From Enzymes to Functional Materials—Towards Activation of Small Molecules

Möller, F.; Piontek, Stefan; Miller, Reece G.; Apfel, Ulf‐Peter

doi:10.1002/chem.201703451

Cited by 58 publications

(59 citation statements)

References 393 publications

(786 reference statements)

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“…Activation of ubiquitous small molecules -that is, chemically simple, naturally abundant and low molecular weight starting reagents -is a primary task with potential impact both in synthetic and energy-oriented strategies. [1][2][3] Two of the most targeted molecules are water and carbon dioxide: they represent the richest source of hydrogen and carbon in nature. In particular, the activation of CO 2 [4][5][6][7] and its subsequent conversion into useful chemicals upon reduction processes, is a primary goal of artificial photosynthesis, aiming at the production of renewable fuels by exploiting solar light.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Conversion of CO₂ to CO by a Competent Fe^I Intermediate Bearing a Schiff Base Ligand

et al. 2020

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Iron complexes with a N2O2‐type N,N′‐bis(salicylaldehyde)‐1,2‐phenylenediamine salophen ligand catalyze the electrochemical reduction of CO2 to CO in acetonitrile with phenol as the proton donor, giving rise to 90–99 % selectivity, faradaic efficiency up to 58 %, and turnover frequency up to 103 s−1 at an overpotential of 0.65 V. This novel class of molecular catalyst for CO2 reduction operate through a mononuclear FeI intermediate, with phenol being involved in the process with first‐order kinetics. The molecular nature of the catalyst and the low cost, easy synthesis and functionalization of the salophen ligand paves the way for catalyst engineering and optimization. Competitive electrodeposition of the coordination complex at the electrode surface results in the formation of iron‐based nanoparticles, which are active towards heterogeneous electrocatalytic processes mainly leading to proton reduction to hydrogen (faradaic efficiency up to 80 %) but also to the direct reduction of CO2 to methane with a faradaic efficiency of 1–2 %.

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Section: Introductionmentioning

confidence: 99%

Electrochemical Conversion of CO₂ to CO by a Competent Fe^I Intermediate Bearing a Schiff Base Ligand

et al. 2020

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“…An in-depth understanding of the hydrogenases' active site structural properties and reactivity is crucial to develop new catalysts for an efficient H 2 production. 4 The potential for technical applications of such bioinspired approaches was recently demonstrated at the example of Fe 4.5 Ni 4.5 S 8 . [5][6][7] This mineral compound reveals striking similarities with the [NiFe]hydrogenase cofactor (Fig.…”

Section: Introductionmentioning

confidence: 99%

[FeFe]-Hydrogenases: recent developments and future perspectives

et al. 2018

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[FeFe]-Hydrogenases are the most efficient enzymes for catalytic hydrogen turnover. Their H2 production efficiency is hitherto unrivalled. However, functional details of the catalytic machinery and possible modes of application are discussed controversially. The incorporation of synthetically modified cofactors and utilization of semi-artificial enzymes only recently allowed us to shed light on key steps of the catalytic cycle. Herein, we summarize the essential findings regarding the redox chemistry of [FeFe]-hydrogenases and discuss their catalytic hydrogen turnover. We furthermore will give an outlook on potential research activities and exploit the utilization of synthetic cofactor mimics.

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“…[1] The bioinorganic cofactors of hydrogenases represent natural blueprints for the design of catalysts with potential value in sustainable H2 production. [2][3][4][5][6] For example, in [FeFe]-hydrogenases a [6Fe-6S] complex has been identified. [7,8] The "H-cluster" comprises a canonical, low-spin [4Fe-4S] cluster covalently linked to a unique diiron site (Fig.…”

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Proton‐Coupled Reduction of the Catalytic [4Fe‐4S] Cluster in [FeFe]‐Hydrogenases

et al. 2017

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In nature, [FeFe]-hydrogenases catalyze the uptake and release of molecular hydrogen (H ) at a unique iron-sulfur cofactor. The absence of an electrochemical overpotential in the H release reaction makes [FeFe]-hydrogenases a prime example of efficient biocatalysis. However, the molecular details of hydrogen turnover are not yet fully understood. Herein, we characterize the initial one-electron reduction of [FeFe]-hydrogenases by infrared spectroscopy and electrochemistry and present evidence for proton-coupled electron transport during the formation of the reduced state Hred'. Charge compensation stabilizes the excess electron at the [4Fe-4S] cluster and maintains a conservative configuration of the diiron site. The role of Hred' in hydrogen turnover and possible implications on the catalytic mechanism are discussed. We propose that regulation of the electronic properties in the periphery of metal cofactors is key to orchestrating multielectron processes.

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From Enzymes to Functional Materials—Towards Activation of Small Molecules

Cited by 58 publications

References 393 publications

Electrochemical Conversion of CO₂ to CO by a Competent Fe^I Intermediate Bearing a Schiff Base Ligand

Electrochemical Conversion of CO₂ to CO by a Competent Fe^I Intermediate Bearing a Schiff Base Ligand

[FeFe]-Hydrogenases: recent developments and future perspectives

Proton‐Coupled Reduction of the Catalytic [4Fe‐4S] Cluster in [FeFe]‐Hydrogenases

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From Enzymes to Functional Materials—Towards Activation of Small Molecules

Cited by 58 publications

References 393 publications

Electrochemical Conversion of CO2 to CO by a Competent FeI Intermediate Bearing a Schiff Base Ligand

Electrochemical Conversion of CO2 to CO by a Competent FeI Intermediate Bearing a Schiff Base Ligand

[FeFe]-Hydrogenases: recent developments and future perspectives

Proton‐Coupled Reduction of the Catalytic [4Fe‐4S] Cluster in [FeFe]‐Hydrogenases

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Electrochemical Conversion of CO₂ to CO by a Competent Fe^I Intermediate Bearing a Schiff Base Ligand

Electrochemical Conversion of CO₂ to CO by a Competent Fe^I Intermediate Bearing a Schiff Base Ligand