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

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(38)

Published: July 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.

Language: Английский

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Pd Nanoparticle Size‐Dependent H^* Coverage for Cu‐Catalyzed Nitrate Electro‐Reduction to Ammonia in Neutral Electrolyte

Small, Journal Year: 2024, Volume and Issue: 20(46)

Published: Aug. 3, 2024

Abstract Electrochemical conversion of nitrate (NO 3 − ) to ammonia (NH is an effective approach reduce pollutants in the environment and also a promising low‐temperature, low‐pressure method for synthesis. However, adequate H * intermediates are highly expected NO hydrogenation, while suppressing competitive hydrogen evolution. Herein, effect coverage on RR synthesis by Cu electrocatalysts investigated. The can be adjusted changing Pd nanoparticle sizes. optimized Pd@Cu with average size 2.88 nm shows best activity RR, achieving maximum Faradaic efficiency 97% (at −0.8 V vs RHE) NH yield 21 mg h −1 cm 2 , from industrial wastewater level 500 ppm – . In situ electrochemical experiments indicate that particles promote hydrogenation via well‐modulated adsorbed species. Coupling anodic glycerol oxidation reaction, ammonium formate successfully obtained as value‐added products membrane electrode assembly electrolyzer. This work provides feasible strategy obtaining size‐dependent hydrogenation.

Language: Английский

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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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A Copper–Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 8012 - 8023

Published: Feb. 18, 2025

The electrocatalytic nitrite reduction (NO2RR) converts nitrogen-containing pollutants to high-value ammonia (NH3) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead low activity NH3 selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper-zinc cyanamide (Cu0.8Zn0.2NCN) with localized structure distortion tailored surface electrostatic potential, allowing asymmetric binding of NO2-. It exhibits outstanding NO2RR performance Faradaic efficiency ∼100% an yield 22 mg h-1 cm-2, among best such process. Theoretical calculations in situ spectroscopic measurements demonstrate that Cu-Zn sites coordinated linear polarized [NCN]2- could transform symmetric [Cu-O-N-O-Cu] CuNCN-NO2- [Cu-N-O-Zn] configuration Cu0.8Zn0.2NCN-NO2-, thus enhancing adsorption bond cleavage. A paired electro-refinery Cu0.8Zn0.2NCN cathode reaches 2000 mA cm-2 at 2.36 V remains fully operational industrial-level 400 >140 h production rate ∼30 mgNH3 cm-2. Our work opens new avenue tailoring potentials using strategy advanced electrocatalysis.

Language: 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, Journal Year: 2024, Volume and Issue: unknown

Published: June 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.

Language: Английский

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Interface engineering of Co nanoparticles decorated by Ir confined in N-doped carbon nanotubes for flexible Zn–air batteries and pH-universal overall water splitting

Rare Metals, Journal Year: 2024, Volume and Issue: 43(12), P. 6447 - 6459

Published: Aug. 5, 2024

Language: Английский

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Exploration of cobalt-based spinel oxide nanocatalysts MCo2O4 (M = Mn, Fe, Co, Ni, Cu, Zn) for glucose electrochemical sensing: NiCo2O4 exhibits largest Faradaic current

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: unknown, P. 156011 - 156011

Published: Sept. 1, 2024

Language: Английский

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Sustainable Upgrading of Biomass: A Thermodynamic Approach to Fine-Tuning Product Selectivity for Glycerol Oxidation

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

For electrochemical glycerol oxidation, thermodynamic insights show that applied bias, more than temperature, drives reaction selectivity—unlocking potential for optimized, targeted reactions.

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

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

Published: March 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.

Language: Английский

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