Spin State Modulation with Oxygen Vacancy Orientates C/N Intermediates for Urea Electrosynthesis of Ultrahigh Efficiency

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

Abstract The co‐electrolysis of CO 2 and NO 3 − to synthesize urea has become an effective pathway alternate the conventional Bosch‐Meiser process, while complexity C‐/N‐containing intermediates for C−N coupling results in electrosynthesis unsatisfactory efficiency. In this work, electronic spin state modulation maneuver with oxygen vacancies (Ov) is unveiled effectively meliorate oriented generation key * NH coupling, furnishing ultrahigh yield 2175.47 µg mg −1 h Faraday efficiency 70.1%. Mechanistic studies expound that Ov can induce conversion high‐spin Ni 2+ (t 2g 6 e g ) Ni@CeO 2−x low‐spin 3+ 1 ), which markedly enhances hybridization degree 3d N 2p orbitals NO, facilitating selective formation . Notably, situ generated serve as a localized proton donor promote electroreduction on adjacent site Ce −O exclusively afford CO, followed by each other efficiently urea. strategy tailored switching active provides reliable reference rectify structure electrocatalysts directional valorization.

Language: Английский

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Predicting electrocatalytic urea synthesis using a two-dimensional descriptor

Communications Chemistry, Journal Year: 2025, Volume and Issue: 8(1)

Published: Feb. 3, 2025

Electrochemical synthesis routes powered by renewable electricity can provide sustainable chemical commodities replacing conventional fossil-based processes. Increasing research focuses on value-added chemicals like the indispensable fertilizer urea, which also constitutes a study case for electrochemical CN-coupling. To guide identification of highly selective catalysts, we aim to new insight analysing existing experimental data selectivity transition metal catalysts towards electrochemically synthesized urea. Firstly, project high dimensional using principal component analysis (PCA) lower dimensions, and thereby confirm that urea is correlated with CO NH3. Furthermore, identified most suitable two-dimensional descriptors prediction out various adsorption energies calculated density functional theory (DFT). We suggest *H *O slabs predict in co-reduction CO2 nitrite ( NO2- ).

Language: Английский

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Boosted Nitrate and CO₂ Reduction for Urea Electrosynthesis on p-Block Bi Dispersed Ru Alloys

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: March 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.

Language: Английский

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Electrocatalytic Reductive Amination of Aldehydes and Ketones with Aqueous Nitrite

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

Published: March 10, 2025

The electrocatalytic utilization of oxidized nitrogen waste for C-N coupling chemistry is an exciting research area with great potential to be adopted as a sustainable method generation organonitrogen molecules. most widely used reaction reductive amination. In this work, we develop alternative electrochemical amination that can proceed in neutral aqueous electrolyte nitrite the nitrogenous reactant and via oxime intermediate. We selection criterion reduction electrocatalysts suited electrosynthesis and, doing so, find Pd highly efficient catalyst reaction, reaching Faradaic efficiency 82% at -0.21 V vs reversible hydrogen electrode. aliphatic or aromatic structure carbonyl impacts efficacy catalyst, substrates leading suppressed formation detrimental alcohol. developed Pb/PbO electrocatalyst selectively performs electrolyte. With acetone model substrate, demonstrate one-pot, two-step conversion isopropyl amine 85% yield 50% global efficiency.

Language: Английский

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