Proton Relays in Molecular Catalysis for Hydrogen Evolution and Oxidation: Lessons From the Mimicry of Hydrogenases and Electrochemical Kinetic Analyses DOI Creative Commons

Matthieu Haake,

Bertrand Reuillard,

Murielle Chavarot‐Kerlidou

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(52)

Published: Nov. 18, 2024

Abstract The active sites of metalloenzymes involved in small molecules activation often contain pendant bases that act as proton relay promoting proton‐coupled electron‐transfer processes. Here we focus on hydrogenases and the reactions they catalyze, i. e. hydrogen evolution oxidation reactions. After a short description these enzymes, review some various biomimetic bioinspired molecular systems relays. We then provide formal electrochemical framework required to decipher key role such enhance catalysis single direction discuss few for H 2 which quantitative kinetic data are available. finally highlight parameters reach bidirectional (both catalyzed) transition reversible catalyzed narrow potential range) well illustrate features from literature.

Language: Английский

Kinetic Isotope Effects and the Mechanism of CO2 Insertion into the Metal-Hydride Bond of fac-(bpy)Re(CO)3H DOI

Mariam Barakat,

Sarah Elhajj,

Riyad Yazji

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(26), P. 12133 - 12145

Published: June 20, 2024

The 1,2-insertion reaction of CO2 into metal–hydride bonds d6-octahedral complexes to give κ1-O-metal-formate products is the key step in various reduction schemes and as a result has attracted extensive mechanistic investigations. For many octahedral catalysts, insertion follows an associative mechanism which interacts directly with coordinated hydride ligand instead more classical dissociative that opens empty coordination site bind substrate metal prior migration step. To better understand mechanism, we conducted systematic quantum chemical investigation on between fac-(bpy)Re(CO)3H (1–Re–H; bpy = 2,2′-bipyridine) starting gas phase then moving THF other solvents increased dielectric constants. Detailed analyses potential energy surfaces (PESs) intrinsic coordinates (IRCs) reveal enabled all media by initial stage making 3c-2e bond carbon metal-hydride most consistent organometallic bridging Re–H–CO2 species. Once bent anchored bond, proceeds rotation motion via cyclic transition state TS2 interchanges Re–O–CHO coordination. combined stages provide asynchronous–concerted pathway for Gibbs free surface highest point. Consideration rate-determining TS gives activation barriers, inverse KIEs, substituent effects, solvent effects agree experimental data available this system. An important new insight revealed results not transfer been assumed some studies. In fact, loose vibration can be identified first solution (TS1) does involve Re–H stretching vibrational mode. Accordingly, imaginary frequency TS1 insensitive deuteration, therefore, leads no significant KIE.

Language: Английский

Citations

2
Suppressing H2 Evolution with Sterically Encumbered Proton Sources to Improve the Faradaic Efficiency for CO2 Reduction to Formate DOI
Andrew D. Cypcar,

Kathleen M. Bui,

Jenny Y. Yang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 14517 - 14523

Published: Sept. 16, 2024

Language: Английский

Citations

2
Switching Electrocatalytic Hydrogen Evolution Pathways through Electronic Tuning of Copper Porphyrins DOI

Xinyang Peng,

Mengchun Zhang,

Haonan Qin

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(13)

Published: Feb. 7, 2024

Abstract 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 ‐lactone groups either a cis trans configuration. Complexes 1–4 have same Cu‐N 4 core site different structures. Although led large anodic shifts reductions, displayed similar HER activities terms close overpotentials. With electrochemical, chemical theoretical results, show that catalytically active species switches from I for 0 . This work thus significant present mechanism‐controllable via catalysts.

Language: Английский

Citations

1
FeCoP sub-nanometric-sheets for electrocatalzing overall water splitting DOI Creative Commons

Long Zhao,

Kexin Meng,

Yibo Guo

et al.

Deleted Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 3, 2024

Renewable electrical energy for electrolysis water can achieve green industrial chains hydrogen production. However, finding efficient electrocatalysts remains a challenge hydrogen. Herein, sub-nanometric FeCoP nanosheets with average thickness of 0.9 nm is constructed through 2D self-assembly driven by cavitation effect ultrasonics and following phosphating. Benefiting from abundant active sites, enhanced H2O molecular adsorption kinetics, highly structural stability, the subcrystalline shows excellent electrocatalytic activities evolution reaction (HER) oxygen reactions (OER). Ultralow overpotential 37 mV achieved at 10 mA·cm−2 HER. When catalyst was used as both cathode anode overall splitting using renewable energy, produced directly applied fuel cell to drive fan more than h. Theoretical calculation indicates that easily adsorbs crystalline one thus speeds up kinetics Volmer step in HER process.

