Proton‐Coupled Electron Transfer Reactions Catalysed by 3 d Metal Complexes

Siewert, Inke

doi:10.1002/chem.201501684

Cited by 59 publications

(31 citation statements)

References 124 publications

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“…17,46,48 This coupling is vital for optimal activity, especially for processes going beyond single-electron transformations, as it can avoid the formation of high-energy intermediates. 16,49 This is particularly important for the multielectron reduction reactions of CO 2 (eqs 1–7 below), which can thermodynamically proceed at relatively modest potentials. 1,22…”

Section: Introductionmentioning

confidence: 99%

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

et al. 2019

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The synthesis of renewable fuels from abundant water or the greenhouse gas CO 2 is a major step toward creating sustainable and scalable energy storage technologies. In the last few decades, much attention has focused on the development of nonprecious metal-based catalysts and, in more recent years, their integration in solid-state support materials and devices that operate in water. This review surveys the literature on 3d metal-based molecular catalysts and focuses on their immobilization on heterogeneous solid-state supports for electro-, photo-, and photoelectrocatalytic synthesis of fuels in aqueous media. The first sections highlight benchmark homogeneous systems using proton and CO 2 reducing 3d transition metal catalysts as well as commonly employed methods for catalyst immobilization, including a discussion of supporting materials and anchoring groups. The subsequent sections elaborate on productive associations between molecular catalysts and a wide range of substrates based on carbon, quantum dots, metal oxide surfaces, and semiconductors. The molecule–material hybrid systems are organized as “dark” cathodes, colloidal photocatalysts, and photocathodes, and their figures of merit are discussed alongside system stability and catalyst integrity. The final section extends the scope of this review to prospects and challenges in targeting catalysis beyond “classical” H 2 evolution and CO 2 reduction to C 1 products, by summarizing cases for higher-value products from N 2 reduction, C x >1 products from CO 2 utilization, and other reductive organic transformations.

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Section: Introductionmentioning

confidence: 99%

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

et al. 2019

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“…However, spatial separation of the redox site and acid/base site is commonly cited in hydrogen atom transfer reactions (often described as orthogonal, bidirectional, or multisite). [52][53][54][55][56][57][58][59][60][61][62][63][64] Separation of the proton and electron source permits independent tuning of the redox potential and pKa to satisfy the thermodynamic requirements for making or breaking X-H bonds (where X = C, N, O) at mild potentials. For example, challenging C-H bonds (with high bond dissociation free energies) are cleaved at relatively mild potentials at the active site of cytochrome P450s.…”

Section: Methodsmentioning

confidence: 99%

Reducing CO2 to HCO2- at Mild Potentials: Lessons from Formate Dehydrogenase

Yang

Kerr²,

Wang³

et al. 2020

Preprint

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The catalytic reduction of CO2 to HCO2- requires a formal transfer of a hydride (two electrons, one proton). Synthetic approaches for inorganic molecular catalysts have exclusively relied on classic metal hydrides, where the proton and electrons originate from the metal (via heterolytic cleavage of an M-H bond). An analysis of the scaling relationships that exist in classic metal hydrides reveal that hydride donors sufficiently hydridic to perform CO2 reduction are only accessible at very reducing electrochemical potentials, which is consistent with known synthetic electrocatalysts. By comparison, the formate dehydrogenase enzymes operate at relatively mild potentials. In contrast to reported synthetic catalysts, none of the major mechanistic proposals for hydride transfer in formate dehydrogenase proceed through a classic metal hydride. Instead, they invoke formal hydride transfer from an orthogonal or bi-directional mechanism, where the proton and electron are not co-located. We discuss the thermodynamic advantages of this approach for favoring CO2 reduction at mild potentials, along with guidelines for replicating this strategy in synthetic systems.

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“…Sie arbeitet mit ihrer Gruppe über die elektrokatalytische Protonenreduktion, Sauerstoffentwicklung und Kohlendioxidreduktion mithilfe neuartiger Koordinationsverbindungen von 3d‐Metallionen. Dieses Thema hat sie vor kurzem in einem Minireview in Chemistry—A European Journal behandelt, und in der Angewandten Chemie hat sie eine elektrokatalytische Wasserstoffproduktion vorgestellt …”

Section: Vorgestellt …unclassified

Médaille Lavoisier: J. Livage / Neue Mitglieder der Academia Europaea Science Award Electrochemistry: B. D. McCloskey / Ernst‐Haage‐Preis: I. Siewert / Einstein‐Stipendium: D. W. Stephan

2015

Angewandte Chemie

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Proton‐Coupled Electron Transfer Reactions Catalysed by 3 d Metal Complexes

Cited by 59 publications

References 124 publications

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes

Reducing CO2 to HCO2- at Mild Potentials: Lessons from Formate Dehydrogenase

Médaille Lavoisier: J. Livage / Neue Mitglieder der Academia Europaea Science Award Electrochemistry: B. D. McCloskey / Ernst‐Haage‐Preis: I. Siewert / Einstein‐Stipendium: D. W. Stephan

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