Engineering Asymmetric Electronic Structure of Co─N─C Single‐Atomic Sites Toward Excellent Electrochemical H₂O₂ Production and Biomass Upgrading

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

Published: March 11, 2025

Abstract To advance electrochemical H 2 O production and unravel catalytic mechanisms, the precise structural coordination of single‐atomic M‐N‐C electrocatalysts is urgently required. Herein, Co─N 5 site with an asymmetric electronic configuration constructed to boost two‐electron oxygen reduction reaction (2e − ORR) compared symmetric 4 , effectively overcoming trade‐off between activity selectivity in production. Both experimental theoretical analyses demonstrate that breaking symmetry sites promotes activation molecules moderates adsorption key *OOH intermediate by disrupting linear scaling relationship for intermediates adsorption. This modulation enables efficient H₂O₂ its effective retention subsequent applications. As a proof concept, achieves rate as high 16.1 mol g cat −1 h flow cell, outperforming most recently reported counterparts. Furthermore, coupling 2e ORR oxidation cellulose‐derived carbohydrates accomplishes formic acid yields (84.1% from glucose 62.0%–92.1% other substrates), underpinning sustainable electro‐refinery biomass valorization at ambient conditions. By elucidating intrinsic 2e⁻ asymmetry sites, this work paves way high‐performance electrosynthesis.

Language: Английский

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Recent Progress in Oxygen Reduction Reaction Toward Hydrogen Peroxide Electrosynthesis and Cooperative Coupling of Anodic Reactions

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

Published: March 13, 2025

Abstract Electrosynthesis of hydrogen peroxide (H 2 O ) via two‐electron oxygen reduction reaction (2e − ORR) is a promising alternative to the anthraquinone oxidation process. To improve overall energy efficiency and economic viability this catalytic process, one pathway develop advanced catalysts decrease overpotential at cathode, other couple 2e ORR with certain anodic reactions full cell voltage while producing valuable chemicals on both electrodes. The performance catalyst depends not only material itself but also environmental factors. Developing electrocatalysts high selectivity activity prerequisite for efficient H electrosynthesis, coupling appropriate would further enhance efficiency. Considering this, here comprehensive review presented latest progress state‐of‐the‐art in different media, microenvironmental modulation mechanisms beyond design, as well electrocatalytic system various reactions. This presents new insights regarding existing challenges opportunities within rapidly advancing field, along viewpoints future development electrosynthesis construction green roadmaps.

Language: Английский

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Solvent-free fabrication of ultrathin two-dimensional metal oxides/sulfides in a fixed interlayer by geometric confinement

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 13, 2025

Language: Английский

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Engineering Asymmetric Electronic Structure of Co─N─C Single‐Atomic Sites Toward Excellent Electrochemical H₂O₂ Production and Biomass Upgrading

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

Published: March 11, 2025

Abstract To advance electrochemical H 2 O production and unravel catalytic mechanisms, the precise structural coordination of single‐atomic M‐N‐C electrocatalysts is urgently required. Herein, Co─N 5 site with an asymmetric electronic configuration constructed to boost two‐electron oxygen reduction reaction (2e − ORR) compared symmetric 4 , effectively overcoming trade‐off between activity selectivity in production. Both experimental theoretical analyses demonstrate that breaking symmetry sites promotes activation molecules moderates adsorption key *OOH intermediate by disrupting linear scaling relationship for intermediates adsorption. This modulation enables efficient H₂O₂ its effective retention subsequent applications. As a proof concept, achieves rate as high 16.1 mol g cat −1 h flow cell, outperforming most recently reported counterparts. Furthermore, coupling 2e ORR oxidation cellulose‐derived carbohydrates accomplishes formic acid yields (84.1% from glucose 62.0%–92.1% other substrates), underpinning sustainable electro‐refinery biomass valorization at ambient conditions. By elucidating intrinsic 2e⁻ asymmetry sites, this work paves way high‐performance electrosynthesis.

