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

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

Metal-free catalysts for hydrogen peroxide production with electrocatalysis and photocatalysis

Chemical Engineering Science, Journal Year: 2025, Volume and Issue: unknown, P. 121621 - 121621

Published: April 1, 2025

Language: Английский