Electrocatalytic Systems for NO_x Valorization in Organonitrogen Synthesis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(3)

Опубликована: Окт. 13, 2023

Inorganic nitrogen oxide (NO

Язык: Английский

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Highly Efficient Electrosynthesis of Glycine over an Atomically Dispersed Iron Catalyst

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(14), С. 10084 - 10092

Опубликована: Март 26, 2024

Glycine is a nonessential amino acid that plays vital role in various biological activities. However, the conventional synthesis of glycine requires sophisticated procedures or toxic feedstocks. Herein, we report an electrochemical pathway for via reductive coupling oxalic and nitrate nitrogen oxides over atomically dispersed Fe–N–C catalysts. A selectivity 70.7% achieved Fe–N–C-700 at −1.0 V versus RHE. Synergy between FeN3C structure pyrrolic facilitates reduction to glyoxylic acid, which crucial producing oxime glycine, could reduce energy barrier *HOOCCH2NH2 intermediate formation thus accelerating conversion glycine. This new approach value-added chemicals using simple carbon sources provide sustainable routes organonitrogen compound production.

Язык: Английский

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Tandem catalysis in electrocatalytic nitrate reduction: Unlocking efficiency and mechanism

Interdisciplinary materials, Год журнала: 2024, Номер 3(2), С. 245 - 269

Опубликована: Фев. 28, 2024

Abstract The electrochemical nitrate reduction reaction (NO 3 RR) holds promise for ecofriendly removal. However, the challenge of achieving high selectivity and efficiency in electrocatalyst systems still significantly hampers mechanism understanding large‐scale application. Tandem catalysts, comprising multiple catalytic components working synergistically, offer promising potential improving NO RR. This review highlights recent progress designing tandem catalysts RR, including noble metal‐related system, transition metal electrocatalysts, pulsed electrocatalysis strategies. Specifically, optimization active sites, interface engineering, synergistic effects between catalyst components, various situ technologies, theory simulations are discussed detail. Challenges opportunities development scaling up RR further discussed, such as stability, durability, mechanisms. By outlining possible solutions future design, this aims to open avenues efficient comprehensive insights into mechanisms energy sustainability environmental safety.

Язык: Английский

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Sustainable Electrosynthesis of Cyclohexanone Oxime through Nitrate Reduction on a Zn–Cu Alloy Catalyst

ACS Catalysis, Год журнала: 2024, Номер 14(5), С. 3287 - 3297

Опубликована: Фев. 15, 2024

Cyclohexanone oxime is an important precursor for Nylon-6 and typically synthesized via the nucleophilic addition–elimination of hydroxylamine with cyclohexanone. Current technologies production are, however, not environment-friendly due to requirement harsh reaction conditions. Here, we report electrochemical method one-pot synthesis cyclohexanone under ambient conditions aqueous nitrate as nitrogen source. A series Zn–Cu alloy catalysts are developed drive reduction nitrate, where intermediate formed in electroreduction process can undergo a chemical present electrolyte produce corresponding oxime. The best performance achieved on Zn93Cu7 electrocatalyst 97% yield 27% Faradaic efficiency at 100 mA/cm2. By analyzing catalytic activities/selectivities different alloys conducting in-depth mechanistic studies situ Raman spectroscopy theoretical calculations, demonstrate that adsorption species plays central role performance. Overall, this work provides attractive strategy build C–N bond organic through reduction, while highlighting importance controlling surface product selectivity electrosynthesis.

Язык: Английский

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Nitrogenous Intermediates in NO_x‐involved Electrocatalytic Reactions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(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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Electrocatalytic C−N Couplings at Cathode and Anode

Advanced Energy Materials, Год журнала: 2024, Номер 14(28)

Опубликована: Фев. 21, 2024

Abstract Electrocatalytic C−N couplings are promising alternatives to construct bonds and synthesize vital chemicals, including amine, amide, amino acid, oxime, imine, nitrile, under ambient conditions. In recent years, the electrocatalytic coupling has attracted a wide range of research interest achieved considerable developments. Here, is systematically reviewed aiming at reductive cathode oxidative anode. cathodic part, reaction systems, corresponding design principles electrocatalysts for different mechanism studies from experimental theoretical aspects, application‐oriented devices summarized. Anodic offers potential approach replace conventional energy‐demand synthesis protocols, an indispensable part green controllable construction unsaturated C = N C≡N bonds. According principle that electron transfer crucial point in anodic coupling, reactions sorted out based on direct indirect paths, respectively. Finally, challenges outlooks this field proposed. appealing topic electrochemistry possesses infinite possibilities future.

Язык: Английский

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Upgrading waste NOx into amino acids via electrocatalysis on Co nanoparticles encapsulated in hollow carbon nanofibers

Science China Chemistry, Год журнала: 2024, Номер 67(6), С. 1946 - 1952

Опубликована: Апрель 18, 2024

Язык: Английский

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Amino Acid Synthesis through C–N Coupling between α-Ketoacids and Hydroxylamine from Nitrate Reduction

ACS Catalysis, Год журнала: 2024, Номер 14(13), С. 10164 - 10171

Опубликована: Июнь 20, 2024

The artificial synthesis of amino acids is an important yet challenging subject. Electrocatalytic C–N coupling from organic and nitrogen sources provides opportunity for this target but with the difficulty bond formation toward production acids. Herein, we report (alanine, glutamic acid, glycine, leucine, valine) nitrate α-ketoacids a hybrid catalyst, cobalt phthalocyanine immobilized on carbon nanotubes (CoPc/CNT). Faradaic efficiency alanine CoPc/CNT as high 61%. CoPc catalyst integrated CNTs can catalyze reduction to hydroxylamine, which switched thermodynamically uphill downhill process. hydroxylamine intermediate attacks α-carbon α-ketoacid form oxime. Amino are produced by oximes catalyzed CNTs. bifunctionality steers tandem catalytic reaction efficient in one pot. This work identifies that enhancing key acid synthesis.

Язык: Английский

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Opportunities and challenges in biomass electrocatalysis and valorization

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 358, С. 124404 - 124404

Опубликована: Июль 14, 2024

Язык: Английский

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Selective electrosynthesis of hydroxylamine from aqueous nitrate/nitrite by suppressing further reduction

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 12, 2024

The electrocatalytic reduction of nitrogenous waste offers a sustainable approach to producing nitrogen-containing chemicals. selective synthesis high-value hydroxylamine (NH2OH) is challenging due the instability NH2OH as an intermediate. Here, we present rational electrocatalyst design strategy for promoting electrosynthesis by suppressing competing pathways further reduction. We screen zinc phthalocyanines (ZnPc) with high energy barrier regulating their intrinsic activity. Additionally, discover that carbon nanotube substrates exhibit significant NH3-producing activity, which can be effectively inhibited coverage ZnPc molecules. In-situ characterizations reveal and HNO are generated intermediates in nitrate NH3, enriched electrode. In H-cell, optimized catalyst demonstrates Faradaic efficiency (FE) 53 ± 1.7% partial current density exceeding 270 mA cm−2 turnover frequency 7.5 0.2 s−1. It also enables rapid cyclohexanone oxime from nitrite FE 64 1.0%. Electroreduction or appealing route but remains its intermediate nature. authors fast tuning metal phthalocyanine activity removing side reaction sites.

Язык: Английский

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