Electrocatalytic reduction of protons to dihydrogen by the cobalt tetraazamacrocyclic complex [Co(N4H)Cl2]+: mechanism and benchmarking of performances

Li, Chengbo; Bagnall, Andrew J.; Sun, Dongyue; Rendon, Julia; Koepf, Matthieu; Gambarelli, Serge; Mouesca, Jean‐Marie; Chavarot‐Kerlidou, Murielle; Artero, Vincent

doi:10.1039/d1se01267c

Cited by 17 publications

(39 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(The calculated TOF max value for TFA without subtracting the background was 19400 s –1 , and I cat / I p = 100; see section S5 in the SI for more details.) Notably, for Et 3 NHBF 4 and CF 3 COOH as proton sources, these are the highest TOF max values achieved so far by a homogeneous cobalt electrocatalyst under nonaqueous conditions. ,,,− I Cat = n F A false[ Cat false] D k false[ normalAcid false] I p = 0.4463 F A false[ Cat false] F v D R T I Cat I p = n 0.4463 R T k false[ normalAcid false] F v I Cat I p = n 0.4463 R T k obs F…”

Section: Resultsmentioning

confidence: 99%

“…This inference is consistent with the similar analysis results, as observed in the case of cobaloxime and related catalysts reported by Costentin, Artero, and coworkers 78 The first-order rate dependency on [acid] under the nonsaturating acid conditions can then be explained by the fact that the intramolecular reaction of the adjacent pyridinol proton with the Co−H hydride is coupled with the (re)protonation of the deprotonated pyridinone group. 67 Contextually, for the cobalt-based [Co(N 4 H)Cl 2 ] + electrocatalyst (where N 4 H is a tetraazamacrocyclic ligand), 67 having adjacent proton-responsive groups, the intramolecular dihydrogen elimination was found to be the rate-determining step. Based on the above-mentioned arguments, we may conclude that the intramolecular interaction between Co(II)−H hydride and adjacent pyridinol−OH proton was responsible for a high catalytic rate of dihydrogen elimination (Figure 4, red arrows).…”

Section: E Ementioning

confidence: 99%

See 1 more Smart Citation

[Fe]-Hydrogenase-Inspired Proton-Shuttle Installation in a Molecular Cobalt Complex for High-Efficiency H₂ Evolution Reaction

Mandal,

Sunil,

Choudhury

2024

ACS Catal.

View full text Add to dashboard Cite

Developing efficient H 2 -evolution artificial electrocatalysts often takes inspiration from the active sites of [FeFe]/[NiFe]-hydrogenases to incorporate smartly designed amine/thiolato-based proton-shuttle motifs. Interestingly, [Fe]-hydrogenase (the third type of hydrogenases) consists of an Fe-bound adjacent pyridinol/pyridinone proton shuttle, which assists in reversible heterolytic H 2 -cleavage during its operation. However, so far, this type of proton-shuttle functionality has not been exploited to develop H 2 -evolution electrocatalysts. We reckoned that installing such a proton-shuttle motif in a suitable redox-active transitionmetal-based complex can facilitate electrocatalytic H 2 generation via easy hydride/proton coupling, through proper positioning of the electrochemically generated metal-hydride and the "protonated" pyridinol form of the proton shuttle. To demonstrate this idea, a rationally designed Co-based complex Co− NHC U, containing an anionic uracil nucleobase, connected with a strong sigma-donor N-heterocyclic carbene (NHC) ligand, has been developed, wherein the anionic uracil motif offers a pyridinone-type proton-responsive site adjacent to the Co center. Gratifyingly, Co− NHC U acts as a highefficiency H 2 -generation electrocatalyst with variable proton sources, achieving maximum turnover frequency (TOF max ) values in the range of 5000−13 700 s −1 (from cyclic voltammetry) or ∼2200−7360 s −1 (from controlled potential electrolysis) with Faradaic efficiencies of 93%−98%, at the overpotential range of 0.50−0.78 V. This system delivered the highest TOF max values achieved to date by any cobalt electrocatalyst in a nonaqueous medium: 10 200−13 700 s −1 with CF 3 COOH and Et 3 NHBF 4 as proton sources. This work could provide insights into the future design principles of homogeneous HER catalysts via capitalizing the power of pyridinone/pyridinol-based proton shuttle motifs coupled with Earth-abundant transition metals.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: E Ementioning

confidence: 99%

[Fe]-Hydrogenase-Inspired Proton-Shuttle Installation in a Molecular Cobalt Complex for High-Efficiency H₂ Evolution Reaction

Mandal,

Sunil,

Choudhury

2024

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…[ 11 ] These univalent metal ion hybrid capacitors have been extensively studied, mainly the former two kinds. [ 12 ]…”

Section: Introductionmentioning

confidence: 99%

“…The alkaline metals such as Li, Na, and K used in conventional hybrid capacitors are highly reactive, and the organic electrolytes, which are explosive, result in insignificant security risks. [ 12b,13 ] Apart from these concerns, the lack of lithium supplies and their unequal distribution on earth rendered them costlier. Divalent ion storage technologies were introduced and developed in this situation to make new EESS.…”

Section: Introductionmentioning

confidence: 99%

Fundamentals and Scientific Challenges in Structural Design of Cathode Materials for Zinc‐Ion Hybrid Supercapacitors

