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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Steric Effects on the Oxygen Reduction Reaction with Cobalt Porphyrin Atropisomers

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6644 - 6649

Published: April 16, 2024

The steric effects on the oxygen reduction reaction (ORR) have been rarely studied because O2 is small in size and ORR catalysts with only difference hindrance are difficult to be designed synthesized. Herein, we report homogeneous catalyzed by four Co porphyrin atropisomers tetrahydrofuran decamethylferrocene HClO4 at 298 K. All active selective for 2H+/2e– an activity order αααα > αααβ ααββ αβαβ. Kinetic studies revealed that same mechanism proton-coupled binding as rate-determining step.

Language: Английский

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One‐Pot Synthesis Inorganic–Organic Hybrid PdNi Bimetallenes for PET Electrocatalytic Value‐Added Transformation

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(34)

Published: Feb. 27, 2024

Abstract Progress is made in the advancement of efficient and durable electrocatalysts for ethylene glycol oxidation reaction (EGOR), which a critical breakthrough conversion waste plastic into high‐value‐added chemicals. Here, an organic ligand‐modified PdNi bimetallenes (PdNi O‐BMs) catalyst designed constructed through one‐pot method. Benefiting from frizzy porous surface structure inorganic–organic hybrid interface modification, O‐BMs undergo electrocatalytic reforming (EG) derived polyethylene terephthalate (PET) to form formic acid. The unique structural advantages result high EGOR performance. Meanwhile, influence Ni ligand on performance confirmed density functional theory calculations. This study reveals advanced strategy synthesis bimetallenes, providing green sustainable new approach PET value‐added transformation.

Language: Английский

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Pivotal Role of Geometry Regulation on O−O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(9)

Published: Jan. 5, 2024

Abstract In this study, we highlight the impact of catalyst geometry on formation O−O bonds in Cu 2 and Fe catalysts. A series complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, catalytic performance these is enhanced their molecular skeletons become more rigid, which contrasts behavior observed our previous investigation analogs. Moreover, mechanistic studies reveal that reactivity bridging O atom results distinct pathways bond systems, coupling takes place between a terminal III −OH μ −O⋅ radical. Whereas it involves two Fe–oxo entities. Furthermore, an in‐depth structure–activity analysis uncovers spatial geometric prerequisites OH radical, ultimately leading to formation. Overall, study emphasizes critical role precisely adjusting catalysts align bonding pathway.

Language: Английский

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Constructing Co₄(SO₄)₄ Clusters within Metal–Organic Frameworks for Efficient Oxygen Electrocatalysis

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(38)

Published: Aug. 3, 2024

Abstract Multinuclear metal clusters are ideal candidates to catalyze small molecule activation reactions involving the transfer of multiple electrons. However, synthesizing active is a big challenge. Herein, on constructing an unparalleled Co 4 (SO ) cluster within porphyrin‐based metal–organic frameworks (MOFs) and electrocatalytic features such for oxygen evolution reaction (OER) reduction (ORR) reported. The II sulfate complexes tetrakis(4‐pyridyl)porphyrin under solvothermal conditions afforded ‐M‐MOFs (M═Co, Cu, Zn). Crystallographic studies revealed that these have same framework structure, having connected by metalloporphyrin units through Co─N pyridyl bonds. In cluster, four ions chemically symmetrically equivalent each coordinated with O atoms give distorted cube‐like structure. Electrocatalytic showed all OER ORR. Importantly, regulating activity units, it confirmed electrocatalysis. With use porphyrins as connecting ‐Co‐MOF displays highest in this series MOFs showing 10 mA cm −2 current density at 357 mV overpotential ORR half‐wave potential 0.83 V versus reversible hydrogen electrode (RHE). Theoretical synergistic effect two proximal facilitating formation O─O This work fundamental significance present construction structures electrocatalysis demonstrate cooperation between during bond process.

