Electrocatalytic reduction of CO₂ and CO to multi-carbon compounds over Cu-based catalysts

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(23), P. 12897 - 12914

Published: Jan. 1, 2021

This tutorial review discusses the similarities and differences between electrocatalytic reduction of CO 2 to C 2+ olefins oxygenates over Cu-based catalysts.

Language: Английский

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High carbon utilization in CO2 reduction to multi-carbon products in acidic media

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(6), P. 564 - 570

Published: June 9, 2022

Language: Английский

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Boosting electrocatalytic CO2–to–ethanol production via asymmetric C–C coupling

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 29, 2022

Abstract Electroreduction of carbon dioxide (CO 2 ) into multicarbon products provides possibility large-scale chemicals production and is therefore significant research commercial interest. However, the efficiency for ethanol (EtOH), a chemical feedstock, impractically low because limited selectivity, especially under high current operation. Here we report new silver–modified copper–oxide catalyst (dCu O/Ag 2.3% that exhibits Faradaic 40.8% energy 22.3% boosted EtOH production. Importantly, it achieves CO –to–ethanol conversion operation with partial density 326.4 mA cm −2 at −0.87 V vs reversible hydrogen electrode to rank highly significantly amongst reported Cu–based catalysts. Based on in situ spectra studies show results from tailored introduction Ag optimize coordinated number oxide state surface Cu sites, which * adsorption steered as both atop bridge configuration trigger asymmetric C–C coupling stablization intermediates.

Language: Английский

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Electrochemical CO2 reduction to ethylene by ultrathin CuO nanoplate arrays

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: April 6, 2022

Electrochemical reduction of CO2 to multi-carbon fuels and chemical feedstocks is an appealing approach mitigate excessive emissions. However, the reported catalysts always show either a low Faradaic efficiency C2+ product or poor long-term stability. Herein, we report facile scalable anodic corrosion method synthesize oxygen-rich ultrathin CuO nanoplate arrays, which form Cu/Cu2O heterogeneous interfaces through self-evolution during electrocatalysis. The catalyst exhibits high C2H4 84.5%, stable electrolysis for ~55 h in flow cell using neutral KCl electrolyte, full-cell ethylene energy 27.6% at 200 mA cm-2 membrane electrode assembly electrolyzer. Mechanism analyses reveal that nanostructures, interfaces, enhanced adsorption *OCCOH intermediate preserve selective prolonged production. robust produced coupled with mild electrolytic conditions facilitates practical application electrochemical reduction.

Language: Английский

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Identification of Cu(100)/Cu(111) Interfaces as Superior Active Sites for CO Dimerization During CO₂ Electroreduction

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 144(1), P. 259 - 269

Published: Dec. 28, 2021

The electrosynthesis of valuable multicarbon chemicals using carbon dioxide (CO2) as a feedstock has substantially progressed recently but still faces considerable challenges. A major difficulty lines in the sluggish kinetics forming carbon-carbon (C-C) bonds, especially neutral media. We report here that oxide-derived copper crystals enclosed by six {100} and eight {111} facets can reduce CO2 to products with high Faradaic efficiency 74.9 ± 1.7% at commercially relevant current density 300 mA cm-2 1 M KHCO3 (pH ∼ 8.4). By combining experimental computational studies, we uncovered Cu(100)/Cu(111) interfaces offer favorable local electronic structure enhances *CO adsorption lowers C-C coupling activation energy barriers, performing superior Cu(100) Cu(111) surfaces, respectively. On this catalyst, no obvious degradation was observed over 50 h continuous operation.

Language: Английский

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Single Pass CO₂ Conversion Exceeding 85% in the Electrosynthesis of Multicarbon Products via Local CO₂ Regeneration

ACS Energy Letters, Journal Year: 2021, Volume and Issue: 6(8), P. 2952 - 2959

Published: July 30, 2021

The carbon dioxide reduction reaction (CO2RR) presents the opportunity to consume CO2 and produce desirable products. However, alkaline conditions required for productive CO2RR result in bulk of input being lost bicarbonate carbonate. This loss imposes a 25% limit on conversion multicarbon (C2+) products systems that use anions as charge carrier—and overcoming this is challenge singular importance field. Here, we find cation exchange membranes (CEMs) do not provide locally conditions, bipolar (BPMs) are unstable, delaminating at membrane–membrane interface. We develop permeable regeneration layer (PCRL) provides an environment catalyst surface enables local regeneration. With PCRL strategy, crossover limited 15% amount converted into products, all cases. Low low flow rate combine enable single pass 85% (at 100 mA/cm2), with C2+ faradaic efficiency full cell voltage comparable anion-conducting membrane electrode assembly.

