Hydrophobic SiO₂ Armor: Stabilizing Cu^δ+ to Enhance CO₂ Electroreduction toward C₂₊ Products in Strong Acidic Environments

ACS Nano, Год журнала: 2024, Номер 18(23), С. 15303 - 15311

Опубликована: Май 28, 2024

Electroreduction of CO2 in highly acidic environments holds promise for enhancing utilization efficiency. Due to the HER interference and structural instability, however, challenges improving selectivity stability toward multicarbon (C2+) products remain. In this study, we proposed an "armor protection" strategy involving deposition ultrathin, hydrophobic SiO2 onto Cu surface (Cu/SiO2) through a simple one-step hydrolysis. Our results confirmed effective inhibition by layer, leading high Faradaic efficiency (FE) up 76.9% C2+ at current density 900 mA cm–2 under strongly condition with pH 1. The observed performance surpassed reported most previously studied Cu-based catalysts CO2RR systems. Furthermore, ultrathin shell was demonstrated effectively prevent reconstruction preserve oxidation state Cuδ+ active sites during CO2RR. Additionally, it hindered accumulation K+ ions on catalyst diffusion situ generated OH– away from electrode, thereby favoring product generation. Raman analyses coupled DFT simulations further elucidated that proficiently modulated *CO adsorption behavior Cu/SiO2 reducing energy, facilitating C–C coupling. This work offers compelling rationally designing exploiting stable environments.

Язык: Английский

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Supramolecularly Built Local Electric Field Microenvironment around Cobalt Phthalocyanine in Covalent Organic Frameworks for Enhanced Photocatalysis

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

The local electric field (LEF) plays an important role in the catalytic process; however, precise construction and manipulation of microenvironment around active site remains a significant challenge. Here, we have developed supramolecular strategy for implementation LEF by introducing host macrocycle 18-crown-6 (18C6) into cobalt phthalocyanine (CoPc)-containing covalent organic framework (COF). Utilizing interaction between 18C6 potassium ion (K+), locally enhanced K+ concentration CoPc can be built to generate catalytically Co site. COF with this supramolecularly realizes activity up 7.79 mmol mmolCo–1 h–1 photocatalytic CO2 reduction reaction (CO2RR), which is 180% improvement compared its counterpart without units. effect subtly controlled fully harnessing K+@18C6 changing salts different counterions. In situ spectroscopy density functional theory calculations show that complexation creates positive stabilizes critical intermediate *COOH involved CO2RR, tuned halide ion-mediated hydrogen-bonding interaction, consequently leading improved performance varying degrees.

Язык: Английский

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Tip carbon encapsulation customizes cationic enrichment and valence stabilization for low K+ acidic CO2 electroreduction

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 19, 2025

Abstract Acidic electrochemical CO 2 conversion is a promising alternative to overcome the low utilization. However, over-reliance on highly concentrated K + inhibit hydrogen evolution reaction also causes (bi)carbonate precipitation interfere with catalytic performance. In this work, under screening and guidance of computational simulations, we present carbon coated tip-like O 3 electrocatalyst for stable efficient acidic synthesize formic acid (HCOOH) concentration. The layer protects oxidized species higher intrinsic activity from reductive corrosion, peripherally formulates tip-induced electric field regulate adverse H attraction desirable enrichment. an electrolyte at pH 0.94, only 0.1 M required achieve Faradaic efficiency (FE) 98.9% 300 mA cm −2 HCOOH long-time stability over100 h. By up-scaling electrode into 25 electrolyzer setup, total current 7 A recorded sustain durable production 291.6 mmol L −1 h .

