Active Hydroxyl‐Mediated Preferential Cleavage of Carbon‐Carbon Bonds in Electrocatalytic Glycerol Oxidation

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

Electrocatalytic glycerol oxidation reaction (GOR) to produce high-value formic acid (FA) is hindered by high formation potential of active species and sluggish C-C bond cleavage kinetics. Herein, Ni single-atom (NiSA) Co (CoSA) dual sites anchored on nitrogen-doped carbon nanotubes embedded with Ni0.1Co0.9 alloy (Ni0.1Co0.9@NiSACoSA-NCNTs) are constructed for electrochemical GOR. Remarkably, it can reach 10 mA cm-2 at a low 1.15 V versus the reversible hydrogen electrode (vs. RHE) realize formate selectivity 93.27 % even conversion 98.81 1.45 vs. RHE. The GOR mechanism pathway systematically elucidated via experimental analyses theoretical calculations. It revealed that hydroxyl (*OH) be produced during NiSA, CoSA, synergistically optimizes electronic structure CoSA sites, reducing energy barriers *OH-mediated bonds dehydrogenation C1 intermediates. This decreases number intermediates steps GOR-to-FA, thus increasing production efficiency. After coupling evolution in membrane assembly cell, 14.26 g 23.10 L H2 100 108 h.

Язык: Английский

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Recent Breakthroughs in Electrocatalytic Reduction of Nitrogen-Oxyanions for Environmentally Benign Ammonia Synthesis

Nano Energy, Год журнала: 2025, Номер unknown, С. 110683 - 110683

Опубликована: Янв. 1, 2025

Язык: Английский

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Doping Mo Triggers Charge Distribution Optimization and P Vacancy of Ni₂P@Ni₁₂P₅ Heterojunction for Industrial Electrocatalytic Production of Adipic Acid and H₂

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Synchronous electrosynthesis of value-added adipic acid (AA) and H2 is extremely crucial for carbon neutrality. However, accomplishing the preparation AA at large current density with high selectivity still challenging. Herein, a robust Mo-doped Ni2P@Ni12P5 heterojunction more P vacancies on Ni foam proposed simultaneous electrooxidation cyclohexanol (CHAOR) to hydrogen evolution reaction (HER) density. Combined X-ray photoelectron spectroscopy, absorption fine structure, electron spin resonance confirm that Mo incorporation induces charge redistribution Ni2P@Ni12P5, where adjusts electrons from P, triggers vacancies. Further experimental theoretical investigations reveal d-band center upshifted, optimizing adsorption energies water electron-rich site boosting HER activity. Besides, Ni3+ generated electron-deficient induced by Mo, alongside OH* triggered concurrently promote CHA dehydrogenation C─C bond cleavage, decreasing energy barrier CHAOR. Consequently, two-electrode flow electrolyzer achieves industrial (>230 mA cm-2) 85.7% yield, 100% Faradaic efficiency production. This study showcases an bifunctional electrocatalyst production productivity.

Язык: Английский

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Recent advances in electrochemical cathodic nitrogen oxide reduction coupled with thermodynamically favorable anodic oxidation

Nano Energy, Год журнала: 2025, Номер unknown, С. 110939 - 110939

Опубликована: Апрель 1, 2025

Язык: Английский

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Self-Powered Energy-Efficient Electrochemical Nitrite Reduction Coupled with Sulfion Oxidation for Ammonia Synthesis and Sulfur Recovery over Hierarchical Cobalt Sulfide Nanostructures

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер unknown, С. 124991 - 124991

Опубликована: Дек. 1, 2024

Язык: Английский

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Active Hydroxyl‐Mediated Preferential Cleavage of Carbon‐Carbon Bonds in Electrocatalytic Glycerol Oxidation

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

Abstract Electrocatalytic glycerol oxidation reaction (GOR) to produce high‐value formic acid (FA) is hindered by high formation potential of active species and sluggish C−C bond cleavage kinetics. Herein, Ni single‐atom (Ni SA ) Co (Co dual sites anchored on nitrogen‐doped carbon nanotubes embedded with 0.1 0.9 alloy @Ni ‐NCNTs) are constructed for electrochemical GOR. Remarkably, it can reach 10 mA cm −2 at a low 1.15 V versus the reversible hydrogen electrode (vs. RHE) realize formate selectivity 93.27 % even conversion 98.81 1.45 vs. RHE. The GOR mechanism pathway systematically elucidated via experimental analyses theoretical calculations. It revealed that hydroxyl (*OH) be produced during , synergistically optimizes electronic structure sites, reducing energy barriers *OH‐mediated bonds dehydrogenation C 1 intermediates. This decreases number intermediates steps GOR‐to‐FA, thus increasing production efficiency. After coupling evolution in membrane assembly cell, 14.26 g 23.10 L H 2 100 108 h.

