Acidic ionic liquid/water solution as both medium and proton source for electrocatalytic H2 evolution by [Ni(P2N2) 2]2+ complexes

Douglas H. Pool, Michael P. Stewart, Molly O'Hagan, Wendy J. Shaw, John Roberts, R Morris Bullock, Daniel L DuBois

Research output: Contribution to journalArticle

60 Citations (Scopus)

Abstract

The electrocatalytic reduction of protons to H2 by [Ni(P Ph 2NC6H4-hex 2)2](BF 4)2 (where PPh 2N C6H4-hex 2 = 1,5-di(4-n-hexylphenyl)-3,7-diphenyl-1,5- diaza-3,7-diphosphacyclooctane) in the highly acidic ionic liquid dibutylformamidium bis(trifluoromethanesulfonyl)amide shows a strong dependence on added water. A turnover frequency of 43,000-53,000 s-1 has been measured for hydrogen production at 25°C when the mole fraction of water (χH2O) is 0.72. The same catalyst in acetonitrile with added dimethylformamidium trifluoromethanesulfonate and water has a turnover frequency of 720 s-1. Thus, the use of an ionic liquid/aqueous solution enhances the observed catalytic rate by more than a factor of 50, compared to a similar acid in a traditional organic solvent. Complexes [Ni(PPh 2NC6H4X 2)2](BF4) 2 (X = H, OMe,CH2P(O)(OEt)2, Br) are also catalysts in the ionic liquid/water mixture, and the observed catalytic rates correlate with the hydrophobicity of X.

Original languageEnglish
Pages (from-to)15634-15639
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume109
Issue number39
DOIs
Publication statusPublished - Sep 25 2012

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Ionic Liquids
Protons
Water
Hydrophobic and Hydrophilic Interactions
Hydrogen
Acids

Keywords

  • Electrocatalysis
  • Homogeneous
  • Hydrogenase
  • Proton relay
  • Renewable energy

ASJC Scopus subject areas

  • General

Cite this

Acidic ionic liquid/water solution as both medium and proton source for electrocatalytic H2 evolution by [Ni(P2N2) 2]2+ complexes. / Pool, Douglas H.; Stewart, Michael P.; O'Hagan, Molly; Shaw, Wendy J.; Roberts, John; Bullock, R Morris; DuBois, Daniel L.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 109, No. 39, 25.09.2012, p. 15634-15639.

Research output: Contribution to journalArticle

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AU - Stewart, Michael P.

AU - O'Hagan, Molly

AU - Shaw, Wendy J.

AU - Roberts, John

AU - Bullock, R Morris

AU - DuBois, Daniel L

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AB - The electrocatalytic reduction of protons to H2 by [Ni(P Ph 2NC6H4-hex 2)2](BF 4)2 (where PPh 2N C6H4-hex 2 = 1,5-di(4-n-hexylphenyl)-3,7-diphenyl-1,5- diaza-3,7-diphosphacyclooctane) in the highly acidic ionic liquid dibutylformamidium bis(trifluoromethanesulfonyl)amide shows a strong dependence on added water. A turnover frequency of 43,000-53,000 s-1 has been measured for hydrogen production at 25°C when the mole fraction of water (χH2O) is 0.72. The same catalyst in acetonitrile with added dimethylformamidium trifluoromethanesulfonate and water has a turnover frequency of 720 s-1. Thus, the use of an ionic liquid/aqueous solution enhances the observed catalytic rate by more than a factor of 50, compared to a similar acid in a traditional organic solvent. Complexes [Ni(PPh 2NC6H4X 2)2](BF4) 2 (X = H, OMe,CH2P(O)(OEt)2, Br) are also catalysts in the ionic liquid/water mixture, and the observed catalytic rates correlate with the hydrophobicity of X.

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