Language: Английский

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Porphyrin‐Based Covalent Organic Frameworks for CO₂ Photo/Electro‐Reduction

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 9, 2025

Photo/electro-catalytic CO2 reduction into high-value products are promising strategies for addressing both environmental problems and energy crisis. Duo to their advantageous visible light absorption ability, adjustable optic/electronic properties, definite active center, post-modification capability, excellent stability, porphyrin-based covalent organic frameworks (COFs) have emerged as attractive photo/electro-catalysts towards reduction. In this review, the research progress of COFs photo/electro-catalytic is summarized including design principles, catalytic performance, reaction mechanism. addition, review also presents some challenges prospects application in reduction, laying base fundamental efforts.

Language: Английский

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A One‐Pot Three‐In‐One Synthetic Strategy to Immobilize Cobalt Corroles on Carbon Nanotubes for Oxygen Electrocatalysis

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(6)

Published: Oct. 27, 2023

Abstract Molecular electrocatalysis requires the immobilization of molecular catalysts on electrode materials for practical uses. Direct adsorption catalyst molecules is simple, but grafting through chemical bonds can significantly improve electrocatalytic efficiency and durability. However, designing synthesizing to simultaneously catalytic activities realize easy electrodes challenging. The study herein reports a one‐pot strategy graft Co corroles pyridine‐modified carbon nanotubes (CNTs) oxygen electrocatalysis. By modifying CNTs with pyridines, resulting function as platforms grab in situ generated axial pyridine ligation Co. Such an combines three effects regulation electrocatalysis, including ligand effect, electron transfer bond effect. hybrid show high Zn–air battery assembled using these displays comparable performance Pt/Ir‐based battery. Moreover, be systematically tuned by different highlighting controllable feature this strategy. Therefore, work significant present three‐in‐one immobilize

Language: Английский

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Covalent Tethering of Cobalt Porphyrins on Phenolic Resins for Electrocatalytic Oxygen Reduction and Evolution Reactions

ChemPhysChem, Journal Year: 2024, Volume and Issue: 25(7)

Published: Feb. 7, 2024

Abstract Using functionalized supporting materials for the immobilization of molecular catalysts is an appealing strategy to improve efficiency electrocatalysis. Herein, we report covalent tethering cobalt porphyrins on phenolic resins ( PR ) improved electrocatalytic oxygen reduction reaction (ORR) and evolution (OER). A porphyrin bearing alkyl bromide substituent was covalently tethered resins, through substitution bromides with hydroxyl groups, afford molecule‐engineered Co‐PR ). The resulted efficient ORR OER by displaying half‐wave potential E 1/2 =0.78 V versus RHE overpotential 420 mV get 10 mA/cm 2 current density. We propose that many residual groups will surround Co play critical roles in facilitating proton electron transfers. Importantly, outperformed unmodified loaded simple physical adsorption (termed Co@PR zinc‐air battery assembled using displayed a performance comparable Pt/C+Ir/C. This work significant present as material support electrocatalysts demonstrate electrocatalysis use resin residues.

Language: Английский

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Engineering heterostructured and hierarchical CoP/CoFeP nanosheet for effective oxygen evolution reaction in alkaline freshwater and seawater

International Journal of Hydrogen Energy, Journal Year: 2024, Volume and Issue: 71, P. 1342 - 1350

Published: May 26, 2024

Language: Английский

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Porphyrin‐Based Covalent Organic Frameworks for CO₂ Photo/Electro‐Reduction

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 9, 2025

Abstract Photo/electro‐catalytic CO 2 reduction into high‐value products are promising strategies for addressing both environmental problems and energy crisis. Duo to their advantageous visible light absorption ability, adjustable optic/electronic properties, definite active center, post‐modification capability, excellent stability, porphyrin‐based covalent organic frameworks (COFs) have emerged as attractive photo/electro‐catalysts towards reduction. In this review, the research progress of COFs photo/electro‐catalytic is summarized including design principles, catalytic performance, reaction mechanism. addition, review also presents some challenges prospects application in reduction, laying base fundamental efforts.

Language: Английский

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