding, Kunlun

AU - Gulec, Ahmet

AU - Johnson, Alexis M.

AU - Drake, Tasha L.

AU - Wu, Weiqiang

AU - Lin, Yuyuan

AU - Weitz, Eric

AU - Marks, Laurence D.

AU - Stair, Peter C

PY - 2016/9/2

Y1 - 2016/9/2

N2 - Supported metal oxide based olefin metathesis catalysts are widely used in the chemical industry. In comparison to their organometallic catalyst cousins, the oxide catalysts have much lower activity due to the very small fraction of active sites. We report that a simple pretreatment of MoO3/SiO2 and WO3/SiO2 under an olefin-containing atmosphere at elevated temperatures leads to a 100-1000-fold increase in the low-temperature propylene metathesis activity. The performance of these catalysts is comparable with those of the well-defined organometallic catalysts. Unprecedentedly, the catalyst can be easily regenerated by inert gas purging at elevated temperatures. Furthermore, using UV resonance Raman spectroscopy and electron microscopy, we provide strong evidence that the active sites for MoO3/SiO2 are derived from monomeric Mo(=O)2 dioxo species.

AB - Supported metal oxide based olefin metathesis catalysts are widely used in the chemical industry. In comparison to their organometallic catalyst cousins, the oxide catalysts have much lower activity due to the very small fraction of active sites. We report that a simple pretreatment of MoO3/SiO2 and WO3/SiO2 under an olefin-containing atmosphere at elevated temperatures leads to a 100-1000-fold increase in the low-temperature propylene metathesis activity. The performance of these catalysts is comparable with those of the well-defined organometallic catalysts. Unprecedentedly, the catalyst can be easily regenerated by inert gas purging at elevated temperatures. Furthermore, using UV resonance Raman spectroscopy and electron microscopy, we provide strong evidence that the active sites for MoO3/SiO2 are derived from monomeric Mo(=O)2 dioxo species.

KW - activation

KW - active site

KW - metal oxides

KW - olefin metathesis

KW - regeneration

UR - http://www.scopus.com/inward/record.url?scp=84984910880&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84984910880&partnerID=8YFLogxK

U2 - 10.1021/acscatal.6b00098

DO - 10.1021/acscatal.6b00098

M3 - Article

VL - 6

SP - 5740

EP - 5746

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 9

ER -