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

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

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

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

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Advances of copper-based metal-organic frameworks and their derivatives in nitrate reduction to ammonia

Journal of environmental chemical engineering, Journal Year: 2025, Volume and Issue: unknown, P. 116076 - 116076

Published: March 1, 2025

Language: Английский

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Intermetallic PtSn Nanosheets with p–d Orbital Hybridization for Selective Hydroxylamine Electrosynthesis

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 9, 2025

The electrocatalytic nitrate reduction to hydroxylamine (NH2OH) is a challenging catalytic process that has gained significant attention. However, its performance hindered by the low selectivity of electrocatalysts. Here, intermetallic PtSn nanosheets with p–d orbital hybridization have been synthesized, which significantly enhances NH2OH. Faradaic efficiency NH2OH reaches maximum 82.83 ± 1.55% at −0.10 V versus reversible hydrogen electrode (vs RHE), and yield achieves 6.15 0.32 mmol h–1 mgcat–1 −0.25 vs RHE. Mechanistic studies reveal between p-block Sn d-block Pt effectively adsorption desorption boost electrochemical synthesis. Given their excellent in synthesis NH2OH, are utilized as cathode an alkaline-acid hybrid Zn–NO3– battery facilitate production achieving FE 80.42%.

Language: Английский

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Paired electrochemical synthesis of glycolic acid and ammonia from polyester and nitrate sewage

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101336 - 101336

Published: April 1, 2025

Language: Английский

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Neighboring clusters as additional adsorption sites to regulate the selectivity of single-atom catalysis

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 162508 - 162508

Published: April 1, 2025

Language: Английский

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Lattice Hydrogen Involved Electrocatalytic Nitrate Reduction to Hydroxylamine

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Electrocatalytic nitrate reduction to hydroxylamine (ENRH) provides a sustainable strategy for NH2OH synthesis under ambient conditions. At present, active hydrogen (*H) derived from water dissociation has been widely used as H-source hydrogenation, bringing big challenge ENRH. On the one hand, insufficient *H would lead accumulation of nitrite. other sufficient with high ability induce over-hydrogenation ammonia. To overcome this challenge, herein, we propose utilize lattice (Hlat) an appropriate We design and construct Cu-MnO2Hx electrocatalyst, in which Cu-triggered Jahn-Teller distortion [MnO6] octahedron significantly increases number Hlat. The Faradaic efficiency yield are 91.1% 396.6 mmol gcat.-1 h-1 over Cu-MnO2Hx, outperforming most reported catalysts. combined results isotopic tracking experiments theoretical calculations prove enrichment buffer functions Hlat, can provide abundant nitrate's selective hydroxylamine.

Language: Английский

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Construction of Atomic-Scale Compressive Strain for Oxime Electrosynthesis

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 16, 2025

Tuning the surface strain is a powerful strategy to enhance catalytic activity of metal nanocatalysts, yet an atomically precise catalyst with intramolecular unlock atomic-level strain-structure-activity relationship still highly desired. Herein, we report synthesis, structural anatomy, and performance toward cyclohexanone oxime electrosynthesis Ag16Cu18(C≡C-C6H11)24 (Ag16Cu18) nanocluster, which has Cu6 ring in center. The Cu-Cu distance only 1.616 Å single crystal, shortest bond Cu nanomaterials date. Furthermore, once Ag16Cu18 was loaded onto carbon paper, ultrashort elongated ∼2.40 Å, showing strong compressive strain. exhibited excellent electrosynthesis, manifested by maximal Faradaic efficiency, yield, yield rate reaching 47.4%, 95.4%, 2.66 mmol·h-1·cm-2 at -0.35 V, respectively. In-situ attenuated total reflection surface-enhanced infrared spectroscopy revealed that sites adjacent Ag atoms primarily reduce NO stabilize it *NH2OH stage, while provide H* for reduction adsorb react *NH2OH, forming simultaneously. Density functional theory calculations confirmed presence ring, facilitates formation adsorption, hence significantly contributing generation. This study not reports case clusters but also provides understanding employing bimetallic nanocluster-based catalysts valuable organic molecules.

Language: Английский

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Synergistic Effect of Cu1Pd1 Electrocatalyst with N/O Asymmetric Coordination for C-O bonds to C N bonds Boosting Hydrogen Production

Applied Catalysis B Environment and Energy, Journal Year: 2025, Volume and Issue: unknown, P. 125580 - 125580

Published: June 1, 2025

Language: Английский

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CO2/NOx-involved Electrochemical C-N Coupling Reactions

Chemical Research in Chinese Universities, Journal Year: 2024, Volume and Issue: 40(5), P. 764 - 775

Published: June 18, 2024

Language: Английский

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