Javed

Najam

Hussain

et al. 2022

Advanced Energy Materials

112

View full text Add to dashboard Cite

One of the most exciting new developments in energy storage technology is Zn‐ion hybrid supercapacitors (ZHSCs). ZHSCs combine Zn‐ion batteries with supercapacitors (SCs) to address the energy and power needs of portable devices and electric automobiles. Low energy density and the development of cathode material are significant issues for ZHSCs. This review provides an in‐depth investigation of charge storage mechanisms from SCs to ZHSCs. The advantages/disadvantages of ZHSCs, the recent development of cathode materials, and the new design for device fabrications are critically summarized. New cathode materials should be developed to achieve high energy density while preserving the inherent power capability and stability. People increasingly engage with smart electronic and hybrid gadgets, demanding flexible, resilient, and highly safe energy storage devices. ZHSC has emerged as a complete alternative to risky sodium‐ion/lithium‐ion technologies. An overview of all reported carbon‐based, biomass‐derived carbons, metal oxides, MOFs, COFs, MXenes, graphene, and composite materials employed for ZHSCs is comprehensively provided. Furthermore, cathode materials for flexible, micro, wire‐shaped, printed, and photo‐rechargeable ZHSCs are also examined with their practical challenges. This review is anticipated to offer valuable recommendations for designing and manipulating cathode materials for high‐performance ZHSCs to achieve real‐world applications.

show abstract

“…32 Addition of acid led to a peak at -1.2V vs Ag/Ag/Cl, suggesting that in the presence of a significant excess of protons, the catalyst follows a stepwise reduction process. 43 In contrast, in the absence of protons, it is a concerted single-step two electrons and two protons additions. Unsurprisingly the presence of protons increases the amplitude of the catalytic wave, showing that proton availability is a determining factor when accessing catalytic performance in this system.…”

mentioning

confidence: 99%

Plasmon-ligand-mediated hydrogen evolution with visible light

Sawka‐Dobrowolska

Dey

Mendalz

et al. 2023

Preprint

View full text Add to dashboard Cite

Plasmonic systems convert light into electrical charges and heat that mediate catalytic transformations. However, the debate about the involvement of hot carriers in the catalytic process remains shredded in controversy. Here, we demonstrate the direct use of plasmon hot electrons in the hydrogen evolution with visible light. A plasmonic nanohybrid system consisting of NiO/Au/[CoII(phen-NH2)2(H2O)2] (phen-NH2 = 1,10-Phenanthrolin-5-amine) that is unstable at water thermolysis temperatures was consciously assembled, ensuring that the plasmon contribution to the catalytic process is solely from hot carriers. With the combination of photoelectrocatalysis and advanced in situ spectroscopies, one could establish the reaction mechanism, which consisted of electron injection into the phenanthroline-ligands followed by two quick, concerted proton-coupled electron transfer steps resulting in the evolution of hydrogen. Light-driven hydrogen evolution with plasmons provides a sustainable route for producing green hydrogen, which modern society strives to achieve.

show abstract

Electrocatalytic reduction of protons to dihydrogen by the cobalt tetraazamacrocyclic complex [Co(N₄H)Cl₂]⁺: mechanism and benchmarking of performances

Abstract: The mechanism of H2 evolution catalyzed by the [Co(N4H)Cl2]+ complex is elucidated with quantitative determination of the rate-constants for the various protonation steps, and the identification of the aliphatic amine to act as a proton relay.

Cited by 17 publications

References 51 publications

[Fe]-Hydrogenase-Inspired Proton-Shuttle Installation in a Molecular Cobalt Complex for High-Efficiency H₂ Evolution Reaction

[Fe]-Hydrogenase-Inspired Proton-Shuttle Installation in a Molecular Cobalt Complex for High-Efficiency H₂ Evolution Reaction

Fundamentals and Scientific Challenges in Structural Design of Cathode Materials for Zinc‐Ion Hybrid Supercapacitors

Plasmon-ligand-mediated hydrogen evolution with visible light

Contact Info

Product

Resources

About

Electrocatalytic reduction of protons to dihydrogen by the cobalt tetraazamacrocyclic complex [Co(N4H)Cl2]+: mechanism and benchmarking of performances

Abstract: The mechanism of H2 evolution catalyzed by the [Co(N4H)Cl2]+ complex is elucidated with quantitative determination of the rate-constants for the various protonation steps, and the identification of the aliphatic amine to act as a proton relay.

Cited by 17 publications

References 51 publications

[Fe]-Hydrogenase-Inspired Proton-Shuttle Installation in a Molecular Cobalt Complex for High-Efficiency H2 Evolution Reaction

[Fe]-Hydrogenase-Inspired Proton-Shuttle Installation in a Molecular Cobalt Complex for High-Efficiency H2 Evolution Reaction

Fundamentals and Scientific Challenges in Structural Design of Cathode Materials for Zinc‐Ion Hybrid Supercapacitors

Plasmon-ligand-mediated hydrogen evolution with visible light

Contact Info

Product

Resources

About

Electrocatalytic reduction of protons to dihydrogen by the cobalt tetraazamacrocyclic complex [Co(N₄H)Cl₂]⁺: mechanism and benchmarking of performances

[Fe]-Hydrogenase-Inspired Proton-Shuttle Installation in a Molecular Cobalt Complex for High-Efficiency H₂ Evolution Reaction

[Fe]-Hydrogenase-Inspired Proton-Shuttle Installation in a Molecular Cobalt Complex for High-Efficiency H₂ Evolution Reaction