Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(11), P. 4583 - 4762

Published: Jan. 1, 2022

Replacing fossil fuels with energy sources and carriers that are sustainable, environmentally benign, affordable is amongst the most pressing challenges for future socio-economic development.

Language: Английский

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Switching Electrocatalytic Hydrogen Evolution Pathways through Electronic Tuning of Copper Porphyrins

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 7, 2024

The electronic structure of metal complexes plays key roles in determining their catalytic features. However, controlling structures to regulate reaction mechanisms is fundamental interest but has been rarely presented. Herein, we report tuning Cu porphyrins switch pathways the hydrogen evolution (HER). Through controllable and regioselective β-oxidation porphyrin 1, synthesized analogues 2-4 with one or two β-lactone groups either a cis trans configuration. Complexes 1-4 have same Cu-N

Language: Английский

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Hydrogen evolution with hot electrons on a plasmonic-molecular catalyst hybrid system

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 10, 2024

Abstract Plasmonic systems convert light into electrical charges and heat, mediating catalytic transformations. However, there is ongoing controversy regarding the involvement of hot carriers in process. In this study, we demonstrate direct utilisation plasmon electrons hydrogen evolution reaction with visible light. We intentionally assemble a plasmonic nanohybrid system comprising NiO/Au/[Co(1,10-Phenanthrolin-5-amine) 2 (H O) ], which unstable at water thermolysis temperatures. This assembly limits thermal contribution while ensuring that are primary contributors to By combining photoelectrocatalysis advanced situ spectroscopies, can substantiate mechanism plasmon-induced play crucial role. These directed phenanthroline ligands, facilitating rapid, concerted proton-electron transfer steps essential for generation. The response modulation aligns distinctive profile carrier-mediated process, featuring positive, though non-essential, heat contribution.

Language: Английский

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Metal carbonyl clusters of groups 8–10: synthesis and catalysis

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(17), P. 9503 - 9539

Published: Jan. 1, 2021

In this review article, we discuss advances in the chemistry of metal carbonyl clusters (MCCs) spanning last three decades, with an emphasis on more recent reports and those involving groups 8–10 elements.

Language: Английский

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Coordination-driven electrocatalysts as an evolving wave of enthusiasm for sustainable hydrogen production

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 500, P. 215496 - 215496

Published: Nov. 6, 2023

Language: Английский

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 2058 - 2070

Published: Jan. 24, 2024

Developing efficient H2-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 hydrogenases) consists an Fe-bound adjacent pyridinol/pyridinone proton shuttle, which assists in reversible heterolytic H2-cleavage during its operation. However, so far, this functionality has not been exploited develop electrocatalysts. We reckoned that installing such a motif suitable redox-active transition-metal-based complex can facilitate electrocatalytic H2 generation via easy hydride/proton coupling, through proper positioning electrochemically generated metal-hydride and "protonated" pyridinol form shuttle. To demonstrate idea, rationally Co-based Co–NHCU, containing anionic uracil nucleobase, connected with strong sigma-donor N-heterocyclic carbene (NHC) ligand, developed, wherein offers pyridinone-type proton-responsive site Co center. Gratifyingly, Co–NHCU acts as high-efficiency H2-generation electrocatalyst variable sources, achieving maximum turnover frequency (TOFmax) values range 5000–13 700 s–1 (from cyclic voltammetry) or ∼2200–7360 controlled potential electrolysis) Faradaic efficiencies 93%–98%, at overpotential 0.50–0.78 V. This system delivered highest TOFmax achieved date by any cobalt nonaqueous medium: 10 200–13 CF3COOH Et3NHBF4 sources. work could provide insights into future design principles homogeneous HER catalysts capitalizing power pyridinone/pyridinol-based shuttle motifs coupled Earth-abundant transition metals.

Language: Английский

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Mechanism-Guided Kinetic Analysis of Electrocatalytic Proton Reduction Mediated by a Cobalt Catalyst Bearing a Pendant Basic Site

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3742 - 3754

Published: Feb. 5, 2024

Cobalt polypyridyl complexes stand out as efficient catalysts for electrochemical proton reduction, but investigations into their operating mechanisms, with broad-reaching implications in catalyst design, have been limited. Herein, we investigate the catalytic activity of a cobalt(II) complex bearing pendant pyridyl base series organic acids spanning 20 pKa units acetonitrile. Structural analysis, well studies, reveals that Co(III) hydride intermediate is formed through reduction Co(II) followed by direct metal protonation initial EC step despite presence base, which commonly thought more kinetically accessible site. Protonation occurs after further reduced overall ECEC pathway. Additionally, when acid used sufficiently strong, can be protonated, and react directly to release H2. With thorough mechanistic understanding, appropriate electroanalytical methods were identified extract rate constants elementary steps over range conditions. Thermodynamic square schemes relating intermediates proposed three electrocatalytic HER mechanisms constructed. These findings reveal full description electrocatalysis mediated this molecular system provide insights strategies improve synthetic fuel-forming operative intermediates.

Language: Английский

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Mechanistic Insights into Electrocatalytic Hydrogen Evolution by an Exceptionally Stable Cobalt Complex

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(18), P. 8484 - 8492

Published: April 19, 2024

Co(aPPy) is one of the most stable and active molecular first-row transition-metal catalysts for proton reduction reported to date. Understanding origin its high performance via mechanistic studies could aid in developing even better catalysts. In this work, catalytic mechanism was electrochemically probed, both organic solvents water. We found that different mechanisms can occur depending on solvent acidity medium. with a strong acid as source, catalysis initiates directly after single-electron CoII CoI, whereas presence weaker acid, cobalt center needs be reduced twice before occurs. aqueous phase, we drastically electrochemical behavior, where complex precatalyst electrocatalytic species. propose catalyst, pyridine ring has dissociated acts relay at pH ≤ 5, which opens up fast protonation pathway CoI intermediate results activity. Furthermore, determined constant potential bulk electrolysis catalyst 3. The thus functions optimally low an environment, shuttle also prevents deactivation.

Language: Английский

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“Ship-in-a-bottle” entrapment of biomolecules in MOF-based xerogel monoliths for high-performance electrochemical hydrogen evolution

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(13), P. 7622 - 7630

Published: Jan. 1, 2024

The “ship-in-a-bottle” entrapment of bioactive molecules in metal–organic framework (MOF)-based xerogel monoliths based on a controlled mesopore architecture was reported.

Language: Английский

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Photocatalytic Hydrogen Production with A Molecular Cobalt Complex in Alkaline Aqueous Solutions

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9493 - 9498

Published: March 26, 2024

The thermodynamic favorability of an alkaline solution for the oxidation water suggests need developing hydrogen evolution reaction (HER) catalysts that can function in basic aqueous solutions so both half reactions overall splitting occur mutually compatible solutions. Although photocatalytic HERs have been reported mostly acidic and a few at pHs mixed organic solutions, visible-light driven HER catalyzed by molecular metal complexes purely remains largely unexplored. Here, we report new cobalt complex with tetrapyridylamine ligand catalyzes photolytic turnover number up to 218 000 pH 9.0. Density functional theory (DFT) calculations suggested modified electron transfer (E)–proton (C)–electron (C) (mod-ECEC) pathway production from protonation CoII–H species. remarkable catalytic activity resulting subtle structural changes scaffold highlights importance studying structure–function relationships catalyst design. Our present work significantly advances development more challenging holds substantial promise solar-driven water-splitting systems.

Language: Английский

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