Homogeneous hydrogenation of CO2 to methyl formate utilizing switchable ionic liquids

Mahendra Yadav, John Linehan, Abhijeet J. Karkamkar, Edwin Van Der Eide, David J. Heldebrant

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Combined capture of CO2 and subsequent hydrogenation allows for base/methanol-promoted homogeneous hydrogenation of CO2 to methyl formate. The CO2, captured as an amidinium methyl carbonate, reacts with H2 with no applied pressure of CO2 in the presence of a catalyst to produce sequentially amidinium formate, then methyl formate. The production of methyl formate releases the base back into the system, thereby reducing one of the flaws of catalytic hydrogenations of CO2: the notable consumption of one mole of base per mole of formate produced. The reaction proceeds under 20 atm of H2 with selectivity to formate favored by the presence of excess base and lower temperatures (110 °C), while excess alcohol and higher temperatures (140 °C) favor methyl formate. Known CO2 hydrogenation catalysts are active in the ionic liquid medium with turnover numbers as high as 5000. It is unclear as to whether the alkyl carbonate or CO2 is hydrogenated, as we show they are in equilibrium in this system. The availability of both CO2 and the alkyl carbonate as reactive species may result in new catalyst designs and free energy pathways for CO2 that may entail different selectivity or kinetic activity.

Original languageEnglish
Pages (from-to)9849-9854
Number of pages6
JournalInorganic Chemistry
Volume53
Issue number18
DOIs
Publication statusPublished - Sep 15 2014

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Ionic Liquids
formic acid
formates
Hydrogenation
hydrogenation
Carbonates
liquids
Catalysts
carbonates
catalysts
Free energy
Methanol
selectivity
Alcohols
Availability
Temperature
Defects
Kinetics
methyl formate
availability

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Homogeneous hydrogenation of CO2 to methyl formate utilizing switchable ionic liquids. / Yadav, Mahendra; Linehan, John; Karkamkar, Abhijeet J.; Van Der Eide, Edwin; Heldebrant, David J.

In: Inorganic Chemistry, Vol. 53, No. 18, 15.09.2014, p. 9849-9854.

Research output: Contribution to journalArticle

Yadav, M, Linehan, J, Karkamkar, AJ, Van Der Eide, E & Heldebrant, DJ 2014, 'Homogeneous hydrogenation of CO2 to methyl formate utilizing switchable ionic liquids', Inorganic Chemistry, vol. 53, no. 18, pp. 9849-9854. https://doi.org/10.1021/ic501378w
Yadav, Mahendra ; Linehan, John ; Karkamkar, Abhijeet J. ; Van Der Eide, Edwin ; Heldebrant, David J. / Homogeneous hydrogenation of CO2 to methyl formate utilizing switchable ionic liquids. In: Inorganic Chemistry. 2014 ; Vol. 53, No. 18. pp. 9849-9854.
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