Language: Английский

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Construction of C–N bonds from small-molecule precursors through heterogeneous electrocatalysis

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(5), P. 303 - 319

Published: April 25, 2022

Language: Английский

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Interfacial Electrolyte Effects on Electrocatalytic CO₂ Reduction

ACS Catalysis, Journal Year: 2021, Volume and Issue: 12(1), P. 331 - 362

Published: Dec. 16, 2021

Electrocatalytic CO2 reduction (CO2RR), powered by renewable energy, has great potential in decreasing the concentration of atmosphere, as well producing high value-added fuels or chemicals. The electrode and electrolyte together determine catalytic performance CO2RR. Despite substantial progress been made design preparation high-performance catalysts, role at electrode–electrolyte interface (EEI) which could largely affect local environment not understood thoroughly. To maximize balance (i.e., activity, selectivity, stability) CO2RR from a standpoint application, fundamental understanding interfacial effects should be emphasized with equal importance to intrinsic properties catalyst. In this Review, we will focus on discussion (effects) electrolytes for We summarize according their compositions chemical environment, include solvents, pH, cations, anions, impurities, additives, modifiers. addition, in-depth investigations detection intermediates during reactions using situ spectroscopy techniques are included. mechanisms, current challenges, future developments, perspectives discussed.

Language: Английский

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Engineering Catalytic Interfaces in Cu^δ+/CeO₂-TiO₂ Photocatalysts for Synergistically Boosting CO₂ Reduction to Ethylene

ACS Nano, Journal Year: 2022, Volume and Issue: 16(2), P. 2306 - 2318

Published: Feb. 9, 2022

Photocatalytic CO2 conversion into a high-value-added C2 product is highly challenging task because of insufficient electron deliverability and sluggish C-C coupling kinetics. Engineering catalytic interfaces in photocatalysts provides promising approach to manipulate photoinduced charge carriers create multiple sites for boosting the generation from reduction. Herein, Cuδ+/CeO2-TiO2 photocatalyst that contains atomically dispersed Cuδ+ anchored on CeO2-TiO2 heterostructures consisting CeO2 nanoparticles porous TiO2 designedly constructed by pyrolytic transformation Cu2+-Ce3+/MIL-125-NH2 precursor. In designed photocatalyst, acts as light-harvesting material generating electron-hole pairs are efficiently separated interfaces, Cu-Ce dual active synergistically facilitate dimerization *CO intermediates, thus lowering energy barrier coupling. As consequence, exhibits production rate 4.51 μmol-1·gcat-1·h-1 73.9% selectivity terms utilization C2H4 under simulated sunlight, with H2O hydrogen source hole scavenger. The photocatalytic mechanism revealed operando spectroscopic methods well theoretical calculations. This study displays rational construction heterogeneous emphasizes synergistic effect enhancing product.

Language: Английский

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Recent Progresses in Electrochemical Carbon Dioxide Reduction on Copper‐Based Catalysts toward Multicarbon Products

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 31(37)

Published: June 26, 2021

Abstract Electrochemical carbon dioxide reduction reaction (CO 2 RR) offers a promising way of effectively converting CO to value‐added chemicals and fuels by utilizing renewable electricity. To date, the electrochemical single‐carbon products, especially monoxide formate, has been well achieved. However, efficient conversion more valuable multicarbon products (e.g., ethylene, ethanol, n ‐propanol, ‐butanol) is difficult still under intense investigation. Here, recent progresses in using copper‐based catalysts are reviewed. First, mechanism RR briefly described. Then, representative approaches catalyst engineering introduced toward formation RR, such as composition, morphology, crystal phase, facet, defect, strain, surface interface. Subsequently, key aspects cell for including electrode, electrolyte, design, also discussed. Finally, advances summarized some personal perspectives this research direction provided.

Language: Английский

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