Chemistry and the hydrogenases

Evans, David; Pickett, Christopher J.

doi:10.1039/b201317g

Cited by 601 publications

(384 citation statements)

References 52 publications

Supporting

Mentioning

372

Contrasting

Unclassified

Order By: Relevance

“…The noble metal, Pt, shows perfect activity for HER, however it is expensive and scarcity on earth. Meanwhile some natural enzymes which contains much less noble metals are also effective HER catalysts 33, 34. By comparing the active center of nitrogenase with different inorganic compounds, the Nørskov group found that the MoS 2 edge possess similar structure and was chosen as a candidate for HER 35.…”

Section: Edges As Active Sitesmentioning

confidence: 99%

Face the Edges: Catalytic Active Sites of Nanomaterials

Wang

2015

Advanced Science

156

View full text Add to dashboard Cite

Edges are special sites in nanomaterials. The atoms residing on the edges have different environments compared to those in other parts of a nanomaterial and, therefore, they may have different properties. Here, recent progress in nanomaterial fields is summarized from the viewpoint of the edges. Typically, edge sites in MoS2 or metals, other than surface atoms, can perform as active centers for catalytic reactions, so the method to enhance performance lies in the optimization of the edge structures. The edges of multicomponent interfaces present even more possibilities to enhance the activities of nanomaterials. Nanoframes and ultrathin nanowires have similarities to conventional edges of nanoparticles, the application of which as catalysts can help to reduce the use of costly materials. Looking beyond this, the edge structures of graphene are also essential for their properties. In short, the edge structure can influence many properties of materials.

show abstract

Section: Edges As Active Sitesmentioning

confidence: 99%

Face the Edges: Catalytic Active Sites of Nanomaterials

Wang

2015

Advanced Science

156

View full text Add to dashboard Cite

show abstract

“…2,3 Since the elucidation of the structures of both [NiFe]-and [FeFe]-hydrogenases revealed that these enzymes feature organometallic active sites including the diatomic ligands CO and CN (Figure 1), [4][5][6][7] inorganic chemists have sought to produce both structural and functional models in an effort to understand and reproduce these enzymes. 8 However, although natural hydrogenases have turnover frequencies exceeding 1000 s -1 at potentials close to the thermodynamic reduction potential of the proton, synthetic models seldom come close to this exquisite reactivity. 9,10 The active site of [FeFe]-hydrogenases, referred to as the H-cluster, is a unique six iron cluster consisting of a [4Fe4S] cluster bridged via a cysteinyl thiolate to a diiron subsite.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Hydrogen Evolution by Fe(II) Carbonyls Featuring a Dithiolate and a Chelating Phosphine

et al. 2014

View full text Add to dashboard Cite

Abstract:Two pentacoordinate mononuclear iron carbonyls of the form (bdt)Fe(CO)P 2 [bdt = benzene-1,2-dithiolate; P 2 = 1,1'-diphenylphosphinoferrocene (1) or methyl-2-{bis(diphenylphosphinomethyl)amino}acetate (2)] were prepared as functional, biomimetic models for the distal iron (Fe d ) of the active site of [FeFe]-hydrogenase. Xray crystal structures of the complexes reveal that, despite similar ν(CO) stretching band frequencies, the two complexes have different coordination geometries. In X-ray crystal structures, the iron center of 1 is in a distorted trigonal bipyramidal arrangement, and that of 2 is in a distorted square pyramidal geometry. Electrochemical investigation shows that both complexes catalyze electrochemical proton reduction from acetic acid at mild overpotential, 0.17 and 0.38 V for 1 and 2, respectively. Although coordinatively unsaturated, the complexes display only weak, reversible binding affinity towards CO(1 bar). However, ligand centered protonation by the strong acid, HBF 4 .OEt 2 , triggers quantitative CO uptake by 1 to form a dicarbonyl analogue [1(H)-CO] + that can be reversibly converted back to 1 by deprotonation using NEt 3 . Both crystallographically determined distances within the bdt ligand and DFT calculations suggest that the iron centers in both 1 and 2 are partially reduced at the expense of partial oxidation of the bdt ligand. Ligand protonation interrupts this extensive electronic delocalization between the Fe and bdt making 1(H) + susceptible to external CO binding.3

show abstract

“…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

View full text Add to dashboard Cite

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.

show abstract

Chemistry and the hydrogenases

Cited by 601 publications

References 52 publications

Face the Edges: Catalytic Active Sites of Nanomaterials

Face the Edges: Catalytic Active Sites of Nanomaterials

Catalytic Hydrogen Evolution by Fe(II) Carbonyls Featuring a Dithiolate and a Chelating Phosphine

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

Contact Info

Product

Resources

About