Stability Issues in Electrochemical CO₂ Reduction: Recent Advances in Fundamental Understanding and Design Strategies

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(51)

Published: Aug. 11, 2023

Electrochemical CO2 reduction reaction (CO2 RR) offers a promising approach to close the anthropogenic carbon cycle and store intermittent renewable energy in fuels or chemicals. On path commercializing this technology, achieving long-term operation stability is central requirement but still confronts challenges. This motivates organize present review systematically discuss issue of RR. starts from fundamental understanding on destabilization mechanisms RR, with focus degradation electrocatalyst change microenvironment during continuous electrolysis. Subsequently, recent efforts catalyst design stabilize active sites are summarized, where increasing atomic binding strength resist surface reconstruction highlighted. Next, optimization electrolysis system enhance by maintaining especially mitigating flooding carbonate problems demonstrated. The manipulation conditions also enables prolong RR lifespan through recovering catalytically mass transport process. finally ends up indicating challenges future opportunities.

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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Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26783 - 26790

Published: Nov. 28, 2023

The electroreduction of CO2 into value-added liquid fuels holds great promise for addressing global environmental and energy challenges. However, achieving highly selective yielding multi-carbon oxygenates through the electrochemical reduction reaction (eCO2RR) is a formidable task, primarily due to sluggish asymmetric C-C coupling reaction. In this study, novel metal-organic framework (CuSn-HAB) with unprecedented heterometallic Sn···Cu dual sites (namely, pair SnN2O2 CuN4 bridged by μ-N atoms) was designed overcome limitation. CuSn-HAB demonstrated an impressive Faradic efficiency (FE) 56(2)% eCO2RR alcohols, current density 68 mA cm-2 at low potential -0.57 V (vs RHE). Notably, no significant degradation observed over continuous 35 h operation specified density. Mechanistic investigations revealed that, in comparison copper site, site exhibits higher affinity oxygen atoms. This enhanced plays pivotal role facilitating generation key intermediate *OCH2. Consequently, compared homometallic Cu···Cu (generally ethylene product), were proved be more thermodynamically favorable between *CO *OCH2, leading formation *CO-*OCH2, which ethanol product.

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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Reaction Environment Regulation for Electrocatalytic CO₂ Reduction in Acids

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(26)

Published: April 19, 2024

The electrocatalytic CO

Language: Английский

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Cooperation of Different Active Sites to Promote CO₂ Electroreduction to Multi‐carbon Products at Ampere‐Level

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 12, 2024

Abstract Electroreduction of CO 2 to C 2+ products provides a promising strategy for reaching the goal carbon neutrality. However, achieving high selectivity at current density remains challenge. In this work, we designed and prepared multi‐sites catalyst, in which Pd was atomically dispersed Cu (Pd−Cu). It found that Pd−Cu catalyst had excellent performance producing from electroreduction. The Faradaic efficiency (FE) could be maintained approximately 80.8 %, even 0.8 A cm −2 least 20 hours. addition, FE above 70 % 1.4 . Experiments functional theory (DFT) calculations revealed three distinct catalytic sites. These active sites allowed efficient conversion , water dissociation, conversion, ultimately leading yields products.

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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Another role of CO-formation catalyst in acidic tandem CO2 electroreduction: Local pH modulator

Joule, Journal Year: 2024, Volume and Issue: 8(6), P. 1772 - 1789

Published: April 10, 2024

Language: Английский

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Synthesis of n‐Propanol from CO₂ Electroreduction on Bicontinuous Cu₂O/Cu Nanodomains

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 9, 2024

n-propanol is an important pharmaceutical and pesticide intermediate. To produce by electrochemical reduction of CO

Language: Английский

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

ACS Nano, Journal Year: 2024, Volume and Issue: 18(23), P. 15303 - 15311

Published: May 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.

Language: Английский

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