A Solid‐Solution with Asymmetric Ni‐O‐Cr Sites for Boosting Protonation toward Anodic Oxidation

Advanced Energy Materials, Год журнала: 2024, Номер 14(38)

Опубликована: Июль 14, 2024

Abstract Replacing the slow protonation process of oxygen evolution reaction (OER) with fast alcohol electro‐oxidation can decrease driving potentials, thus improving overall efficiency electrochemical devices. However, formation effective catalytic sites for oxidation remains challenging in accelerating to inhibit metal leaching and improve catalyst stability. Herein, asymmetric Ni‐O‐Cr are constructed by alloying Cr into NiO matrix optimize coordination environments, showing significantly enhanced stability during electro‐oxidation. The maintain constant valence states Ni oxidation, efficiently suppressing dissolution even at high potentials. In situ characterizations combined theoretical calculations indicate that adsorption activation OH* molecules compared pure NiO, increasing anodic kinetics. results also smaller gap 3 d ‐O 2 p strengthens charge transfer, leading This work gives insights boosting using sites‐enriched solid‐solution electrocatalysts.

Язык: Английский

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Efficient Electrocatalytic Oxidation of Glycerol to Formate Coupled with Nitrate Reduction over Cu‐Doped NiCo Alloy Supported on Nickel Foam

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(46)

Опубликована: Авг. 12, 2024

Abstract Electrooxidation of biomass‐derived glycerol which is regarded as a main byproduct industrial biodiesel production, an innovative strategy to produce value‐added chemicals, but currently showcases slow kinetics, limited Faraday efficiency, and unclear catalytic mechanism. Herein, we report high‐efficiency electrooxidation into formate via Cu doped NiCo alloy catalyst supported on nickel foam (Cu−NiCo/NF) in coupled system paired with nitrate reduction. The designed Cu−NiCo/NF delivers only 1.23 V vs . RHE at 10 mA cm −2 , record efficiency 93.8 %. superior performance ascribed the rapid generation Ni III −OOH Co species favorable coupling surface *O reactive intermediates. Using bifunctional catalyst, synchronously produces NH 3 formate, showing 290 mV lower than hydrogen evolution reaction, together excellent long‐term stability for up 144 h. This work lays out new guidelines reliable strategies from design electrochemical refinery.

Язык: Английский

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CoSe₂@NiSe‐CoSe₂ Heterojunction for Enhanced Electrocatalytic 5‐Hydroxymethylfurfural Oxidation Coupled with Hydrogen Evolution

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

Abstract Electrochemical 5‐hydroxymethylfurfural oxidation reaction (HMFOR) offers a promising approach to producing valuable chemicals and facilitating coupled H 2 production. A significant challenge in the HMFOR lies elucidating interaction mechanisms between active sites (HMF). However, unpredictable reconstruction of during catalytic process complicates understanding these mechanisms. In this study, novel heterojunction (CoSe @NiSe‐CoSe /NF) is synthesized using straightforward hydrothermal method combined with classical selenization. This demonstrates exceptional electrocatalytic performance for direct HMF oxidation, achieving Faradaic efficiency 2,5‐furanedicarboxylic acid (FDCA) up 97.9%. Notably, it requires only 1.29 V versus RHE achieve current density 10 mA cm −2 HMFOR‐assisted hydrogen evolution (HER). The high activity primarily arises from interfacial electron redistribution. Specifically, Co modulates band structure Ni, Se serving as intermediary. modulation increases adsorption energy reduces barrier rate‐determining step HMFOR. research not achieves selective synthesis high‐value but also provides comprehensive analysis structure‐performance relationship catalyst, offering new pathway development efficient heterogeneous catalysts.

Язык: Английский

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Electrochemical reduction of carbon dioxide to produce formic acid coupled with oxidative conversion of biomass

Journal of Energy Chemistry, Год журнала: 2024, Номер 92, С. 705 - 729

Опубликована: Фев. 6, 2024

Язык: Английский

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Promoting Electrocatalytic Glycerol C─C Bond Cleavage to Formate Coupled with H₂ Production Over a Cu_xNi_2–xP Catalyst

Advanced Energy Materials, Год журнала: 2024, Номер unknown

Опубликована: Июнь 10, 2024

Abstract Electrocatalytic oxidation of glycerol, an oversupplied byproduct the biodiesel industry, into high‐valued chemicals is alluring to diminishing current dependence on fossil energy. Formic acid important glycerol product that serves as a high‐energy‐density fuel and crucial precursor for fine chemical industry while developing electrocatalyst efficiently convert formic remains challenge. Herein, Cu‐doped nickel phosphide (Cu x Ni 2– P) electrocatalyst, achieving formate productivity ≈11 mol m −2 h −1 at 1.54 V versus RHE over broad concentration range (10–100 ) reported, which greater than threefolds 2 P. Furthermore, Cu P can enhance cleavage C─C bond in reducing production intermediates thus attaining high selectivity formate. In situ experiments integrated with density functional theory (DFT) calculation revealed doping promote generation III ─OOH species enrich substrates local environments surface, facilitating reaction efficiency. Finally, study designed membrane‐free flow electrolyzer continuous upgrading formate, 16.4 mmol coupled 0.68 L H 1.75 8 h.

