Ultralow Coordination Copper Sites Compartmentalized within Ordered Pores for Highly Efficient Electrosynthesis of n-Propanol from CO₂

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 25, 2025

Coordinatively unsaturated copper (Cu) has been demonstrated to be effective for electrifying CO2 reduction into C3 products by adjusting the coupling of C1-C2 intermediates. Nevertheless, intuitive impacts ultralow coordination Cu sites on are scarcely elucidated due lack synthetic recipes with low numbers and its vulnerability aggregation under reductive potentials. Herein, computational predictions revealed that higher levels coordinative unsaturation favored adsorption C1 C2 Building upon correlations, we constructed an catalyst from in situ oxide nanoparticles (CuO NPs) compartmentalized within ordered porous matrix, achieving a remarkable Faradaic efficiency (FE) n-propanol (n-PrOH) electroreduction, reaching up 27.4% H-cell at -0.8 VRHE 11.8% 300 mA cm-2 flow cell. The presence maintenance during rigorous electrolysis process contributed outstanding performances, as verified combination spectroscopy techniques, disclosing formed featured strong *C1 *C2 intermediates lead n-PrOH.

Language: Английский

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Direct low concentration CO2 electroreduction to multicarbon products via rate-determining step tuning

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 29, 2024

Direct converting low concentration CO2 in industrial exhaust gases to high-value multi-carbon products via renewable-energy-powered electrochemical catalysis provides a sustainable strategy for utilization with minimized separation and purification capital energy cost. Nonetheless, the electrocatalytic conversion of dilute into value-added chemicals (C2+ products, e.g., ethylene) is frequently impeded by rate weak carbon intermediates' surface adsorption strength. Here, we fabricate range Cu catalysts comprising fine-tuned Cu(111)/Cu2O(111) interface boundary density crystal structures aimed at optimizing rate-determining step decreasing thermodynamic barriers adsorption. Utilizing engineering, attain Faradaic efficiency (51.9 ± 2.8) % partial current (34.5 6.4) mA·cm−2 C2+ feed condition (5% v/v), comparing state-of-art electrolysis. In contrast prevailing belief that activation ( $${{CO}}_{2}+{e}^{-}+\, * \,\to {}^{ }{CO}_{2}^{-}$$ ) governs reaction rate, discover that, under conditions, shifts generation *COOH $${}^{ } {{CO}}_{2}^{-}+{H}_{2}O\to {COOH}+{{OH}}^{-}({aq})$$ Cu0/Cu1+ boundary, resulting better production performance. The development operate resembling waste holds promise reduction. authors report vacuum calcination approach regulating on Cu-based can electro-catalyze low-concentration CO2.

Language: Английский

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Highly Selective CO2 Electroreduction to Multi‐carbon Alcohols via Amine Modified Copper Nanoparticles at Acidic Conditions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(49)

Published: Aug. 13, 2024

Abstract Electroreduction of CO 2 into multi‐carbon (C2+) products (e.g. C2+ alcohols) offers a promising way for utilization. Use strong alkaline electrolytes is favorable to producing products. However, can react with hydroxide form carbonate/bicarbonate, which results in low carbon utilization efficiency and poor stability. Using acidic electrolyte an efficient solve the problems, but it challenge achieve high selectivity Here we report that amine modified copper nanoparticles exhibit at condition. The Faradaic (FE) reach up 81.8 % media (pH=2) total current density 410 mA cm −2 over n‐butylamine Cu. Especially FE alcohols 52.6 %, higher than those reported electroreduction In addition, single‐pass towards production 60 %. Detailed studies demonstrate molecule on surface Cu cannot only enhance formation, adsorption coverage *CO, also provide hydrophobic environment, result

Language: Английский

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Strategies for Improving Product Selectivity in Electrocatalytic Carbon Dioxide Reduction Using Copper‐Based Catalysts

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(51)

Published: Aug. 29, 2024

Abstract As an effective approach to converting carbon oxide (CO 2 ) into value‐added carbonaceous products, the electrochemical CO reduction reaction (ECO RR) has shown considerable potential for neutrality, addressing global pollution and climate issues. Copper (Cu)‐based electrocatalysts (CuECs) are acknowledged as important candidates ECO RR of multi‐carbon products. Nevertheless, complicated electron transfer multiple competitive pathways in production process raise challenges product selectivity. While achieving high current density structural stability, improving selectivity CuECs become crucial their practical applications. Herein, overview fundamental thermodynamic kinetic principles presented. Then, typical strategies summarized increasing CuEC formation products from , including morphological control, component design, defect interface design. The catalyst catalytic performance, mechanisms involved these reviewed. Finally, major future prospects high‐performance discussed.

