Catalysis of Electrochemical Reduction of Weak Acids to Produce H<sub>2</sub>: Role of O‒H…S Hydrogen Bonding

Chen, Jinzhu; Vannucci, Aaron K.; Mebi, Charles A.; Okumura, Noriko; Borowski, Susan C.; Lockett, L. Tori; Swenson, Matthew T.; Lichtenberger, Dennis L.; Evans, Dennis H.; Glass, Richard S.

doi:10.1080/10426507.2010.523035

Cited by 4 publications

(3 citation statements)

References 28 publications

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“…Under these conditions, complex 2 displayed a quasi‐reversible redox event at E 1/2 =−1.26 V vs Fe +/0 (with a peak separation, E p,c −E p,a =ΔE p =60 mV) (Figure 3A, red trace). We tentatively attribute this process to a two‐electron reduction of the complex (Fe I Fe I /Fe 0 Fe 0 ), in line with closely related systems featuring benzene‐dithiolate (bdt 2− ) bridging ligands, for which a single step two‐electron reduction has been characterized [70–73] . The peak currents of the redox process were found to vary linearly with the square root of the scan rate (from 10 to 1000 mV s −1 ), indicating a diffusion controlled redox event (Figure S8) [74] .…”

Section: Resultssupporting

confidence: 64%

“…We tentatively attribute this process to a two-electron reduction of the complex (Fe I Fe I / Fe 0 Fe 0 ), in line with closely related systems featuring benzenedithiolate (bdt 2À ) bridging ligands, for which a single step twoelectron reduction has been characterized. [70][71][72][73] The peak currents of the redox process were found to vary linearly with the square root of the scan rate (from 10 to 1000 mV s À 1 ), indicating a diffusion controlled redox event (Figure S8). [74] At more reducing potentials, an irreversible reduction at E p,c = À 2.44 V vs Fe + /0 was observed, followed by a (quasi-) reversible process at E 1/2 = À 2.55 V vs Fe + /0 (ΔE p = 78 mV).…”

Section: Resultsmentioning

confidence: 99%

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Non‐Covalent Integration of a [FeFe]‐Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution

Zamader

Reuillard

Pécaut

et al. 2022

Chemistry A European J

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Surface integration of molecular catalysts inspired from the active sites of hydrogenase enzymes represents a promising route towards developing noble metal-free and sustainable technologies for H 2 production. Efficient and stable catalyst anchoring is a key aspect to enable this approach. Herein, we report the preparation and electrochemical characterization of an original diironhexacarbonyl complex including two pyrene groups per catalytic unit in order to allow for its smooth integration, through π-interactions, onto multiwalled carbon nanotube-based electrodes. In this configuration, the grafted catalyst could reach turnover numbers for H 2 production (TON H2 ) of up to 4 � 2 × 10 3 within 20 h of bulk electrolysis, operating at neutral pH. Post operando analysis of catalyst functionalized electrodes revealed the degradation of the catalytic unit occurred via loss of the iron carbonyl units, while the anchoring groups and most part of the ligand remained attached onto multiwalled carbon nanotubes.

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Section: Resultssupporting

confidence: 64%

Section: Resultsmentioning

confidence: 99%

Non‐Covalent Integration of a [FeFe]‐Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution

Zamader

Reuillard

Pécaut

et al. 2022

Chemistry A European J

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“…We recently reported a new metallopolymer catalyst system built around a customized [2Fe-2S] catalyst site with a bridging aryldithiolato ligand which exhibits remarkable catalytic activity, air stability, and chemical stability (21). The electrocatalytic mechanism of the [2Fe-2S] catalysts with aryldithiolato ligands is known from previous studies and these catalysts operate at rates of 10 5 s −1 and faster (27)(28)(29)(30). The readily synthesized and watersoluble metallopolymer composed of tertiary amine side-chain groups, PDMAEMA-g-[2Fe-2S] (Fig.…”

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Increasing the rate of the hydrogen evolution reaction in neutral water with protic buffer electrolytes

Clary

Karayilan

McCleary-Petersen

et al. 2020

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

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Electrocatalytic generation of H2 is challenging in neutral pH water, where high catalytic currents for the hydrogen evolution reaction (HER) are particularly sensitive to the proton source and solution characteristics. A tris(hydroxymethyl)aminomethane (TRIS) solution at pH 7 with a [2Fe-2S]-metallopolymer electrocatalyst gave catalytic current densities around two orders of magnitude greater than either a more conventional sodium phosphate solution or a potassium chloride (KCl) electrolyte solution. For a planar polycrystalline Pt disk electrode, a TRIS solution at pH 7 increased the catalytic current densities for H2 generation by 50 mA/cm2 at current densities over 100 mA/cm2 compared to a sodium phosphate solution. As a special feature of this study, TRIS is acting not only as the primary source of protons and the buffer of the pH, but the protonated TRIS ([TRIS-H]+) is also the sole cation of the electrolyte. A species that is simultaneously the proton source, buffer, and sole electrolyte is termed a protic buffer electrolyte (PBE). The structure–activity relationships of the TRIS PBE that increase the HER rate of the metallopolymer and platinum catalysts are discussed. These results suggest that appropriately designed PBEs can improve HER rates of any homogeneous or heterogeneous electrocatalyst system. General guidelines for selecting a PBE to improve the catalytic current density of HER systems are offered.

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Hydrogen generation: Aromatic dithiolate-bridged metal carbonyl complexes as hydrogenase catalytic site models

Pandey

Natarajan

Kaur‐Ghumaan

2015

Journal of Inorganic Biochemistry

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Catalysis of Electrochemical Reduction of Weak Acids to Produce H₂: Role of O‒H…S Hydrogen Bonding

Cited by 4 publications

References 28 publications

Non‐Covalent Integration of a [FeFe]‐Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution

Non‐Covalent Integration of a [FeFe]‐Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution

Increasing the rate of the hydrogen evolution reaction in neutral water with protic buffer electrolytes

Hydrogen generation: Aromatic dithiolate-bridged metal carbonyl complexes as hydrogenase catalytic site models

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Catalysis of Electrochemical Reduction of Weak Acids to Produce H2: Role of O‒H…S Hydrogen Bonding

Cited by 4 publications

References 28 publications

Non‐Covalent Integration of a [FeFe]‐Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution

Non‐Covalent Integration of a [FeFe]‐Hydrogenase Mimic to Multiwalled Carbon Nanotubes for Electrocatalytic Hydrogen Evolution

Increasing the rate of the hydrogen evolution reaction in neutral water with protic buffer electrolytes

Hydrogen generation: Aromatic dithiolate-bridged metal carbonyl complexes as hydrogenase catalytic site models

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Catalysis of Electrochemical Reduction of Weak Acids to Produce H₂: Role of O‒H…S Hydrogen Bonding