Ligand-based electronic effects on the electrocatalytic hydrogen production by thiosemicarbazone nickel complexes

Papadakis, Michael; Barrozo, Alexandre; Straistari, Tatiana; Queyriaux, Nicolas; Putri, Anisa; Fize, Jennifer; Giorgi, Michel; Réglier, Marius; Massin, Julien; Hardré, Renaud; Orio, Maylis

doi:10.1039/c9dt04775a

Cited by 21 publications

(50 citation statements)

References 76 publications

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“…The theoretical determination of the quantities associated to the electrochemical and chemical steps was shown to help to determine which pathway is favoured among all possible sequences. Many studies made use of detailed DFT calculations to inspect free energy landscapes and to identify the predominant pathway for proton reduction among all possible sequences in the case of molecular electrocatalysts 61,62,292,294,[297][298][299][300][301][302][303][304][305][306][307][308][309] and hydrogenase models (Fig. 16).…”

Section: Reaction Mechanismsmentioning

confidence: 99%

Successes, challenges, and opportunities for quantum chemistry in understanding metalloenzymes for solar fuels research

Orio

Pantazis

2021

Chem. Commun.

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Section: Reaction Mechanismsmentioning

confidence: 99%

Successes, challenges, and opportunities for quantum chemistry in understanding metalloenzymes for solar fuels research

Orio

Pantazis

2021

Chem. Commun.

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“…The through‐structure effects displayed opposing outcomes as factors that reduced overpotential also decreased turnover frequency (TOF) and vice versa [7] . This trend is also well documented in electrocatalysts for the hydrogen evolution reaction (HER) [10] . In contrast, through‐space substituent effects provide a means to both lower the overpotential and increase TOF [11] .…”

Section: Introductionmentioning

confidence: 87%

“…In contrast, through‐space substituent effects provide a means to both lower the overpotential and increase TOF [11] . The effect of through‐space interactions on electrocatalysis has also been evaluated through the introduction of a secondary coordination sphere [9,10,12,13] . Ligands with bulky groups, fixed charge sites, and hydrogen‐bonding proton relay pendents are of growing interest as they may play an important role in generating and stabilizing reactive intermediates during catalysis [9,14] .…”

Section: Introductionmentioning

confidence: 99%

“…[7] This trend is also well documented in electrocatalysts for the hydrogen evolution reaction (HER). [10] In contrast, through-space substituent effects provide a means to both lower the overpotential and increase TOF. [11] The effect of through-space interactions on electrocatalysis has also been evaluated through the introduction of a secondary coordination sphere.…”

Section: Introductionmentioning

confidence: 99%

“…[11] The effect of through-space interactions on electrocatalysis has also been evaluated through the introduction of a secondary coordination sphere. [9,10,12,13] Ligands with bulky groups, fixed charge sites, and hydrogen-bonding proton relay pendents are of growing interest as they may play an important role in generating and stabilizing reactive intermediates during catalysis. [9,14] For example, incorporation of charged groups in the second coordination sphere, as part of the ligand framework or as appended groups, have been shown to reduce the reduction potential of the complex via through-space interactions.…”

Section: Introductionmentioning

confidence: 99%

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Copper bis(thiosemicarbazone) Complexes with Pendent Polyamines: Effects of Proton Relays and Charged Moieties on Electrocatalytic HER

et al. 2020

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A series of new bis(thiosemicarbazonato) Cu(II) complexes with pendent polyamines, diacetyl-(N,-dimethylethylenediaminothiosemicarbazonato)-(N'-methyl-3-thio-semicarbazonato)butane-2,3-diimine)-copper(II) (Cu-1), diacetyl-bis (N-dimethylethylenediamino-3-thiosemicarbazonato)butane-2,3-diimine)-copper(II) (Cu-3), and their cationic derivatives Cu-2 and Cu-4, have been synthesized and fully characterized by spectroscopic, electrochemical, and X-ray diffraction methods. Complexes Cu-1-Cu-4 are analogues of Cu(ATSM), which contains a similar N 2 S 2 donor core with terminal non-coordinating amines. Substitution of the methyl group(s) of the terminal amines of H 2 ATSM with N,N-dimethylethylenediamine followed by alkylation generates a charged quaternary amine in the ligand framework. The charged site tunes the redox potentials of the complexes with minimal changes in their physical and electronic properties. The HER activity of all four copper complexes were evaluated in acetonitrile with glacial acetic acid. All of the complexes have lower HER overpotentials than Cu(ATSM), which is attributed to charge effects. The pendent amines of Cu-1 and Cu-3 have the lowest HER overpotential as the pendent tertiary amine also serves as a proton relay to enhance proton rearrangement under catalytic conditions. Complex Cu-3 showed the highest activity with a TOF of 12 × 10 3 s À 1 , an overpotential of 0.65 V, and faradaic efficiency of 100 %.

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A bis(thiosemicarbazonato)‐zinc complex, an electrocatalyst for hydrogen evolution and oxidation via ligand‐assisted metal‐centered reactivity

Yang

Wang

et al. 2022

Applied Organom Chemis

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Based on that hydrogen energy is widely used in fuel cells, the design and research of new catalysts for both hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs) are becoming increasingly important. A new catalyst for both hydrogen evolution and oxidation, based on a zinc complex, [Zn‐ATSE]2, is designed and provided by the reaction of Zn (CH3CO2)2 with diacetyl‐2‐(4‐N‐ethyl‐3‐thiosemicarbazone)‐3‐(4‐N‐amino‐3‐thiosemicarbazone) (H2ATSE) in our group. Electrochemical investigations show that [Zn‐ATSE]2 can electro‐catalyze hydrogen evolution from acetic acid with a turnover frequency (TOF) of 64 mol H2 mol catalyst−1 h−1 under an overpotential of 914.6 mV. Moreover, [Zn‐ATSE]2 also can electro‐catalyze hydrogen oxidation with a TOF of 13.52 s−1. The results can be attributed to the hydrazine group of [Zn‐ATSE]2 that can form a ligand‐based radical species. Possible electrocatalytic cycles for H2 production and oxidation by [Zn‐ATSE]2 are afforded. We hope these findings can afford a new method for the design of electrocatalysts for both H2 evolution and H2 oxidation.

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Ligand-based electronic effects on the electrocatalytic hydrogen production by thiosemicarbazone nickel complexes

Abstract: This work reports on the synthesis and characterization of a series of mononuclear thiosemicarbazone nickel complexes that display significant catalytic activity for hydrogen production in DMF using trifluoroacetic acid as the proton source.

Cited by 21 publications

References 76 publications

Successes, challenges, and opportunities for quantum chemistry in understanding metalloenzymes for solar fuels research

Successes, challenges, and opportunities for quantum chemistry in understanding metalloenzymes for solar fuels research

Copper bis(thiosemicarbazone) Complexes with Pendent Polyamines: Effects of Proton Relays and Charged Moieties on Electrocatalytic HER

A bis(thiosemicarbazonato)‐zinc complex, an electrocatalyst for hydrogen evolution and oxidation via ligand‐assisted metal‐centered reactivity

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