Identification of the Highly Active Co–N₄ Coordination Motif for Selective Oxygen Reduction to Hydrogen Peroxide

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(32), С. 14505 - 14516

Опубликована: Авг. 3, 2022

Electrosynthesis of hydrogen peroxide (H

Язык: Английский

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Polarization Engineering of Covalent Triazine Frameworks for Highly Efficient Photosynthesis of Hydrogen Peroxide from Molecular Oxygen and Water

Advanced Materials, Год журнала: 2022, Номер 34(28)

Опубликована: Май 7, 2022

Two-electron oxygen photoreduction to hydrogen peroxide (H2 O2 ) is seriously inhibited by its sluggish charge kinetics. Herein, a polarization engineering strategy demonstrated grafting (thio)urea functional groups onto covalent triazine frameworks (CTFs), giving rise significantly promoted separation/transport and obviously enhanced proton transfer. The thiourea-functionalized CTF (Bpt-CTF) presents substantial improvement in the photocatalytic H2 production rate 3268.1 µmol h-1 g-1 with no sacrificial agents or cocatalysts that over an order of magnitude higher than unfunctionalized (Dc-CTF), remarkable quantum efficiency 8.6% at 400 nm. Mechanistic studies reveal performance attributed prominently two-electron reduction reaction forming endoperoxide unit highly concentrated holes thiourea site. generated from water oxidation subsequently consumed (ORR), thereby boosting overall findings suggest powerful functional-groups-mediated method for development efficient metal-free polymer-based photocatalysts.

Язык: Английский

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Cation‐Vacancy‐Enriched Nickel Phosphide for Efficient Electrosynthesis of Hydrogen Peroxides

Advanced Materials, Год журнала: 2022, Номер 34(16)

Опубликована: Фев. 22, 2022

Electrocatalytic hydrogen peroxide (H2 O2 ) synthesis via the two-electron oxygen reduction reaction (2e ORR) pathway is becoming increasingly important due to green production process. Here, cationic vacancies on nickel phosphide, as a proof-of-concept regulate catalyst's physicochemical properties, are introduced for efficient H2 electrosynthesis. The as-fabricated Ni (VNi )-enriched Ni2-x P-VNi electrocatalyst exhibits remarkable 2e ORR performance with molar fraction of >95% and Faradaic efficiencies >90% in all pH conditions under wide range applied potentials. Impressively, as-created VNi possesses superb long-term durability over 50 h, suppassing recently reported catalysts Operando X-ray absorption near-edge spectroscopy (XANES) synchrotron Fourier transform infrared (SR-FTIR) combining theoretical calculations reveal that excellent catalytic originates from -induced geometric electronic structural optimization, thus promoting adsorption favored "end-on" configuration. It believed demonstrated cation vacancy engineering an effective strategy toward creating active heterogeneous atomic precision.

Язык: Английский

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Engineering the Local Atomic Environments of Indium Single‐Atom Catalysts for Efficient Electrochemical Production of Hydrogen Peroxide

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(12)

Опубликована: Янв. 19, 2022

The in-depth understanding of local atomic environment-property relationships p-block metal single-atom catalysts toward the 2 e- oxygen reduction reaction (ORR) has rarely been reported. Here, guided by first-principles calculations, we develop a heteroatom-modified In-based metal-organic framework-assisted approach to accurately synthesize an optimal catalyst, in which single In atoms are anchored combined N,S-dual first coordination and B second supported hollow carbon rods (In SAs/NSBC). SAs/NSBC catalyst exhibits high H2 O2 selectivity above 95 % wide range pH. Furthermore, SAs/NSBC-modified natural air diffusion electrode unprecedented production rate 6.49 mol peroxide gcatalyst-1 h-1 0.1 M KOH electrolyte 6.71 PBS electrolyte. This strategy enables design next-generation high-performance materials, provides practical guidance for electrosynthesis.