Language: Английский

Citations

1
Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis DOI Open Access
Qian Zhao, Qingxin Zhang, Yuhan Xu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(47)

Published: Aug. 15, 2024

Abstract Improving proton transfer is vital for electrocatalysis with porous materials. Although several strategies are reported to assist in channels, few studies dedicated improving at the local environments of active sites Herein, we report on new Co‐corrole‐based organic polymers (POPs) improved electrocatalytic oxygen reduction reaction (ORR) and evolution (OER). By tuning pore sizes installing relays Co corrole sites, designed synthesized POP‐2‐OH both channels sites. This POP shows remarkable activity ORR E 1/2 =0.91 V vs RHE OER η 10 =255 mV. Therefore, this work significant present a strategy improve site materials highlight key role such structural functionalization boosting electrocatalysis.

Language: Английский

Citations

1
Proton Relays in Molecular Catalysis for Hydrogen Evolution and Oxidation: Lessons From the Mimicry of Hydrogenases and Electrochemical Kinetic Analyses DOI Creative Commons

Matthieu Haake,

Bertrand Reuillard,

Murielle Chavarot‐Kerlidou

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(52)

Published: Nov. 18, 2024

Abstract The active sites of metalloenzymes involved in small molecules activation often contain pendant bases that act as proton relay promoting proton‐coupled electron‐transfer processes. Here we focus on hydrogenases and the reactions they catalyze, i. e. hydrogen evolution oxidation reactions. After a short description these enzymes, review some various biomimetic bioinspired molecular systems relays. We then provide formal electrochemical framework required to decipher key role such enhance catalysis single direction discuss few for H 2 which quantitative kinetic data are available. finally highlight parameters reach bidirectional (both catalyzed) transition reversible catalyzed narrow potential range) well illustrate features from literature.

Language: Английский

Citations

1
Electrocatalytic hydrogen evolution reaction with a Cu porphyrin bearing meso-CF3 substituents DOI

Wenzi Li,

Xinyang Peng,

Haonan Qin

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(48), P. 19121 - 19125

Published: Jan. 1, 2024

A Cu porphyrin bearing four meso -CF 3 substituents is synthesized and displays higher activity than reported porphyrins for the electrocatalytic hydrogen evolution reaction.

Language: Английский

Citations

1
On the role of hydrogen bond acceptors in electrocatalytic hydride formation DOI Creative Commons
Jong-Hwa Shon,

Kirti Singh,

Natalia D. Loewen

et al.

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: unknown, P. 102312 - 102312

Published: Dec. 1, 2024

Language: Английский

Citations

1
Mechanistic Insight into Electrocatalytic Co2 Reduction to Formate by the Iron(I) Porphyrin Complex DOI
Yaqing Wang, Wenzhen Lai

Published: Jan. 1, 2024

Electrocatalytic reduction of CO2 into value-added chemicals has been considered as a promising pathway to alleviate the energy crisis and global warming. Iron porphyrins have extensively studied for electrocatalytic reaction (CO2RR) are well documented promote CO2-to-CO conversion. However, mechanism CO2-to-HCOO- conversion by Fe porphyrin remains unclear. Here, means density functional theory (DFT) calculations, we investigated detailed novel catalyst HCOO- in its Fe(I) state. Our results demonstrated that proceeds through C-protonation an FeII-OCO·- complex rather than hydrolysis FeIII-COOH or insertion Fe-H bond. Moreover, is not stable intermediate. The protonation hydroxyl group with concomitant C-OH bond cleavage produce CO thermodynamically kinetically unfeasible. Instead, can undergo coordination switch followed conformational change form active production HCOO-. single-electron gives FeII-COOH, which leads formation insights gained from this work may be useful designing electrocatalysts selective formate.

Language: Английский

Citations

0
Kinetic Analysis of Proton-Coupled Electron Transfer at an Electrode-Immobilized Complex DOI Creative Commons
Charlotte L. Montgomery,

J. K. Lee,

Carrie L. Donley

et al.

ACS electrochemistry., Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 13, 2024

An alkyne-terminated cobalt complex, [Co(Cp)(dppe≡H)(Cl)]+ (Cp = cyclopentadienyl; dppe≡H 1,2-bis-(di-(4-ethynyl-phenyl)phosphino)ethane), (Co≡H) was immobilized onto a glassy carbon electrode using two attachment strategies: Cu(I) catalyzed azide–alkyne click chemistry and reductive electropolymerization. The modified electrodes prepared through electropolymerization exhibit current densities peak resolutions for the electrochemical reduction of species, which are amenable to electroanalytical quantification coupled chemical reactions. Through shift analysis cyclic voltammograms recorded in presence 4-chloroanilinium tetrafluoroborate, we quantified proton transfer rate constant stepwise proton-coupled electron reaction that reduces electrode-immobilized [H–Co(Cp)(dppe≡H)]+ (kPTapp (9.3 ± 1.8) × 105 M–1 s–1). extraction kinetic parameters an elementary complex represents first experimental measurement its type lays crucial groundwork analyses hybrid catalyst–electrode architectures.

Language: Английский

Citations

0