Electrochemical reduction of protonated cyclopentadienylcobalt phosphine complexes

Koelle, U.; Paul, S.

doi:10.1021/ic00236a007

Cited by 125 publications

(116 citation statements)

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“…Synthetic catalysts compare favorably to, and in some cases exceed, the efficiency of the biomimetic models. In the presence of sacrificial chemical reductants, mononuclear and binuclear metal complexes of Co, Ni, and Rh are known to effect catalytic hydrogen evolution electrochemically or photochemically (28)(29)(30)(31)(32)(33)(34)(35)(36). Intimate mechanistic details, however, are known in only a few cases (37), and the different possibilities, such as protonation of a hydride vs. uni-or bimolecular reductive elimination (right side, WS1, Scheme 2), in general have not yet been unraveled.…”

Section: Methodsmentioning

confidence: 99%

Powering the planet: Chemical challenges in solar energy utilization

Lewis

Nocera

2006

Proc. Natl. Acad. Sci. U.S.A.

7,595

5,540

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Global energy consumption is projected to increase, even in the face of substantial declines in energy intensity, at least 2-fold by midcentury relative to the present because of population and economic growth. This demand could be met, in principle, from fossil energy resources, particularly coal. However, the cumulative nature of CO 2 emissions in the atmosphere demands that holding atmospheric CO 2 levels to even twice their preanthropogenic values by midcentury will require invention, development, and deployment of schemes for carbon-neutral energy production on a scale commensurate with, or larger than, the entire present-day energy supply from all sources combined. Among renewable energy resources, solar energy is by far the largest exploitable resource, providing more energy in 1 hour to the earth than all of the energy consumed by humans in an entire year. In view of the intermittency of insolation, if solar energy is to be a major primary energy source, it must be stored and dispatched on demand to the end user. An especially attractive approach is to store solar-converted energy in the form of chemical bonds, i.e., in a photosynthetic process at a year-round average efficiency significantly higher than current plants or algae, to reduce land-area requirements. Scientific challenges involved with this process include schemes to capture and convert solar energy and then store the energy in the form of chemical bonds, producing oxygen from water and a reduced fuel such as hydrogen, methane, methanol, or other hydrocarbon species.

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Section: Methodsmentioning

confidence: 99%

Powering the planet: Chemical challenges in solar energy utilization

Lewis

Nocera

2006

Proc. Natl. Acad. Sci. U.S.A.

7,595

5,540

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“…Electrocatalysis of this reaction can be achieved homogeneously via protonation and electrochemical (or photochemical) reduction of a suitable Brønsted base in solution [4,5]. Advances in this area have afforded molecular electrocatalysts that employ cobalt, molybdenum, nickel, or iron [6][7][8][9][10][11], instead of platinum that is currently the preferred electrocatalyst for proton reduction in water [12].…”

Section: Introductionmentioning

confidence: 99%

Kinetic and thermodynamic aspects of the electrocatalysis of acid reduction in organic solvent using molecular diiron-dithiolate compounds

Quentel

Gloaguen

2013

Electrochimica Acta

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To cite this version:Francois Quentel, Frederic Gloaguen. Kinetic and thermodynamic aspects of the electrocatalysis of acid reduction in organic solvent using molecular diiron-dithiolate compounds. 2015. AbstractIn an attempt to obtain molecular H 2 production electrocatalysts achieving balanced basicity and reduction potential, we focused on the mono-substituted diiron-dithiolate derivative [Fe 2 (µ-bdt)(CO) 5 (P(OMe) 3 )] (bdt = benzenedithiolate). The electrocatalytic efficiency of this iron-iron hydrogenase model was determined by cyclic voltammetry in acetonitrile using ptoluenesulfonic acid as a proton source. Detailed analysis of the current -potential responses and comparison with the all-CO diiron-dithiolate parent compound clearly show that the effect of the chemical properties on the electrocatalytic efficiency is not fully determined by the turnover frequency under pseudo-first-order approximation and the overpotential defined as the difference between the reduction potential of the electrocatalysts in the absence of acid and the reversible potential of the couple H 2 /acid.

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“…3,4,6 Transition metal complexes that are structurally distinct from the hydrogenase H-cluster effect catalytic hydrogen evolution at comparable, and in some cases more positive, potentials than the biomimetic diiron model systems. Cobaltocene, 7 [CpCo(PR 3 ) 2 ] + , 8 metalloporphyrins, 9 and certain macrocyclic complexes of cobalt 10,11 and nickel, 12 effect catalytic hydrogen evolution either in the presence of sacrificial chemical reductants or electrocatalytically.…”

mentioning

confidence: 99%

Electrocatalytic hydrogen evolution by cobalt difluoroboryl-diglyoximate complexes

et al. 2005

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In the presence of moderately strong acids in CH 3 CN, cobalt complexes with BF 2 -bridged diglyoxime ligands are active catalysts for the reduction of protons to H 2 at potentials as positive as 20.28 V vs. SCE.The search for transition metal complexes that are capable of catalyzing the reduction of protons to dihydrogen at low overpotentials presents an exciting challenge for coordination chemists.1 Much attention has been drawn to structural and functional models of the active sites of hydrogenases, especially the H-clusters of the Fe-only hydrogenases, which feature dithiolatebridged, bimetallic iron cofactors that are rich in CO and CN 2 auxiliary ligands.2,3 The Fe-only hydrogenases catalyze the reduction of protons to dihydrogen at the thermodynamic potential for H 2 uptake/production (ca. 20.41 V vs. NHE at pH 5 7 in water, or ca. 20.65 vs. SCE), 4,5 whereas current biomimetic model compounds only catalyze hydrogen evolution at significantly more negative potentials (from ca. 21.1 to 22 V vs. SCE).3,4,6 Transition metal complexes that are structurally distinct from the hydrogenase H-cluster effect catalytic hydrogen evolution at comparable, and in some cases more positive, potentials than the biomimetic diiron model systems.

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Electrochemical reduction of protonated cyclopentadienylcobalt phosphine complexes

Cited by 125 publications

References 0 publications

Powering the planet: Chemical challenges in solar energy utilization

Powering the planet: Chemical challenges in solar energy utilization

Kinetic and thermodynamic aspects of the electrocatalysis of acid reduction in organic solvent using molecular diiron-dithiolate compounds

Electrocatalytic hydrogen evolution by cobalt difluoroboryl-diglyoximate complexes

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