Language: Английский

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Crown ether functionalization boosts CO2 electroreduction to ethylene on copper-based MOFs

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

Published: Jan. 1, 2025

Incorporating crown ether into Cu-based MOFs tailors the microenvironment at electrolyte–catalyst interface, enhancing Faradaic efficiency of electrochemical CO 2 reduction reaction to ethylene (C H 4 ).

Language: Английский

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Progress in Cu‐Based Catalyst Design for Sustained Electrocatalytic CO₂ to C₂₊ Conversion

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Abstract The electrocatalytic conversion of CO 2 into valuable multi‐carbon (C 2+ ) products using Cu‐based catalysts has attracted significant attention. This review provides a comprehensive overview recent advances in catalyst design to improve C selectivity and operational stability. It begins with an analysis the fundamental reaction pathways for formation, encompassing both established emerging mechanisms, which offer critical insights design. In situ techniques, essential validating these by real‐time observation intermediates material evolution, are also introduced. A key focus this is placed on how enhance through manipulation, particularly emphasizing catalytic site construction promote C─C coupling via increasing * coverage optimizing protonation. Additionally, challenge maintaining activity under conditions discussed, highlighting reduction active charged Cu species materials reconstruction as major obstacles. To address these, describes strategies preserve sites control including novel utilization mitigation reconstruction. By presenting developments challenges ahead, aims guide future conversion.

Language: Английский

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Stabilizing Oxidation State of Cu via Ce Doping into La₂CuO₄ for Enhanced Electroreduction of CO₂ to Multicarbon Products

Small Methods, Journal Year: 2025, Volume and Issue: unknown

Published: March 4, 2025

Stabilizing oxidation state of Cu (Cuδ+, δ > 0) sites is the key-enabling issue for electrocatalytic carbon dioxide (CO2) reduction reaction (eCO2RR) to multicarbon (C2+) products. The present study addresses this challenge by introducing cerium (Ce) doping into La2CuO4. Ce facilitates f-d orbital coupling between 4f and 3d orbitals, suppressing electron enrichment around atoms transferring electrons from orbitals via a Cu-O-Ce chain. These changes modulate electronic structure Cu, reduce distance neighboring atoms, optimize binding energy surface-adsorbed CO (*CO), lower barrier *CO dimerization. As result, La1.95Ce0.05CuO4 catalyst achieves Faradaic efficiency up 81% C2+ products maintains high stability over 50 h operation. This work highlights unique role in stabilizing Cuδ+ hence enhancing C-C coupling, providing pathway designing efficient catalysts eCO2RR.

Language: Английский

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Selective formaldehyde condensation on phosphorus-rich copper catalyst to produce liquid C3+ chemicals in electrocatalytic CO2 reduction

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: May 22, 2025

Language: Английский

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Enhanced CO2 Electroreduction to ethylene on Cu nanocube coated with nitrogen-doped carbon shell in-situ electro-derived from metal-organic framework

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 499, P. 156694 - 156694

Published: Oct. 13, 2024

Language: Английский

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Ag Stabilized Cu⁺/Cu⁰ Interface Catalysts for Enhanced CO₂ Electroreduction to C₂₊ Products at Ampere Level Current Density

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Electrochemical carbon dioxide reduction reaction (CO2RR) to yield multicarbon (C2+) products still suffers from a great hardship, which requires high current density and Faradaic efficiency (FE) accompanied by favorable stability for the purpose of industrial applications. Herein, we display 5.6 atom % Ag/Cu2O–Cu catalyst with abundant steady Ag/Cu+/Cu0 interfaces efficient conversion CO2-to-C2+ at ampere level density. attains desirable FE 76.5 ± 1.2% toward C2+ 1.0 A/cm2 in 1 M KOH electrolyte remains stable CO2 electrolysis 0.50 20 h using flow cell apparatus. In situ Raman spectrometry functional theory calculations indicate that interface can promote through adjusting energy barrier formation dimerization *CO intermediates. The synergistically heterogeneous activity, selectivity, electroreduction via tandem route *COOH, *CO, *OCCO intermediates over cooperative sites.

Language: Английский

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