Sub-1 nm Cu₂O Nanosheets for the Electrochemical CO₂ Reduction and Valence State–Activity Relationship

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 26133 - 26143

Published: Nov. 17, 2023

The copper-based (Cu-based) electrocatalytic materials effectively carry out the carbon dioxide reduction reaction (CO2RR) toward C2+ products, yet superiority and stability of oxidation state Cu are still worth studying. Herein, we designed prepared three Cu-based electrocatalysts with different states to study valence state-activity relationship. Among these electrocatalysts, Cu2O nanosheets thickness only 0.9 nm show an extremely high Faraday efficiency (FEC2+) ∼81%, FEC2+ has increase 37% compared traditional CuOx phase. ultrathin two-dimensional (2D) nanosheet structure abundant oxygen vacancies can stabilize improve selectivity for products in CO2RR. In situ Raman spectroscopy density functional theory calculations demonstrate that rich Cu+ 2D is most suitable *CO adsorption coverage on catalyst surface, which promotes C-C coupling This work provides excellent CO2RR products.

Language: Английский

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SiO₂ assisted Cu⁰–Cu⁺–NH₂ composite interfaces for efficient CO₂ electroreduction to C₂₊ products

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 12(2), P. 1218 - 1232

Published: Dec. 13, 2023

SiO 2 assisted abundant Cu 0 –Cu + –NH composite interfaces enhance the adsorption and activation of CO H O, strengthen intermediates, promote C–C coupling to produce C 2+ products.

Language: Английский

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Accelerating multielectron reduction at CuxO nanograins interfaces with controlled local electric field

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 15, 2023

Regulating electron transport rate and ion concentrations in the local microenvironment of active site can overcome slow kinetics unfavorable thermodynamics CO2 electroreduction. However, simultaneous optimization both is hindered by synthetic constraints poor mechanistic understanding. Here we leverage laser-assisted manufacturing for synthesizing CuxO bipyramids with controlled tip angles abundant nanograins, elucidate mechanism relationship between transport/ion electrocatalytic performance. Potassium/OH- adsorption tests finite element simulations corroborate contributions from strong electric field at sharp tip. In situ Fourier transform infrared spectrometry differential electrochemical mass unveil dynamic evolution critical *CO/*OCCOH intermediates product profiles, complemented theoretical calculations that thermodynamic improved coupling Cu+/Cu2+ interfaces. Through modulating concentrations, achieve high Faradaic efficiency 81% ~900 mA cm-2 C2+ products via CO2RR. Similar enhancement also observed nitrate reduction reaction (NITRR), achieving 81.83 mg h-1 ammonia yield per milligram catalyst. Coupling CO2RR NITRR systems demonstrates potential valorizing flue gases wastes, which suggests a practical approach carbon-nitrogen cycling.

Language: Английский

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Porphyrin-based metal–organic frameworks for photo(electro)catalytic CO₂ reduction

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(15), P. 5311 - 5335

Published: Jan. 1, 2024

The panorama of the latest developments emerging porphyrin-based MOFs for photo(electro)catalytic CO 2 reduction is shown.

Language: Английский

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Facet-switching of rate-determining step on copper in CO ₂ -to-ethylene electroreduction

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(25)

Published: June 10, 2024

Reduction of carbon dioxide (CO

Language: Английский

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Not One, Not Two, But at Least Three: Activity Origin of Copper Single-Atom Catalysts toward CO₂/CO Electroreduction to C₂₊ Products

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 14954 - 14958

Published: May 28, 2024

Copper (Cu) single-atom catalysts (SACs) exhibit great potential for generating multicarbon (C2+) products, but the intrinsic activity of Cu (Cu1) under realistic conditions remains controversial. Herein, we perform extensive calculations with explicit solvation to investigate underlying mechanism SACs, disclosing absence C2+ in Cu1 sites regardless different substrates. The original (first taking stably anchored on carbon nitride as an example) cannot facilitate *CO hydrogenation and CO–CO coupling due lack active nearby, they are unstable operation, causing leaching aggregation form small clusters. derived clusters composed at least three atoms can efficiently promote coupling, revealed by kinetic analyses. We extend modeling other typical SACs reveal that all inactive, while performance Cu-cluster is substrate-dependent. This study offers mechanistic insights into provides practical guidance their rational optimization.

