Interfacial Asymmetrically Coordinated Zn−MOF for High‐Efficiency Electrosynthetic Oxime

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract Oximes are important intermediates for various chemicals synthesis such as pharmaceuticals, among which one vital precursor producing neurological disease, antimicrobial and anticancer agents is piperidone oxime (PDO). Compared with conventional thermocatalytic method, it's more attractive to synthesize PDO via green electrocatalytic technology especially utilizing waste nitrogen oxides gas source. However, there great challenges in catalyst design high‐efficiency electrosynthetic due the low electron transport rate multiple competing reactions. Herein, we propose an interfacial coordination strategy based on metal–organic frameworks (MOF) electrocatalyst first time promote electrosynthesis, by building Zn−O bridges between graphite felt (GF) zeolitic imidazolate framework (ZIF‐7/CGF). Specially, ZIF‐7/CGF delivers a Faraday efficiency (FE) of 75.9 % yield up 73.1 1‐methyl‐4‐piperidone oxime, far superior without (a FE 10.7 10.3 %). In‐depth mechanism study shows that introducing can transfer induce Zn sites transforming into distorted tetrahedron (Zn‐N 3 O) mode, benefits adsorption conversion. The developed presents wide universalities towards oximes electrosynthesis adapts other MOF materials (ZIF‐8, ZIF‐4). This work provides new insights organic upgrading cycle through rational surficial coordinated electrocatalysts.

Язык: Английский

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Tuning NO coverage promotes ampere-level electrosynthesis of a nylon-6 precursor

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

The electrocatalytic synthesis of cyclohexanone oxime from NO and with high Faradaic efficiency at ampere-level current density is highly desirable but challenging. Here, theoretical calculations reveal that coverage on the Ag catalyst plays a critical role in electrosynthesis. We then adjust local concentration experimentally by tuning reaction rate. find low benefits NH₃ formation, whereas delivers N-2 (N₂O N₂) products. A mechanistic study indicates increasing coverage, active sites transfer bridge step to hollow terrace sites, which results weaker adsorption O* species, leading stable existence NH₂OH* intermediate rather than decomposing form NH₃. However, N‒N coupling also easily occurs coverage. This understanding further inspires us develop doping strategy break equivalent surface can inhibit NO–NO thus realize density. Ru-doped developed, realizing 86% 1.0 cm^{− 2}, far exceeding reported performance.

Язык: Английский

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Tailoring Activation Intermediates of CO₂ Initiates C–N Coupling for Highly Selective Urea Electrosynthesis

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

Опубликована: Март 4, 2025

Electrocatalyzed reduction of CO2 and NO3- to synthesize urea is a highly desirable, but challenging reaction. The bottleneck this reaction the C-N coupling intermediates. In particular, uncertainty multielectron intermediates severely affects selectivity activity processes involving multiple electron proton transfers. Here, we present novel tandem catalyst with two compatible single-atom active sites Au Cu on red phosphorus (RP-AuCu) that efficiently converts urea. Experimental theoretical prediction results confirmed center promotes transfer between molecules phosphorus, thereby regulating activation produce electrophilic *COOH. addition, can enhance attack *COOH species *NH2, thus promoting selective formation bonds. Consequently, RP-AuCu exhibited yield 22.9 mmol gcat.-1 h-1 Faraday efficiency 88.5% (-0.6 VRHE), representing one highest levels electrocatalytic synthesis. This work deepens understanding mechanism provides an interesting design approach for efficient sustainable production compounds.

Язык: Английский

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Cu‐Based Nanomaterials for Oxime Electrosynthesis: Advances, Challenges, and Perspectives

cMat., Год журнала: 2025, Номер 2(1)

Опубликована: Март 1, 2025

ABSTRACT Cu‐based nanomaterials have demonstrated great potential for catalyzing the electrosynthesis of oxime compounds, a type organonitrogen molecule that finds versatile applications in pharmaceutical industry, medicine production, chemical feedstocks, and other fields. This review first explains significance compounds compares conventional synthetic approach with emerging electrochemical method. Then, including compounds/composites, bimetallic alloys, high entropy single‐atom catalysts are described some explicit examples to elucidate structure‐performance relationship clearly. Finally, current challenges future perspectives this rapidly developing evolving field analyzed critical thoughts. is anticipated stimulate more research efforts be dedicated fast‐growing yet quite promising field.

Язык: Английский

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Nitrogenous Intermediates in NO_x‐involved Electrocatalytic Reactions

Angewandte Chemie, Год журнала: 2024, Номер 136(15)

Опубликована: Янв. 16, 2024

Abstract Chemical manufacturing utilizing renewable sources and energy emerges as a promising path towards sustainability carbon neutrality. The electrocatalytic reactions involving nitrogen oxides (NO x ) offered potential strategy for synthesizing various nitrogenous chemicals. However, it is currently hindered by low selectivity/efficiency limited reaction pathways, mainly due to the difficulties in controllable generation utilization of intermediates. In this minireview, focusing on intermediates NO ‐involved reactions, we discuss newly developed methodologies studying controlling generation, conversion, intermediates, which enable recent developments that yield products, including ammonia (NH 3 ), organonitrogen molecules, compounds exhibiting unconventional oxidation states. Furthermore, also make an outlook highlight future directions emerging field reactions.

Язык: Английский

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