High‐Valence Oxides for High Performance Oxygen Evolution Electrocatalysis

Advanced Science, Год журнала: 2023, Номер 10(22)

Опубликована: Май 30, 2023

Valence tuning of transition metal oxides is an effective approach to design high-performance catalysts, particularly for the oxygen evolution reaction (OER) that underpins solar/electric water splitting and metal-air batteries. Recently, high-valence (HVOs) are reported show superior OER performance, in association with fundamental dynamics charge transfer intermediates. Particularly considered adsorbate mechanism (AEM) lattice oxygen-mediated (LOM). High-valence states enhance performance mainly by optimizing e

Язык: Английский

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An Ultrasmall Ordered High-Entropy Intermetallic with Multiple Active Sites for the Oxygen Reduction Reaction

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 1174 - 1184

Опубликована: Дек. 28, 2023

Controlling multimetallic ensembles at the atomic level is significantly challenging, particularly for high-entropy alloys with more than five elements. Herein, we report an innovative ultrasmall (∼2 nm) PtFeCoNiCuZn intermetallic (PFCNCZ-HEI) a well-ordered structure synthesized by using space-confined strategy. By exploiting these combined metals, PFCNCZ-HEI nanoparticles achieve ultrahigh mass activity of 2.403 A mgPt–1 0.90 V vs reversible hydrogen electrode oxygen reduction reaction, which up to 19-fold higher that state-of-the-art commercial Pt/C. proton exchange membrane fuel cell assembled as cathode (0.03 mgPt cm–2) exhibits power density 1.4 W cm–2 and high mass-normalized rated 45 mgPt–1. Furthermore, theoretical calculations reveal outer electrons non-noble-metal atoms on surface nanoparticle are modulated show characteristics multiple active centers. This work offers promising catalyst design direction developing highly ordered HEI electrocatalysis.

Язык: Английский

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Steric Effects on the Oxygen Reduction Reaction with Cobalt Porphyrin Atropisomers

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6644 - 6649

Опубликована: Апрель 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.

Язык: Английский

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Lattice Strained Induced Spin Regulation in Co−N/S Coordination‐Framework Enhanced Oxygen Reduction Reaction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(16)

Опубликована: Фев. 23, 2024

Abstract Oxygen reduction reaction (ORR) is the bottleneck of metal‐air batteries and fuel cells. Strain regulation can change geometry adjust surface charge distribution catalysts, which a powerful strategy to optimize ORR activity. The introduction controlled strain material still difficult achieve. Herein, we present temperature‐pressure‐induced achieve lattice for metal coordination polymers. Through systematic study effect on performance, relationship between geometric electronic effects further understood confirmed. strained Co‐DABDT (DABDT=2,5‐diaminobenzene‐1,4‐dithiol) with 2 % compression exhibits superior half‐wave potential 0.81 V. Theoretical analysis reveals that changes spin‐charge densities around S atoms Co‐DABDT, then regulates hydrogen bond interaction intermediates promote catalytic process. This work helps understand mechanism from atomic level.

Язык: Английский

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Selective construction of molecular Solomon links and figure-eight knots by fine-tuning unsymmetrical ligands

Science China Chemistry, Год журнала: 2023, Номер 66(10), С. 2885 - 2891

Опубликована: Сен. 7, 2023

Язык: Английский

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Stabilizing iron single atoms with electrospun hollow carbon nanofibers as self-standing air-electrodes for long-time Zn − air batteries

Journal of Colloid and Interface Science, Год журнала: 2023, Номер 651, С. 525 - 533

Опубликована: Авг. 3, 2023

Язык: Английский

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Solar-driven CO2 conversion to methane and methanol using different nanostructured Cu2O-based catalysts modified with Au nanoparticles

Journal of Energy Chemistry, Год журнала: 2023, Номер 91, С. 287 - 298

Опубликована: Ноя. 14, 2023

Язык: Английский

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Water and Air Stable Copper(I) Complexes of Tetracationic Catenane Ligands for Oxidative C−C Cross‐Coupling

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(28)

Опубликована: Апрель 25, 2024

Abstract Aqueous soluble and stable Cu(I) molecular catalysts featuring a catenane ligand composed of two dicationic, mutually repelling but mechanically interlocked macrocycles are reported. The interlocking not only fine‐tunes the coordination sphere kinetically stabilizes against air oxidation disproportionation, also buries hydrophobic portions ligands prevents their dissociation which necessary for good water solubility sustained activity. These complexes can catalyze oxidative C−C coupling indoles tetrahydroisoquinolines in water, using H 2 O as green oxidant with substrate scope. successful use exploiting aqueous catalysis thus highlights many unexplored potential mechanical bond design element exploring transition metal under challenging conditions.

Язык: Английский

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Highly Efficient Self‐Assembly of Heterometallic [2]Catenanes and Cyclic Bis[2]catenanes via Orthogonal Metal‐Coordination Interactions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 13, 2024

Although catenated cages have been widely constructed due to their unique and elegant topological structures, cyclic catenanes formed by the connection of multiple catenane units rarely reported. Herein, based on orthogonal metal-coordination-driven self-assembly, we prepare a series heterometallic [2]catenanes bis[2]catenanes, whose structures are clearly evidenced single-crystal X-ray analysis. Owing positively charged nature, as well potential synergistic effect Cu(I) Pt(II) metal ions, bis[2]catenanes display broad-spectrum antibacterial activity. This work not only provides an efficient strategy for construction but also explores applications superior agents, which will promote advanced supramolecular biomedical applications.

Язык: Английский

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Selective Four‐Electron Reduction of Oxygen by a Nonheme Heterobimetallic CuFe Complex

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(48)

Опубликована: Окт. 14, 2023

We report herein the first nonheme CuFe oxygen reduction catalyst ([CuII (bpbp)(μ-OAc)2 FeIII ]2+ , CuFe-OAc), which serves as a functional model of cytochrome c oxidase and can catalyze to water with turnover frequency 2.4×103 s-1 selectivity 96.0 % in presence Et3 NH+ . This performance significantly outcompetes its homobimetallic analogues (2.7 CuCu-OAc %H2 O2 98.9 %, inactive FeFe-OAc) under same conditions. Structure-activity relationship studies, combination density theory calculation, show that center efficiently mediates O-O bond cleavage via CuII (μ-η1 : η2 -O2 )FeIII peroxo intermediate ligand possesses distinctive coordinating electronic character. Our work sheds light on nature Cu/Fe heterobimetallic cooperation catalysis demonstrates potential this synergistic effect design catalysts.

Язык: Английский

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