Language: Английский

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Investigation and Mitigation of Carbon Deposition over Copper Catalyst during Electrochemical CO₂ Reduction

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(4), P. 151 - 160

Published: March 1, 2024

Copper (Cu) is considered to be the most effective catalyst for electrochemical conversion of carbon dioxide (CO2) into value-added hydrocarbons, but its stability still faces considerable challenge. Here, we report poisoning effect deposition during CO2 reduction on active sites Cu electrode─a critical deactivation factor that often overlooked. We find that, *C, an intermediate toward methane formation, could desorb electrode surface form species. reveal a strong correlation between formation and deposition, reaction conditions favoring production result in more deposition. The deposited blocks consequently causes rapid deterioration catalytic performance. further demonstrate can mitigated by increasing roughness pH electrolyte. This work offers new guidance designing stable catalysts reduction.

Language: Английский

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Dynamic Cu⁰/Cu⁺ Interface Promotes Acidic CO₂ Electroreduction

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8310 - 8316

Published: May 13, 2024

Acidic CO2 electroreduction reaction (CO2RR) shows advantages in high carbon utilization efficiency yet encounters great challenges suppressing undesired hydrogen evolution competition and increasing C2+ product selectivity. Although it is known that Cu0/Cu+ interfaces are conducive to C–C coupling processes, the oxidation state of copper cannot be well maintained under strong reductive condition large current electrolysis operation. Herein, we propose an I2 addition involved strategy protect Cu promote dynamic during acidic CO2RR. With electrolyte, a Faraday above 70% can achieved at 0.4–0.6 A cm–2 even low K+ concentration 0.3 M, which comparable those reported performances with almost ten times higher concentrations (2–3 M). This electrolytes significantly avoids salt crystallization transport channel enhance electrolyzer's stability. As proved by surface Pourbaix diagram experimental results, adding excessive into electrolyte boosts generation CuI; also, CuI metallic coexist electrochemical reduction conditions, demonstrating redox loop → exists. The holds key constructing interface, tightly bound adsorption *CO intermediate further promotes process.

Language: Английский

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Deciphering the Stability Mechanism of Cu Active Sites in CO₂ Electroreduction via Suppression of Antibonding Orbital Occupancy in the O 2p-Cu 3d Hybridization

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1351 - 1362

Published: Jan. 11, 2024

Copper-based catalysts, hallmarked by their ideal C–C coupling energy facilitated the symbiotic presence of Cu+ and Cu0 active sites, are poised to revolutionize selective electrochemical reduction CO2 C2H4. Regrettably, these catalysts beleaguered unavoidable diminution during reaction process, resulting in suboptimal C2H4 yields. To circumvent this limitation, we have judiciously mitigated antibonding orbital occupancy O 2p 3d hybridization introducing Cu defects into Cu2O, thereby augmenting Cu–O bond strength stabilize sites further decipher stabilization mechanism Cu+. This structural refinement, illuminated meticulous DFT calculations, fosters a heightened free threshold for hydrogen evolution (HER), while orchestrating thermodynamically favorable milieu enhanced within Cu-deficient Cu2O (Cuv-Cu2O). Empirically, Cuv-Cu2O has outperformed its pure counterpart, exhibiting prominent C2H4/CO ratio 1.69 as opposed 1.01, without conceding significant ground production over an 8 h span at −1.3 V vs RHE. endeavor not only delineates critical influence on reveals deep about but also charts pioneering pathway realm advanced materials design.

Language: Английский

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Crystal Engineering of MOF‐Derived Bimetallic Oxide Solid Solution Anchored with Au Nanoparticles for Photocatalytic CO₂ Reduction to Syngas and C₂ Hydrocarbons

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 20, 2024

Abstract Considering that CO 2 reduction is mostly a multielectron reaction, it necessary for the photocatalysts to integrate multiple catalytic sites and cooperate synergistically achieve efficient photocatalytic various products, such as C hydrocarbons. Herein, through crystal engineering, we designed constructed metal–organic framework‐derived Zr/Ti bimetallic oxide solid solution support, which was confirmed by X‐ray diffraction, electron microscopy absorption spectroscopy. After anchoring Au nanoparticles, composite photocatalyst exhibited excellent performances toward syngas (H production rates of 271.6 260.6 μmol g −1 h ) even hydrocarbons (C H 4 6 6.80 4.05 ). According control experiments theoretical calculations, strong interaction between support nanoparticles found be beneficial binding intermediates reducing reduction, highlighting synergy effect system with active sites.

Language: Английский

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