Язык: Английский

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Metal single-site catalyst design for electrocatalytic production of hydrogen peroxide at industrial-relevant currents

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 12, 2023

Direct hydrogen peroxide (H2O2) electrosynthesis via the two-electron oxygen reduction reaction is a sustainable alternative to traditional energy-intensive anthraquinone technology. However, high-performance and scalable electrocatalysts with industrial-relevant production rates remain be challenging, partially due insufficient atomic level understanding in catalyst design. Here we utilize theoretical approaches identify transition-metal single-site catalysts for using *OOH binding energy as descriptor. The predictions are then used guidance synthesize desired cobalt O-modified Co-(pyrrolic N)4 configuration that can achieve current densities up 300 mA cm-2 96-100% Faradaic efficiencies H2O2 at record rate of 11,527 mmol h-1 gcat-1. Here, show feasibility versatility metal design various commercial carbon phthalocyanine starting materials high applicability acidic, neutral alkaline electrolytes.

Язык: Английский

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A Pentagonal Defect-Rich Metal-Free Carbon Electrocatalyst for Boosting Acidic O₂ Reduction to H₂O₂ Production

Journal of the American Chemical Society, Год журнала: 2023, Номер unknown

Опубликована: Май 9, 2023

Metal-free carbon-based materials are considered one of the most promising two-electron oxygen reduction reaction (2e– ORR) electrocatalysts for green synthesis hydrogen peroxide (H2O2). However, reported carbon perform much more effectively in alkalis than acids. Herein, by creatively using fullerene (C60) as precursor subject to ammonia treatment, we designed and synthesized a pentagonal defect-rich nitrogen-doped nanomaterial (PD/N–C). It achieves outstanding ORR activity, 2e– selectivity, stability acidic electrolytes, surpassing benchmark PtHg4 alloy catalyst. Impressively, flow cell based on PD/N–C catalyst nearly 100% Faraday efficiency with remarkable H2O2 yield, representing best improvement among all metal-free catalysts. Experimental theoretical results reveal that such superb performance originates from synergism between defects nitrogen dopants. This work presents an effective strategy design construction highly efficient acid-resistant production beyond.

Язык: Английский

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Electrified water treatment: fundamentals and roles of electrode materials

Nature Reviews Materials, Год журнала: 2023, Номер 8(7), С. 472 - 490

Опубликована: Май 30, 2023

Язык: Английский

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Conductive Two-Dimensional Magnesium Metal–Organic Frameworks for High-Efficiency O₂ Electroreduction to H₂O₂

ACS Catalysis, Год журнала: 2022, Номер 12(10), С. 6092 - 6099

Опубликована: Май 6, 2022

Direct electrosynthesis of H2O2 via a two-electron oxygen reduction reaction (2e– ORR) under ambient conditions is emerging as promising solution toward on-site applications for the replacement energy-consuming, waste-intensive, and indirect anthraquinone process. To date, state-of-the-art 2e– ORR catalysis mostly performed with transition-metal-based materials, while main-group element-based catalysts are much less established, which there an urgent need proper understanding. Herein, we report conductive two-dimensionally layered Mg3(hexaiminotriphenylene)2 electrocatalyst selective hydrogenation O2 to synthesize (selectivity >90%) robust high catalytic efficiency. In situ spectroscopic monitoring reactions kinetic studies not only illustrate mechanisms on but confirm that Mg2+ center serving real active site responsible critical intermediate OOH* forming event. Additionally, in-depth density functional theory calculations further discuss excellent activity selectivity production.

Язык: Английский

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Recent advances in electrocatalytic oxygen reduction for on-site hydrogen peroxide synthesis in acidic media

Journal of Energy Chemistry, Год журнала: 2021, Номер 67, С. 432 - 450

Опубликована: Окт. 28, 2021

Язык: Английский

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Facilitating two-electron oxygen reduction with pyrrolic nitrogen sites for electrochemical hydrogen peroxide production

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июль 22, 2023

Abstract Electrocatalytic hydrogen peroxide (H 2 O ) production via the two-electron oxygen reduction reaction is a promising alternative to energy-intensive and high-pollution anthraquinone oxidation process. However, developing advanced electrocatalysts with high H yield, selectivity, durability still challenging, because of limited quantity easy passivation active sites on typical metal-containing catalysts, especially for state-of-the-art single-atom ones. To address this, we report graphene/mesoporous carbon composite high-rate high-efficiency 2e − catalysis. The coordination pyrrolic-N -modulates adsorption configuration *OOH species provide kinetically favorable pathway production. Consequently, yield approaches 30 mol g −1 h Faradaic efficiency 80% excellent durability, yielding concentration 7.2 L . This strategy manipulating reactants multiple non-metal provides design efficient durable metal-free electrocatalyst reduction.

Язык: Английский

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