Язык: Английский

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Delineating Catalyst Deactivation Mechanisms in Electrocatalytic Glycerol Oxidation toward Biodiesel Wastewater/CO₂ Co-valorization

Environmental Science & Technology, Год журнала: 2025, Номер unknown

Опубликована: Фев. 7, 2025

Biodiesel plays a key role in achieving economy-wide decarbonization but its production discharges significant amounts of CO2 and glycerol-laden wastewater. Given the increasing abundance biodiesel wastewater low redox potential glycerol, coupling glycerol oxidation reaction (GOR) with electrolysis has emerged as an attractive strategy to achieve sustainable management, utilization, green chemical synthesis single unit process. Despite need for highly stable catalysts, few studies have examined electrocatalyst deactivation environmental waste streams. Here, we present first-of-a-kind diagnostic study that investigates nickel (Ni) catalyst stability during GOR synthetic wastewaters. A current decline 99.7% was observed within 24 h operation. This coincided 80% decrease surface active Ni(II)/Ni(III) concentrations, 190-fold increases interfacial impedance, appearance electrode C-bonds suggested coverage by reactants intermediates likely main contributor loss catalytic activity. Analyses more complex electrolytes containing methanol oleate emergence distinct mechanisms through restricted NiOOH formation. Altogether, this details several previously unreported mechanisms. These findings can ultimately help inform future design toward practical valorization.

Язык: Английский

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A Transition‐Metal‐Based Bifunctional Electrocatalyst for Coupling Glucose Upgrade with Nitrate Reduction

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 10, 2025

Abstract The integration of glucose oxidation reaction (GOR) and nitrate reduction (NO 3 − RR) in an electrolyzer affords a sustainable approach to produce high value‐added products remove pollutants. Herein, 3D hierarchical architecture consisting defect‐rich copper–cobalt nanosheets immobilized by cobalt phosphide‐modified nickel foam (D‐CuCo/CoP/NF) is rationally designed as bifunctional electrocatalyst for GOR NO RR. resulting self‐standing electrode displayed remarkable activity. Only 1.29 V vs. RHE required yield current density 100 mA cm −2 . Glucose efficiently converted into formate with selectivity value 93.4% Faraday efficiency (FE) 90.3%. as‐prepared D‐CuCo/CoP/NF also capable transforming nitrates valuable ammonia, leading FE 96.9% rate 802.9 µmol h −1 Such performance renders it the best electrocatalysts Mechanistic studies revealed that defects catalyst greatly facilitated adsorption both Cu(OH) 2 Co 3+ ‐O/Co 4+ ‐O species served active sites reaction. A GOR||NO RR hybrid flow cell constructed using electrode, at voltage 1.35 V.

Язык: Английский

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Flower‐Shaped Zinc Oxide Nanostructures Loaded with Au Nanoparticles for Efficient and Highly Stable Production of Dihydroxyacetone from Glycerol Oxidation

Advanced Sustainable Systems, Год журнала: 2025, Номер unknown

Опубликована: Фев. 9, 2025

Abstract The selective oxidation of glycerol to dihydroxyacetone (DHA) represents a critical method for efficiently utilizing glycerol, primary byproduct biodiesel production. However, the challenge balancing catalyst activity and recycling stability significantly limits practical application this process. Herein, conversion performance is effectively modulated by controlling nanostructure support in Au‐supported catalysts. Zinc oxide carriers with morphologies nanorods (NRs), nanoflowers (NFs), nanoparticles (NPs) are successfully prepared loaded Au obtain series Au/ZnO‐Z Among them, composed flower‐shaped zinc nanostructures NPs (Au/ZnO‐NF) exhibits optimal performance, 92.9% DHA selectivity 69.5%. Notably, Au/ZnO‐NF demonstrates exceptional cycling surpassing most currently reported catalysts, maintaining 75.2% 75.1% even after five cycles. Comprehensive characterization experimental analysis demonstrat that catalysts exhibit low reduction temperatures, smallest nanoparticle size, excellent crystallinity, enhance adsorption O 2 polyols at secondary hydroxyl moiety.

Язык: Английский

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Electrooxidation of Glycerol to Formic Acid: from Catalyst Design Strategies to Key Coupled Systems

ChemSusChem, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Abstract As a major by‐product of biodiesel production, glycerol offers significant economic potential when effectively utilized. The electrooxidation to formic acid in couped systems has attracted considerable attentions due its environmental friendliness, cost‐effectiveness, low energy consumption and production high‐value‐added chemicals. This concept presents the key strategies for catalyst design rational construction representative coupled towards efficient acid. Firstly, we overview from four aspects, including heteroatom doping, vacancy engineering, interface component construct highly active sites tune electronic properties electrocatalysts. Subsequently, discuss oxidation acid, highlight importance high‐value added Finally, conclude by outlining current challenges proposing future perspectives, arouse further research interest facilitate development.

Язык: Английский

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