Tuning Main Group Element‐based Metal–Organic Framework to Boost Electrocatalytic Nitrogen Reduction Under Ambient Conditions

Small, Journal Year: 2023, Volume and Issue: 20(9)

Published: Oct. 19, 2023

Abstract Main group element‐based materials are emerging catalysts for ammonia (NH 3 ) production via a sustainable electrochemical nitrogen reduction reaction (N 2 RR) pathway under ambient conditions. However, their N RR performances less explored due to the limited active behavior and unclear mechanism. Here, an aluminum‐based defective metal–organic framework (MOF), aluminum‐fumarate (Al‐Fum), is investigated. As proof of concept, pristine Al‐Fum MOF synthesized by solvothermal process, defect engineering method namely solvent‐assisted linker exchange, applied create Al sites. The sites play important role in ensuring activity Al‐Fum. It found that only enables stable effective RR, terms highest rate 53.9 µg(NH h −1 mg cat (in 0.4 m K SO 4 Faradaic efficiency 73.8% 0.1 at −0.15 V vs reversible hydrogen electrode) Density functional theory calculations confirm activation can be achieved on Such also allow subsequent protonation process alternating associative This characteristic gives main Al‐based MOFs ability serve as promising electrocatalysts other attractive applications.

Language: Английский

Selective Partial Reduction of Nitroarenes to the Hydrazoarene Catalyzed by Amine‐Modified Ordered Mesoporous Silica Immobilized Ionic Liquid (OMSIIL) Stabilised RuNPs

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(13)

Published: March 7, 2024

Abstract Ruthenium nanoparticles stabilised by an amine‐modified Ordered Mesoporous Silica Immobilized Ionic Liquid (OMSIIL) are efficient catalysts for the partial reduction of nitrobenzene to hydrazobenzene with 100 % selectivity as well complete aniline. High was obtained when reaction conducted in ethanol 0.5 mol% catalyst and NaBH 4 hydrogen donor whereas aniline sole product water dimethylamine borane (DMAB) used donor. Interestingly, while a range electron poor nitroarenes were reduced corresponding hydrazoarene high selectivities good conversions, substituted donating groups resulted Composition‐time profiles suggest that reductions sodium borohydride occur via condensation pathway those using source may go direct pathway. This is first example selective ruthenium nanoparticle‐based initial TOF 320 mol converted Ru −1 h markedly higher than previous literature reports. A study performance function surface modification revealed each component has dramatic effect on efficacy RuNPs COK‐12 modified imidazolium‐based ionic liquid primary amine gave highest conversion removal either or replacement tertiary marked efficiency.

Language: Английский

Surface Enhanced Raman Spectroscopy Studies on the “Hot Spot” Localized Area from Free Collision Behavior of Gold Nanoparticle-Gold Single Crystal Microplate

Acta Chimica Sinica, Journal Year: 2024, Volume and Issue: 82(3), P. 281 - 281

Published: Jan. 1, 2024

Language: Английский