Язык: Английский

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Low-Cost, Facile, and Scalable Manufacturing of Single-Molecule-Integrated Catalytic Electrodes

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

To surmount the shortcomings of powder-based catalysts and small electrode sizes, development meter-scale integrated materials is essential for practical electrocatalytic applications, which requires fine control over effective surface grafting catalytic active sites on large-size electrodes as well addressing challenge balancing cost-effective large-scale manufacturing with highly stable operation. Herein, we report a low-cost, facile, scalable method directly constructing single-molecule-integrated using commercially available, flexible, size-tailored conductive carbon textiles (e.g., graphite felt) well-defined planar conjugated molecules metallophthalocyanines) via heterostacking steered cross-scale heterointerfacial assembly. This universal unlocks limitations traditional approaches that involve integrating catalysts, particles, binders Nafion), supported paper) through multiple processing steps typically result in centimeter-level electrodes. Meaningfully, our enables precise size, composition, microenvironment, structure to match various environments. As proof concept, an thiophene-gilded cobalt phthalocyanine demonstrates outstanding activity stability CO2 electroconversion alkaline, neutral, acidic media under industrially relevant current densities, even flowing paired-electrolysis system. study provides comprehensive scientific data engineering guidance systematic design scalable, binder-free electrodes, thereby promising drive sustainable energy-efficient electrolysis industrial scene.

Язык: Английский

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Acidic electroreduction CO2 to formic acid via interfacial modification of Bi nanoparticles at industrial-level current

Nano Research, Год журнала: 2024, Номер 17(7), С. 5817 - 5825

Опубликована: Март 23, 2024

Язык: Английский

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Flow-electrode capacitive separation of organic acid products and recovery of alkali cations after acidic CO ₂ electrolysis

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(41)

Опубликована: Окт. 3, 2024

Acidic CO

Язык: Английский

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Solid Electrolytes for Low-Temperature Carbon Dioxide Valorization: A Review

Environmental Science & Technology, Год журнала: 2024, Номер 58(25), С. 10881 - 10896

Опубликована: Июнь 11, 2024

One of the most promising approaches to address global challenge climate change is electrochemical carbon capture and utilization. Solid electrolytes can play a crucial role in establishing chemical-free pathway for CO2. Furthermore, they be applied electrocatalytic CO2 reduction reactions (CO2RR) increase utilization, produce high-purity liquid chemicals, advance hybrid electro-biosystems. This review article begins by covering fundamentals processes capture, emphasizing advantages utilizing solid electrolytes. Additionally, it highlights recent advancements use polymer electrolyte or layer CO2RR with multiple functions. The also explores avenues future research fully harness potential electrolytes, including integration performance assessment under realistic conditions. Finally, this discusses opportunities challenges, aiming contribute establishment green sustainable society through valorization.

Язык: Английский

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Salt Precipitation and Water Flooding Intrinsic to Electrocatalytic CO2 Reduction in Acidic Membrane Electrode Assemblies: Fundamentals and Remedies

EES Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

The fundamentals of salt precipitation and water flooding in membrane electrode assemblies for acidic electrocatalytic CO 2 reduction are discussed potential remedies via engineering electrodes, electrolytes, membranes proposed.

Язык: Английский

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Highly Selective Acidic CO₂ Electroreduction with Large Current on Polypyrrole‐Modified Ag Catalyst by Local Microenvironment Modulation

Advanced Energy Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 2, 2025

Abstract Electrocatalytic carbon dioxide reduction (CO 2 RR) holds great promise for capture and utilization. In acidic media, CO RR enables efficient conversion, but with low selectivity due to the competitive hydrogen evolution reaction (HER) catalyst corrosion. Herein, conductive polymer polypyrrole (PPy) coated Ag nanoparticles (NPs) catalysts (Ag@PPy) different thicknesses are designed synthesized, which could create a hydrophobic environment that reduces accessibility of H O NPs thereby inhibiting HER. The coating PPy layer also protects from corrosion improves stability system. Among them, Ag@PPy‐2 appropriate thickness showed up 91.7% electrocatalytic high durability in electrolyte at −300 mA cm −2 . Density functional theory (DFT) calculation shows not only inhibit HER, reduce energy barrier, improve efficiency CO. This study may provide some new ideas design advanced selective by local microenvironmental engineering.

Язык: Английский

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Carbon-supported nickel–molybdenum alloy/tungsten carbide nanoparticles as efficient bifunctional catalysts for hydrogen evolution and oxidation reactions in alkaline media

International Journal of Hydrogen Energy, Год журнала: 2025, Номер 114, С. 229 - 238

Опубликована: Март 1, 2025

Язык: Английский

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