Unraveling Dynamic Structural Evolution of Single Atom Catalyst via In Situ Surface-Enhanced Infrared Absorption Spectroscopy

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Metal–nitrogen-carbon (M–N-C) single-atom catalysts (SACs) have been widely applied in catalyzing electrochemical redox reactions. However, their long-term catalytic stabilities greatly limit practical applications. This work investigates the dynamic evolution of two model Cu–N–C SACs with different Cu–N coordinations, namely Cu1/Npyri-C and Cu1/Npyrr-C, CO reduction reaction (CORR), based on a collection situ characterizations including attenuated total reflectance surface-enhanced infrared absorption spectroscopy, X-ray quasi-in electron paramagnetic resonance spectroscopy ultraviolet–visible complemented by theoretical calculations. Our findings reveal that Cu nanoparticle formation rate over Cu1/Npyrr-C is more than 6 times higher during CORR. Quasi-in UV–vis measurements demonstrate hydrogen radicals can be produced CORR, which will attack bonds SACs, causing leaching Cu2+ followed subsequent to form nanoparticles. Kinetic calculations show displays better stability resulting from stronger Cu–Npyri bonds. study deepens understanding deactivation mechanism reactions provides guidance for design next-generation enhanced durability.

Язык: Английский

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Electrochemical Reduction of CO₂ to CH₃OH Catalyzed by an Iron Porphyrinoid

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 4, 2025

Designing catalysts for the selective reduction of CO2, resulting in products having commercial value, is an important area contemporary research. Several molecular have been reported to facilitate CO2 (both electrochemical and photochemical) yield 2e–/2H+ electron-reduced products, CO HCOOH, beyond rare. This partly because factors that control selectivity 2e– are not yet understood. An iron chlorin complex with a pendent amine functionality its second sphere, known selectively catalyze CO2RR HCOOH very low overpotential from formal Fe(I) state, can Fe(0) state by 6e–/6H+, forming CH3OH as major product Faradaic ∼50%. Mechanistic investigations using situ spectro-electrochemistry indicate reactivity low-spin d7 FeI–COOH intermediate species generated during crucial determining this reaction. In weakly acidic conditions, C-protonation species, which also chemically prepared spectroscopically characterized, leads HCOOH. The O-protonation, leading C–OH bond cleavage eventually CH3OH, ∼3 kcal/mol higher energy be achieved more solutions. Hydrogen bonding catalyst stabilizes reactive intermediates formed enables 6e–/6H+ CH3OH.

Язык: Английский

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Modulation of Single‐Iron‐Atom Coordination Environment Toward Three‐Electron Oxygen Reduction for Photocatalytic CH₄ Conversion to CH₃OH

Small, Год журнала: 2025, Номер unknown

Опубликована: Фев. 11, 2025

Abstract By modifying the coordination environment of single‐Fe‐atom active site, effective regulation photocatalytic oxygen reduction pathway can be achieved to attain high activity for oxidation CH 4 3 OH in an aqueous solution. A comprehensive investigation is conducted study impact different numbers single Fe atoms on reaction over carbon nitride. Among which, 1 /C 3‐x N with a Fe‐N3 exhibit exceptional performance oxidation, reaching remarkable methanol yield 928.27 µmol g cat −1 , much higher than and 4‐x (308.47 473.26 respectively). Based collection situ characterizations time‐dependent density functional theory calculations, it determined that optimal number possesses optimized electronic configuration enables three‐electron generate hydroxyl radicals conversion OH.

Язык: Английский

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Carbon-based nanomaterials for carbon neutralization through electrochemical CO2 reduction and C–N coupling

Matter, Год журнала: 2025, Номер 8(5), С. 102077 - 102077

Опубликована: Май 1, 2025

Язык: Английский

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Enhancement Mechanism of CO₂RR toward Methanol on a Ball-Milled CoPc-CNT Electrocatalyst: A Covalent Anchoring Strategy

Energy & Fuels, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

Язык: Английский

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Importance of local coordination microenvironment in regulating CO2 electroreduction catalyzed by Cr-corrole-based single-atom catalysts

Journal of Colloid and Interface Science, Год журнала: 2025, Номер 696, С. 137856 - 137856

Опубликована: Май 10, 2025

Язык: Английский

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