Piperazine-Linked Metalphthalocyanine Frameworks for Highly Efficient Visible-Light-Driven H₂O₂ Photosynthesis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(46), P. 21328 - 21336

Published: Nov. 9, 2022

Artificial photosynthesis of H2O2 from O2 reduction provides an energy-saving, safe, and green approach. However, it is still critical to develop highly active selective 2e– oxygen reaction photocatalysts for efficient production owing the unsatisfactory productivity. Herein, two new two-dimensional piperazine-linked CoPc-based covalent organic frameworks (COFs), namely, CoPc-BTM-COF CoPc-DAB-COF, were afforded nucleophilic substitution hexadecafluorophthalocyaninato cobalt(II) (CoPcF16) with 1,2,4,5-benzenetetramine (BTM) or 3,3′-diaminobenzidine (DAB). Powder X-ray diffraction analysis in combination electron microscopy a series spectroscopic technologies reveals their crystalline porous framework fully conjugated structure eclipsed π-stacking model. Ultraviolet–visible diffuse reflectance absorption spectra unveil excellent light capacity wide range 400–1000 nm. This, together enhanced photo-induced charge separation transport efficiency as disclosed by photocurrent response photoluminescence measurements, endows as-prepared COFs superior photocatalytic activity toward O2-to-H2O2 conversion under visible-light irradiation (λ > 400 nm). In particular, exhibits record-high yield 2096 μmol h–1 g–1 among COF-based impressive apparent quantum 7.2% at 630 The present result should be helpful fabricating high-performance low-cost visible-light-driven photosynthesis.

Language: Английский

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CoIn dual-atom catalyst for hydrogen peroxide production via oxygen reduction reaction in acid

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 8, 2023

The two-electron oxygen reduction reaction in acid is highly attractive to produce H2O2, a commodity chemical vital various industry and household scenarios, which still hindered by the sluggish kinetics. Herein, both density function theory calculation in-situ characterization demonstrate that dual-atom CoIn catalyst, O-affinitive In atom triggers favorable stable adsorption of hydroxyl, effectively optimizes OOH on neighboring Co. As result, Co atoms shifts pathway for efficient H2O2 production acid. partial current reaches 1.92 mA cm-2 at 0.65 V rotating ring-disk electrode test, while rate as high 9.68 mol g-1 h-1 three-phase flow cell. Additionally, CoIn-N-C presents excellent stability during long-term operation, verifying practicability catalyst. This work provides inspiring insights into rational design active catalysts other catalytic systems.

Language: Английский

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Mesoporous carbon spheres with programmable interiors as efficient nanoreactors for H2O2 electrosynthesis

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

Published: Feb. 1, 2024

Abstract The nanoreactor holds great promise as it emulates the natural processes of living organisms to facilitate chemical reactions, offering immense potential in catalytic energy conversion owing its unique structural functionality. Here, we propose utilization precisely engineered carbon spheres building blocks, integrating micromechanics and controllable synthesis explore their functionalities two-electron oxygen reduction reactions. After conducting rigorous experiments simulations, present compelling evidence for enhanced mass transfer microenvironment modulation effects offered by these mesoporous hollow spheres, particularly when possessing a suitably sized architecture. Impressively, pivotal achievement lies successful screening potent, selective, durable reaction catalyst direct medical-grade hydrogen peroxide disinfectant. Serving an exemplary demonstration engineering screening, this work highlights various well-designed carbon-based nanoreactors extensive applications.

Language: Английский

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Unveiling Favorable Microenvironment on Porous Doped Carbon Nanosheets for Superior H₂O₂ Electrosynthesis in Neutral Media

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(19)

Published: Feb. 21, 2024

Abstract Designing effective electrocatalysts tailored for targeted reactions requires fundamental insights into the structure dependence of reaction microenvironment. Herein, inspired by finite element simulations, N,O co‐doped carbon nanosheets featuring a hierarchical micro/mesoporous to form an oxygen‐rich and local alkaline‐like microenvironment two‐electron oxygen reduction (2e − ORR) in neutral medium are designed. The situ ex test results confirmed that architecture can elevate pH accelerate generation intermediates (*O 2 , *OOH), leading high‐efficiency H O production. Utilizing this favorable microenvironment, N,O‐CNS 0.5 demonstrated exceptional electrosynthesis performance media, achieving superior yield rate (6705 mmol g catalyst −1 h flow cell). Additionally, comparative experiments density‐functional theory calculations provided confirmation bi‐doping N as active origin responsible electrochemical 2e ORR. This study synergistically manipulates sites, providing opportunity efficient electro‐production medium.

Language: Английский

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Understanding Advanced Transition Metal‐Based Two Electron Oxygen Reduction Electrocatalysts from the Perspective of Phase Engineering

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: March 8, 2024

Abstract Non‐noble transition metal (TM)‐based compounds have recently become a focal point of extensive research interest as electrocatalysts for the two electron oxygen reduction (2e − ORR) process. To efficiently drive this reaction, these TM‐based must bear unique physiochemical properties, which are strongly dependent on their phase structures. Consequently, adopting engineering strategies toward structure has emerged cutting‐edge scientific pursuit, crucial achieving high activity, selectivity, and stability in electrocatalytic This comprehensive review addresses intricate field applied to non‐noble 2e ORR. First, connotation fundamental concepts related kinetics thermodynamics succinctly elucidated. Subsequently, focus shifts detailed discussion various approaches, including elemental doping, defect creation, heterostructure construction, coordination tuning, crystalline design, polymorphic transformation boost or revive ORR performance (selectivity, stability) catalysts, accompanied by an insightful exploration phase‐performance correlation. Finally, proposes fresh perspectives current challenges opportunities burgeoning field, together with several critical directions future development electrocatalysts.