Язык: Английский

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Electrochemical alcohol oxidation reaction on Precious‐Metal‐Free catalysts: Mechanism, activity, and selectivity

Carbon Neutralization, Год журнала: 2024, Номер 3(2), С. 285 - 312

Опубликована: Март 1, 2024

Abstract The electrochemical alcohol oxidation reaction (AOR) is pivotal for the development of sustainable energy. complete alcohols has attracted extensive attention as a vital process in fuel cells. Moreover, an alternative to oxygen evolution reaction, selective emerges effective means lower energy expenditure associated with electrolytic hydrogen production while yielding high‐value products. Nonprecious metal materials have been widely applied catalysis due their cost‐effectiveness and excellent durability. In recent years, leveraging advantages nonprecious electrocatalytic AOR, researchers delved into catalytic mechanisms various efficient catalysts fabricated evaluated. This review provides overview current advancements diverse systems centered around materials. It systematically summarizes shared traits distinctions characteristics across systems, thereby laying theoretical foundation developing novel catalyst that are efficient, stable, highly selective. will facilitate utilization further toward alcohols.

Язык: Английский

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Interfacial Spinel Local Interlocking Strategy Toward Structural Integrity in P3 Oxide Cathodes

ACS Nano, Год журнала: 2024, Номер 18(20), С. 12945 - 12956

Опубликована: Май 8, 2024

P3-layered transition oxide cathodes have garnered considerable attention owing to their high initial capacity, rapid Na+ kinetics, and less energy consumption during the synthesis process. Despite these merits, practical application is hindered by substantial capacity degradation resulting from unfavorable structural transformations, Mn dissolution migration. In this study, we systematically investigated failure mechanisms of P3 cathodes, encompassing dissolution, migration, irreversible P3–O3′ phase transition, culminating in severe collapse. To address challenges, proposed an interfacial spinel local interlocking strategy utilizing P3/spinel intergrowth as a proof-of-concept material. As result, demonstrated enhanced cycling performance. The effectiveness suppressing migration maintaining structure was validated through depth-etching X-ray photoelectron spectroscopy, absorption situ synchrotron-based diffraction. This engineering presents promising avenue for development advanced cathode materials sodium-ion batteries.

Язык: Английский

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Adsorption–Activation Bifunctional Center of Al/Co‐Base Catalyst for Boosting 5‐Hydroxymethylfurfural Oxidation

Advanced Energy Materials, Год журнала: 2024, Номер 14(43)

Опубликована: Авг. 2, 2024

Abstract Electrocatalytic conversion of biomass‐derived 5‐hydroxymethylfurfural (HMF) to value‐added 2,5‐furandicarboxylic acid (FDCA) is great significance in compensating for the rapid consumption fossil resources. However, it a challenge further improve performance HMF electrocatalytic oxidation (HMFOR) by synergistic kinetics (active sites) and thermodynamics (adsorption sites). In this work, Al(OH) 3 /Co(OH) 2 successfully fabricated as an efficient catalyst, its catalytic mechanism clarified. Extended X‐ray absorption fine structure (EXAFS) analysis demonstrate that electrochemically generated Co 3+ main site oxidation. The equilibrium adsorption capacity reach 57.0 mg g −1 , which effectively increase initial concentration substrate promoted reaction rate. combined results, based on 24 stable cycles FDCA yield retention rate 98.6% after 180 days, are highest ever achieved. Additionally, shown system can oxidize four other substrates. Therefore, work provides insight into hydroxide catalyst owes efficiency synergy between active sites.

Язык: Английский

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Inhibiting the Deep Reconstruction of Ni‐Based Interface by Coordination of Chalcogen Anions for Efficient and Stable Glycerol Electrooxidation

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Июль 22, 2024

Abstract Recently, Ni‐based chalcogenides havedemonstrated remarkable activity and selectivity for alcohol electrooxidation, but the mechanisms remain debated. This study synthesizes electrodeswith different chalcogen anion coordination on nickel nanorod arrays (NiO x /Ni,NiS /Ni, NiSe /Ni NRAs). NRAsshowcases superior performance (Faradaic efficiency 92.9%) in glycerolelectrooxidation reaction (GOR). In situ spectroscopy reveals that NiSecoordination inhibits deep oxidative reconstruction of interface, preventingNiOOH phase formation during GOR, enhancing stability /NiNRAs. Conversely, NiS NiO lead to with NiOOHphase formation, limiting GOR performance. Differently, competingreaction oxygen evolution (OER) leads deepreconstruction NiSex interface due instability Ni‐Sebonds, inducing degradation dissolution Se components. Furthermechanism investigation elucidates rate‐determining step (RDS) ofGOR at involves oxidation *C 2 H 3 O intermediatesthrough adsorption, favoring stable formate production.Contrarily, RDS , NiOOHinterfaces predominantly focus decarboxylation multi‐carbon intermediates, raisingenergy barriers over‐oxidizing CO . These results providenew insights designing non‐oxide catalysts forefficient electrocatalytic oxidation.

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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