Modulation of Co spin state at Co3O4 crystalline-amorphous interfaces for CO oxidation and N2O decomposition

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 26, 2025

Modulation of electronic spin states in cobalt-based catalysts is an effective strategy for molecule activations. Crystalline-amorphous interfaces often exhibit unique catalytic properties due to disruptions long-range order and alterations structure. However, the mechanisms activation at remain elusive. Herein, we present a Co3O4 spinel-based catalyst featuring crystalline-amorphous interfaces. Characterization analyses confirm that tetrahedral Co2+ selectively etched from bulk spinel, forming amorphous CoO islands on surface. The resultant symmetry breaking coordination field induces reconstruction Co3+ 3 d orbitals, leading high-spin states. In CO oxidation, interface serves as novel active sites with lower energy barrier, facilitated by lattice oxygen activation. N2O decomposition, promotes reassociation dissociated through quantum exchange interactions. This work provides straightforward approach modulating state elucidates their role properties, but molecular these study presents

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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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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Lattice Oxygen-Driven Co-Adsorption of Carbon Dioxide and Nitrate on Copper: A Pathway to Efficient Urea Electrosynthesis

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

Published: Feb. 10, 2025

The electrochemical coupling of CO2 and NO3– on copper-based catalysts presents a sustainable strategy for urea production while simultaneously addressing wastewater denitrification. However, the inefficient random adsorption copper surface limits interaction key carbon nitrogen intermediates, thereby impeding efficient C–N coupling. In this study, we demonstrate that residual lattice oxygen in oxide-derived nanosheets (OL-Cu) can effectively tune electron distribution, thus activating neighboring atoms generating electron-deficient (Cuδ+) sites. These Cuδ+ sites enhance stabilize *CO which enables directional at adjacent This mechanism shortens pathway achieves yield up to 298.67 mmol h–1 g–1 −0.7 V versus RHE, with an average Faradaic efficiency 31.71% high current density ∼95 mA cm–2. situ spectroscopic measurements confirmed formation tracked evolution intermediates (i.e., *CO, *NO, *OCNO, *NOCONO) during synthesis. Density functional theory calculations revealed promote coadsorption *NO3, as well *OCNO significantly improving kinetics. study underscores critical role facilitating selectivity.

Language: Английский

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In situ/Operando Investigation for Heterogeneous Electro-Catalysts: From Model Catalysts to State-of-the-Art Catalysts

ACS Energy Letters, Journal Year: 2024, Volume and Issue: 9(9), P. 4414 - 4440

Published: Aug. 17, 2024

Electrochemical reactions, including water splitting, oxygen reduction, hydrogen oxidation, carbon dioxide nitrogen oxide etc., are critical for sustainable energy conversion and storage. Achieving high efficiency in these reactions requires catalysts with superior activity, selectivity, stability, often realized through nanostructured metal catalysts. However, practical challenges such as low selectivity catalytic degradation persist. In situ operando characterization techniques offer real-time insights into catalyst behavior under reaction conditions, enabling a deeper understanding of structure–performance relationships and, therefore, guiding the design optimization electro-catalysts. This review discusses common situ/operando techniques, highlights their applications model catalysts, single-atom single-crystal further explores combinational analysis to study complex nanocatalysts. Finally, we provide suggestions perspectives on development advance field electrochemical catalysis.

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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A multi-site Ru-Cu/CeO2 photocatalyst for boosting C-N coupling toward urea synthesis

Science Bulletin, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

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Multiple active site metal-based catalysts for C-N coupling reactions and the beyond

Next Materials, Journal Year: 2025, Volume and Issue: 8, P. 100555 - 100555

Published: Feb. 21, 2025

Language: Английский

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Elucidating Relay Catalysis on Copper Clusters With Satellite Single Atoms for Enhanced Urea Electrosynthesis

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

Published: March 10, 2025

Relay catalysis represents significant efficacy in alleviating competition among different reactants during coupling reactions. However, a comprehensive understanding of the reaction mechanism underlying relay for urea electrosynthesis remains challenging. Herein, we have developed catalyst (CuAC-CuSA@NC) comprising Cu atomic clusters (CuAC) with satellite Cu─N4 single atoms (CuSA) sites on nitrogen-doped porous interconnected carbon skeleton (NC), enabling elucidation process co-reduction CO2 and NO3 -. The designed CuAC-CuSA@NC exhibits an approximately threefold higher yield rate compared to that CuSA@NC at -1.3 V versus RHE. Ex-situ experimental results in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy analysis reveal formation sequence between *NH2 *NH2CO species increasing reduction potential. combination theoretical calculations further elucidates pathway involves "CuAC" facilitating conversion *NO3 *NOx, followed by hydrogenation form *H from water dissociation promoted "CuSA" sites, which subsequently couples *CO2 produce urea. This work provides novel insights into investigation reactions, but not limit to, synthesis.

Language: Английский

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Stabilization of Cu^δ+ Sites Within MnO₂ for Superior Urea Electro‐Synthesis

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(41)

Published: Sept. 2, 2024

Abstract Electrocatalytic C‐N coupling between NO 3 ‐ and CO 2 has emerged as a sustainable route for urea production. However, identifying catalytic active sites designing efficient electrocatalysts remain significant challenges. Herein, the synthesis of Cu‐doped MnO nanotube (denoted Cu‐MnO ) with stable Cu δ+ ‐oxygen vacancies (O vs )‐Mn 3+ dual is reported. Compared pure , doping can effectively enhance production performance in co‐reduction . Thus, catalyst exhibits maximum Faradaic efficiency (FE) 54.7% highest yield rate 116.7 mmol h −1 g cat. flow cell. Remarkably, remains over 78 across wide potential range. Further experimental theoretical results elucidate unique role solid‐solution stabilizing ‐O ‐Mn endowing superior structural electrochemical stabilities. This thermodynamically promotes formation kinetically lowers energy barrier coupling.

Language: Английский

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