Language: Английский

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Efficient Neutral H2O2 Electrosynthesis from Favorable Reaction Microenvironments via Porous Carbon Carrier Engineering

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 20, 2024

The efficient electrosynthesis of hydrogen peroxide (H

Language: Английский

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Tuning the Formation Kinetics of *OOH Intermediate with Hollow Bowl-Like Carbon by Pulsed Electroreduction for Enhanced H₂O₂ Production

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 28, 2025

The electrochemical synthesis of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e- ORR) is a promising alternative to conventional anthraquinone method. However, due local alkalinization near catalyst surface, restricted replenishment and insufficient activated water molecule supply limit formation key *OOH intermediate. Herein, pulsed electrocatalysis approach based on structurally optimized S/N/O tridoped hollow carbon bowl has been proposed overcome this challenge. In an H-type electrolytic cell, method achieves superior H2O2 yield rate 55.6 mg h-1 mgcat.-1, approximately 1.6 times higher than potentiostatic (34.2 mgcat.-1), while maintaining Faradaic efficiency above 94.6%. situ characterizations, finite element simulations, density functional theory analyses unveil that application potentials mitigates OH- concentration, enhances activation proton generation, facilitates production within bowl-like structure. These effects synergistically accelerate kinetics intermediate by efficient generation *O2 *H2O intermediates, leading yields. This work develops strategy tune catalytic environments for diverse applications.

Language: Английский

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Nanoengineering of Porous 2D Structures with Tunable Fluid Transport Behavior for Exceptional H₂O₂ Electrosynthesis

Nano Letters, Journal Year: 2024, Volume and Issue: 24(5), P. 1650 - 1659

Published: Jan. 24, 2024

Precision nanoengineering of porous two-dimensional structures has emerged as a promising avenue for finely tuning catalytic reactions. However, understanding the pore-structure-dependent performance remains challenging, given lack comprehensive guidelines, appropriate material models, and precise synthesis strategies. Here, we propose optimization carbon materials through utilization mesopores with 5–10 nm diameter to facilitate fluid acceleration, guided by finite element simulations. As proof concept, optimized mesoporous nanosheet sample exhibited exceptional electrocatalytic performance, demonstrating high selectivity (>95%) notable diffusion-limiting disk current density −3.1 mA cm–2 H2O2 production. Impressively, electrolysis process in flow cell achieved production rate 14.39 mol gcatalyst–1 h–1 yield medical-grade disinfectant-worthy solution. Our pore engineering research focuses on modulating oxygen reduction reaction activity affecting local transport behavior, providing insights into mesoscale mechanism.

Language: Английский

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Metalloenzyme‐Inspired Cluster Fabrication within Mesoporous Channels Featuring Optimized Catalytic Microenvironments for Efficient Neutral pH H₂O₂ Electrosynthesis

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 17, 2025

Abstract In nature, some metalloenzymes facilitate highly efficient catalytic transformations of small molecules, primarily attributed to the effective coupling between their metal cluster active sites and surrounding microenvironment. Inspired by this, a thermotropic redispersion strategy incorporate bismuth nanoclusters (Bi NCs) into mesoporous channels, mimicking metalloenzyme‐like catalysis enhance two‐electron oxygen reduction reaction (2e − ORR) for neutral pH H 2 O electrosynthesis, is developed. This model electrocatalyst exhibits exceptional 2e ORR performance with >95% selectivity across 0.2–0.6 V vs RHE in electrolyte. Notably, system produces up 7.2 wt% solution at an industrially relevant current density ≈320 mA cm −2 , 90% Faradaic efficiency over 120 h flow cell, demonstrating significant practical potential. Mechanistic insights reveal that introduction Bi NCs enhances adsorption *OOH intermediate, facilitating process. Moreover, channels carbon support create favorable microenvironment aeration local alkalinity, further boosting productivity. catalyst design mimics optimal integration site microenvironment, offering valuable rational nature‐inspired small‐molecule catalysts.

Language: Английский

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Dual‐Engineering of Porous Structure and Carbon Edge Enables Highly Selective H₂O₂ Electrosynthesis

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(47)

Published: July 19, 2023

Abstract Edge engineering has emerged as a powerful strategy to activate inert carbon surfaces, and thus achieve notable enhanced electrocatalytic activity. However, the rational manipulation of edges catalytic performance remains formidable challenge, primarily hindered by immature synthesis methods obscured understanding structure‐activity relationship. Herein, an organic–inorganic hybrid co‐assembly is used fabricate series mesoporous nanofibers (MCNFs) with controllable edge site densities impact population on electrochemical oxygen reduction reaction (ORR) pathways investigated. The optimized MCNFs catalyst exhibits remarkable 2e − ORR performance, evidenced high H 2 O selectivity (>90%) across wide potential window 0.6 V large cathodic current density −3.0 mA cm −2 (at 0.2 vs. reversible hydrogen electrode). Strikingly, sites can be changed tune activity selectivity. Experimental validation functional theory calculations confirm that presence defects optimize adsorption strength *OOH intermediates balance process. This study provides new path in carbon‐based electrocatalysts.

Language: Английский

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