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

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

Published: Jan. 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.

Language: Английский

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Phosphorus‐Modulated Cobalt Nanosheets with Confined Metal Defects for Enhanced Kinetics in Nitrite‐Glycerol Co‐Electrolysis

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

Published: March 27, 2025

Abstract Exploring advanced electrocatalysts for the paired electrolysis of nitrite reduction reaction (NO 2 RR) and glycerol oxidation (GOR) is significance co‐production value‐added chemicals, but remains a great challenge. Herein, novel phosphorus‐modulated cobalt nanosheet with low‐coordination metallic sites (P 3 ‐Co) developed as an electrocatalyst efficient nitrite‐glycerol co‐electrolysis. The membrane electrode assembled NO RR‖GOR electrolyzer realizes promising operation performance high Faradaic efficiencies yields NH (98.2%, 29.3 mg h −1 cm −2 ) formate (93.4%, 85.7 at 1.5 V, well superior catalytic stability over long‐term 300 100 mA . in situ characterizations theoretical calculations are employed to reveal origin intrinsic activity P ‐Co, suggesting that metal Co defects P‐modulation beneficial optimizing electronic structure adsorption/activation barriers N‐containing intermediates accelerated conversion kinetics both GOR RR. This work offers guidance exploiting highly‐active generation high‐value‐added products.

Language: Английский

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

Nano Energy, Journal Year: 2025, Volume and Issue: unknown, P. 110683 - 110683

Published: Jan. 1, 2025

Language: Английский

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

Environmental Science & Technology, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

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

Published: April 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.

Language: Английский

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

Nano Energy, Journal Year: 2025, Volume and Issue: unknown, P. 110939 - 110939

Published: April 1, 2025

Language: 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, Journal Year: 2024, Volume and Issue: unknown, P. 124991 - 124991

Published: Dec. 1, 2024

Language: Английский

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

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

Published: Jan. 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.

Language: Английский

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

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

Published: Feb. 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.

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

Published: Feb. 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.

Language: Английский

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