Catalysis of the electrochemical H evolution by di-iron sub-site models

Capon, Jean‐François; Gloaguen, Frédéric; Schollhammer, Philippe; Talarmin, Jean

doi:10.1016/j.ccr.2004.11.018

Cited by 253 publications

(190 citation statements)

References 50 publications

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“…In the presence of acetic acid (HOAc) both complexes are efficient electrocatalysts for the reduction of protons to molecular hydrogen (acetonitrile, glassy carbon cathode, SI Appendix), in line with previous observations (18). The electrocatalytic proton reduction potentials coincide with the Fe 0 Fe I reduction of complexes 1 and 2, being shifted 500 mV less negatively than the proton reduction under identical conditions (Fig.…”

Section: Resultssupporting

confidence: 89%

“…The elucidation of the protein structure of the [2Fe2S]hydrogenases revealed their active center (14), which has served as a huge impetus for synthetic chemists exploring properties of its structural models (15)(16)(17). It has already been demonstrated that several of these models are active electrocatalysts, producing molecular hydrogen when a certain cathodic potential is applied (18). † The structure of the Fe 2 (-S 2 ) core appears crucial for this activity, but the remaining ligands attached to the active site, in the natural systems generally CO, CN Ϫ , and thiolate-sulfur, can be replaced without much consequence (although the cyanide ligand can be protonated to [Fe]CNH) (21).…”

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confidence: 99%

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Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

Kluwer

Kapre²,

Hartl³

et al. 2009

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

211

137

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The large-scale production of clean energy is one of the major challenges society is currently facing. Molecular hydrogen is envisaged as a key green fuel for the future, but it becomes a sustainable alternative for classical fuels only if it is also produced in a clean fashion. Here, we report a supramolecular biomimetic approach to form a catalyst that produces molecular hydrogen using light as the energy source. It is composed of an assembly of chromophores to a bis(thiolate)-bridged diiron ([2Fe2S]) based hydrogenase catalyst. The supramolecular building block approach introduced in this article enabled the easy formation of a series of complexes, which are all thoroughly characterized, revealing that the photoactivity of the catalyst assembly strongly depends on its nature. The active species, formed from different complexes, appears to be the [Fe 2(-pdt)(CO)4{PPh2(4-py)}2] (3) with 2 different types of porphyrins (5a and 5b) coordinated to it. The modular supramolecular approach was important in this study as with a limited number of building blocks several different complexes were generated.photocatalysis ͉ self-assembly ͉ supramolecular chemistry ͉ metalloporphyrin chromophore ͉ Stern-Volmer plot S upramolecular chemistry, defined by Nobel Prize Laureate Jean-Marie Lehn as the ''chemistry beyond the molecule,'' has changed the way we look at molecules (1). Besides exploring reactivity of molecules, interaction between molecules has become of dominant importance as it provides new means of controlling properties of chemical systems. Supramolecular chemistry has rapidly evolved into a mature field, and the implementation of supramolecular strategies has resulted in breakthroughs in several disciplines (2-4). The reversible character of noncovalent chemistry gives rise to concepts such as adaptation and self-correction, creating fundamentally different system properties compared with traditional covalent strategies. The modular character associated with the building block approach in supramolecular chemistry provides an easy strategy to generate large libraries of analogous structures of nanosize dimension. Such libraries are of interest in research areas where accurate prediction of particular properties of chemical systems is inadequate or impossible. For example, means to predict the selectivity provided by transition metal catalyst are lacking, and therefore high throughput screening of libraries of catalysts is still the most powerful method to find catalyst systems with desired selectivities. Indeed, we and others have introduced supramolecular ways to make transition metal catalysts and used the building block approach to create large libraries of related catalysts, some of which show unrivaled selectivities (5-9).Stimulated by these exciting results, we were wondering whether supramolecular strategies could also provide solutions to other challenges in catalysis. One of the greatest challenges our society is currently facing is the large-scale production of clean energy (10). Molecular hydrogen is e...

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Section: Resultssupporting

confidence: 89%

mentioning

confidence: 99%

Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

Kluwer

Kapre²,

Hartl³

et al. 2009

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

211

137

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“…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]. Given the interest of developing H 2 -production electrocatalysts based on cheap and abundant materials, synthetic models of the iron-iron hydrogenase enzymes have been the subject of numerous studies [13][14][15][16][17][18]. Diiron-dithiolate compounds of the type [Fe 2 (µ-SRS)(CO) 6-x L x ] (R = organic group, L = electron-donor ligand, x ≤ 4) have been shown to electrocatalyze the reduction of acid in organic solvents [19][20][21] and, very recently, in aqueous micellar solutions [22,23](for examples of photo-driven H 2 -production by diiron-dithiolate compounds see [24,25]).…”

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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“…Dithiolate-bridged diiron complexes of the type [Fe 2 (CO) 6 -(l-dithiolate)] have been intensely studied [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] due to their structural resemblance with the two-iron unit of the H-cluster active site of [FeFe]-hydrogenases, enzymes that catalyse the reversible interconversion of protons-electrons and hydrogen. A key step in electrocatalytic proton reduction is protonation of the diiron centre, but [Fe 2 (CO) 6 (l-dithiolate)] complexes are not basic enough to undergo protonation except by extremely strong acids [20][21][22].…”

Section: Introductionmentioning

confidence: 99%

A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2) n S}] (M = Fe, Ru; n = 2, 3)

2017

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A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M 2 (CO) 4 (l-dppm){l-S(CH 2 ) n S}] (M 5 Fe, Ru; n 5 2, 3) -diphosphine)(l-dithiolate)]. Consequently a large number of diphosphine-bridged diiron-dithiolate complexes have been reported [23][24][25][26][27][28][29][30][31][32] but surprisingly little attention has been paid to their proton-reduction chemistry [27-32] even though some, for example [Fe 2 (CO) 4 (l-dppf)(l-pdt)] (dppf = 1,1 0 -bis(diphenylphosphino)ferrocene), have been shown to be efficient proton-reduction catalysts [29]. Similarly, given the large number of diiron complexes tested as proton-reduction catalysts, related diruthenium complexes have not been widely studied [53][54][55][56]. Herein we detail a comparative investigation of the electrochemistry and proton-reduction behaviour of diiron and diruthenium complexes [M 2 (CO) 4 (ldppm)(l-pdt)] [24,27,57] and [M 2 (CO) 4 (l-dppm)(l-edt)] [26,27,57] (Fig. 1). ExperimentalComplexes 1-4 were prepared according to published methods [24,26,27,57] (see ESI for details). IR spectra were recorded on a Nicolet 6700 FT-IR spectrometer in a solution cell fitted with calcium fluoride plates, subtraction Electronic supplementary material The online version of this article

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Catalysis of the electrochemical H evolution by di-iron sub-site models

Cited by 253 publications

References 50 publications

Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

Self-assembled biomimetic [2Fe2S]-hydrogenase-based photocatalyst for molecular hydrogen evolution

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

A comparative study of the electrochemical and proton-reduction behaviour of diphosphine-dithiolate complexes [M2(CO)4(μ-dppm){μ-S(CH2) n S}] (M = Fe, Ru; n = 2, 3)

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