Language: Английский

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Dual‐Functional Catalyst of Amorphous TiO₂ Embedded in Mesoporous Carbon Hollow Spheres for H₂O₂ Electrosynthesis

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

Published: March 12, 2025

Abstract H 2 O production in coupled electrochemical systems, where is generated through 2e‐pathway of water oxidation (2e‐WOR) at anode and oxygen reduction (2e‐ORR) cathode, offers an advanced alternative to the anthraquinone process. However, efficiency such system often hindered by limited activity selectivity electrocatalysts. Herein, a dual‐functional catalyst composed amorphous TiO embedded mesoporous carbon hollow spheres (TiO x @MCHS) reported, which exhibits exceptional electrocatalytic performance for both 2e‐WOR 2e‐ORR. By employing @MCHS‐loaded electrodes as cathode membrane‐free flow cell with 4 м K CO 3 /KHCO electrolyte, rate 108.3 µmol min −1 cm −2 Faradaic (FE) ≈145% are achieved voltage ≈2.5 V under constant current 240 mA (anode: 1 , cathode: ). Experimental computational results reveal crucial role low‐coordinated Ti optimizing adsorption intermediates involved two electrode reaction pathways, thereby enhancing these processes. This work establishes new paradigm development electrocatalysts design novel coupled‐electrolysis enabling scalable sustainable electrosynthesis.

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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Engineering Localized Alkalinity and Oxygen Enrichment for Efficient Acidic O₂‐to‐H₂O₂ Electroreduction via Carbon‐Based Triphase Interfaces

Small, Journal Year: 2025, Volume and Issue: unknown

Published: March 27, 2025

The sustainable production of hydrogen peroxide (H2O2) via the two-electron oxygen reduction reaction (2e⁻ ORR) on carbon-based catalysts offers a compelling alternative to energy-intensive anthraquinone process. However, slow kinetics 2e⁻ ORR in acidic media limits its efficiency. Herein, novel strategy is introduced overcome this limitation by engineering needle-shaped hydrophobic carbon felt embedded with hard as natural air diffusion electrode (ADE). In situ and ex characterization show design creates an oxygen-enriched, locally alkaline microenvironment at triphase interface, which accelerates confining enrichment within layer. Quantitatively, oxygen-enriched hydrothermal electrocatalyst achieves remarkable H2O2 selectivity 95.47% near-zero overpotential high rate 487.82 mg L-1 h-1 200 mA cm-2. Furthermore, density functional theory calculations reveal that carboxyl ether groups optimize O2 * OOH* adsorption, promoting desired pathway. Importantly, ADE not only exhibits exceptional performance long-term stability but also demonstrates significantly reduced global warming potential compared conventional methods, highlighting revolutionize industrial-scale electrosynthesis replacing commercial black-based cathodes.

Language: Английский

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Recent advances in green H2O2 production via metal-based functional materials: applications, strategies, and catalytic mechanisms

Rare Metals, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Language: Английский

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Frustrated Lewis Pairs Boosting Electrochemical Production of Hydrogen Peroxide on Bi‐TiO_2−x Nanocatalysts

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

Published: April 30, 2025

Abstract Electrocatalytic two‐electron oxygen reduction (2e − ORR) offers an environmentally friendly route for H 2 O production, yet faces challenges in activation and *OOH intermediate stabilization. Here, Bi‐TiO 2−x nanocatalysts are introduced featuring frustrated Lewis acid‐base pairs (FLPs) active sites, where the Bi single atoms with electron‐deficient characteristics serve as acidic (LA) sites surrounding vacancy (O V ) act basic (LB) sites. The catalyst exhibits high selectivity up to 96.5%. Furthermore, a flowing electrolytic cell, reaches 93.9% yield of 1.56 mol g −1 h at −50 mA cm −2 is able maintain stable reaction 54 h. Theoretical calculations situ spectroscopic analyses indicate that FLPs structure can effectively promote dissociation during reaction, provide protons subsequent facilitate formation intermediates. coupling system 2e ORR ethylene glycol oxidation significantly improves 98.9% 3.02 , meanwhile, anode simultaneously produces formic acid co‐product, which utilization resources.

Language: Английский

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Hydrogen Peroxide Electrosynthesis via Selective Oxygen Reduction Reactions Through Interfacial Reaction Microenvironment Engineering

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 28, 2024

Abstract The electrochemical two‐electron oxygen reduction reaction (2e − ORR) offers a compelling alternative for decentralized and on‐site H 2 O production compared to the conventional anthraquinone process. To advance this electrosynthesis system, there is growing interest in optimizing interfacial microenvironment boost electrocatalytic performance. This review consolidates recent advancements engineering selective conversion of . Starting with fundamental insights into mechanisms, an overview various strategies constructing favorable local environment, including adjusting electrode wettability, enhancing mesoscale mass transfer, elevating pH, incorporating electrolyte additives, employing pulsed electrocatalysis techniques provided. Alongside these regulation strategies, corresponding analyses technical remarks are also presented. Finally, summary outlook on critical challenges, suggesting future research directions inspire accelerate practical application delivered.

Language: Английский

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