A cobalt hydride catalyst for the hydrogenation of CO2: Pathways for catalysis and deactivation

Matthew S. Jeletic; Monte L. Helm; Elliott B. Hulley; Michael T. Mock; Aaron M. Appel; John C. Linehan

doi:10.1021/cs5009927

A cobalt hydride catalyst for the hydrogenation of CO₂: Pathways for catalysis and deactivation

Matthew S. Jeletic, Monte L. Helm, Elliott B. Hulley, Michael T. Mock, Aaron M. Appel, John C. Linehan

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

70 Citations (Scopus)

Abstract

The complex Co(dmpe)₂H catalyzes the hydrogenation of CO₂ at 1 atm and 21 °C with significant improvement in turnover frequency relative to previously reported second- and third-row transition-metal complexes. New studies are presented to elucidate the catalytic mechanism as well as pathways for catalyst deactivation. The catalytic rate was optimized through the choice of the base to match the pK_a of the [Co(dmpe)₂(H)₂]⁺ intermediate. With a strong enough base, the catalytic rate has a zeroth-order dependence on the base concentration and the pressure of hydrogen and a first-order dependence on the pressure of CO₂. However, for CO₂:H₂ ratios greater than 1, the catalytically inactive species [(μ-dmpe)(Co(dmpe)₂)₂]²⁺ and [Co(dmpe)₂CO]⁺ were observed.

Original language	English
Pages (from-to)	3755-3762
Number of pages	8
Journal	ACS Catalysis
Volume	4
Issue number	10
DOIs	https://doi.org/10.1021/cs5009927
Publication status	Published - Oct 3 2014

Keywords

CO
catalysis
cobalt
high-pressure NMR
hydrogenation

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1021/cs5009927

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title = "A cobalt hydride catalyst for the hydrogenation of CO2: Pathways for catalysis and deactivation",

abstract = "The complex Co(dmpe)2H catalyzes the hydrogenation of CO2 at 1 atm and 21 °C with significant improvement in turnover frequency relative to previously reported second- and third-row transition-metal complexes. New studies are presented to elucidate the catalytic mechanism as well as pathways for catalyst deactivation. The catalytic rate was optimized through the choice of the base to match the pKa of the [Co(dmpe)2(H)2]+ intermediate. With a strong enough base, the catalytic rate has a zeroth-order dependence on the base concentration and the pressure of hydrogen and a first-order dependence on the pressure of CO2. However, for CO2:H2 ratios greater than 1, the catalytically inactive species [(μ-dmpe)(Co(dmpe)2)2]2+ and [Co(dmpe)2CO]+ were observed.",

keywords = "CO, catalysis, cobalt, high-pressure NMR, hydrogenation",

author = "Jeletic, {Matthew S.} and Helm, {Monte L.} and Hulley, {Elliott B.} and Mock, {Michael T.} and Appel, {Aaron M.} and Linehan, {John C.}",

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T1 - A cobalt hydride catalyst for the hydrogenation of CO2

T2 - Pathways for catalysis and deactivation

AU - Jeletic, Matthew S.

AU - Helm, Monte L.

AU - Hulley, Elliott B.

AU - Mock, Michael T.

AU - Appel, Aaron M.

AU - Linehan, John C.

PY - 2014/10/3

Y1 - 2014/10/3

N2 - The complex Co(dmpe)2H catalyzes the hydrogenation of CO2 at 1 atm and 21 °C with significant improvement in turnover frequency relative to previously reported second- and third-row transition-metal complexes. New studies are presented to elucidate the catalytic mechanism as well as pathways for catalyst deactivation. The catalytic rate was optimized through the choice of the base to match the pKa of the [Co(dmpe)2(H)2]+ intermediate. With a strong enough base, the catalytic rate has a zeroth-order dependence on the base concentration and the pressure of hydrogen and a first-order dependence on the pressure of CO2. However, for CO2:H2 ratios greater than 1, the catalytically inactive species [(μ-dmpe)(Co(dmpe)2)2]2+ and [Co(dmpe)2CO]+ were observed.

AB - The complex Co(dmpe)2H catalyzes the hydrogenation of CO2 at 1 atm and 21 °C with significant improvement in turnover frequency relative to previously reported second- and third-row transition-metal complexes. New studies are presented to elucidate the catalytic mechanism as well as pathways for catalyst deactivation. The catalytic rate was optimized through the choice of the base to match the pKa of the [Co(dmpe)2(H)2]+ intermediate. With a strong enough base, the catalytic rate has a zeroth-order dependence on the base concentration and the pressure of hydrogen and a first-order dependence on the pressure of CO2. However, for CO2:H2 ratios greater than 1, the catalytically inactive species [(μ-dmpe)(Co(dmpe)2)2]2+ and [Co(dmpe)2CO]+ were observed.

KW - CO

KW - catalysis

KW - cobalt

KW - high-pressure NMR

KW - hydrogenation

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