Tailoring CO₂ Adsorption Configuration with Spatial Confinement Switches Electroreduction Product from Formate to Acetate

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

Опубликована: Фев. 5, 2025

Multi-proton-coupled electron transfer, multitudinous intermediates, and unavoidable competing hydrogen evolution reaction during CO2 electroreduction make it tricky to control high selectivity for specific products. Here, we present spatial confinement of Fe single atoms (FeN2S2) by adjacent FeS clusters (Fe4S4) orientate the transition adsorption configuration from C,O-side O-end, which triggers a shift activated first-step protonation C–C coupling, thus switching target product HCOOH in Faraday efficiency (FE: 90.6%) on FeN2S2 CH3COOH 82.3%) Fe4S4/FeN2S2. The strength *OCHO upon solitary site is linearly related coordination number Fe–S, with predominantly produced over single-atom (ortho-substituted S atoms). Fe4S4 cluster functions as switch reduction product, can not only optimize electronic structure neighboring but also impel complete hydrocarbon intermediate *CH3, followed coupling CO2* *CH3 via synergistic catalysis This strategy provides new avenue modulate reactant model desirable pathways, potential applications diverse multistep electrochemical processes controlled selectivity.

Язык: Английский

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Unraveling the Mechanism of Cu/CeO₂ Interface Modulation for CO₂ Electroreduction Into C₂₊/CH₄

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Abstract Cu shows unique characteristics for electrochemical CO 2 reduction reaction (CO RR) to hydrocarbons and oxygenates due the moderate adsorption energy of key intermediate *CO. However, it remains a challenge selectively control RR towards C 1 (e.g., CH 4 ) or 2+ H 5 OH) through simple interface engineering. Herein, series inverse catalysts, composed CeO nanoparticles over substrate (Cu‐CeO ‐x), are subtly designed tackle issues. It is verified decoration induces highly active Cu/CeO interfacial sites that enhance conversion *CO intermediates into , while conducive generation. With increase deposition, selectivity present volcano‐type increasing tendency with maximum faradic efficiency 62.6% 51.3%, respectively. In‐situ infrared spectroscopy theoretical calculations reveal loading allows cooperate efficiently promote coupling *CO/*CHO intermediates, thus enhancing selectivity. In contrast, excessive suppresses C─C but boosts unilaterally hydrogenation, promoting production. This work provides effective strategies regulate by modulating metal/oxide interfaces.

Язык: Английский

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Optimizing C─C Coupling on Cu⁰/Cu⁺/Ga Interfaces by Enhancing Active Hydrogen Absorption for Excellent CO₂‐to‐C₂₊ Electrosynthesis

Small, Год журнала: 2025, Номер unknown

Опубликована: Март 5, 2025

The electrocatalytic reduction of CO2 (CO2RR) to high-value chemicals and fuels offers a promising route for clean carbon cycle. However, it often suffers from low catalytic activity poor selectivity. Heterostructure construction has been shown be an effective strategy producing multi-carbon products, but the synergistic mechanisms between multiple active sites resulting reconstruction process remain unclear. In this study, Ga2O3/CuO heterostructure is established via simple sol-gel method produce C2+ products. Experimental results demonstrate that Ga2O3 stabilizes Cu+ form Cu0/Cu+/Ga centers enhances water-splitting ability during reaction. improved hydrogen absorption on Ga site shifts C─C coupling reaction pathway *OCCO asymmetric *OCCHO path with lower energy barrier. As result, catalysts exhibit superior CO2RR performance, achieving 70.1% Faradaic efficiency at -1.2 VRHE in flow cell, ethylene reaching 58.3% remaining stable 10 h.

Язык: Английский

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Enhanced Local CO Coverage on Cu Quantum Dots for Boosting Electrocatalytic CO₂ Reduction to Ethylene

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 29, 2024

Abstract Ethylene (C 2 H 4 ) electrosynthesis from the electrocatalytic CO reduction process holds enormous potential applications in industrial production. However, sluggish kinetics of C─C coupling often result low yield and poor selectivity for C Herein, performance Cu catalysts varying sizes is investigated, prepared via a cryo‐mediated liquid phase exfoliation technique, electrochemical to . The activity gradually increase as size decreases tens nanometers few nanometers. Impressively, 5 nm quantum dots (Cu‐5) achieve maximum Faradaic efficiency (FE) 81.5% half‐cell cathodic energy (CEE) 42.2% with large partial current density 1.1 A cm −2 at −0.93 V versus reversible hydrogen electrode. Structural characterization situ spectroscopic analysis reveal that Cu‐5 dots, dominated by (100) facet, provide an abundance active sites enhance adsorption activation, promoting formation *CO intermediates. accumulation intermediates on facilitates CO‐CHO reaction, thus enhancing production rate.

Язык: Английский

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Gold Single Atom Doped Defective Nanoporous Copper Octahedrons for Electrocatalytic Reduction of Carbon Dioxide to Ethylene

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Янв. 24, 2025

Electrocatalytic CO2 reduction into high-value multicarbon products offers a sustainable approach to closing the anthropogenic carbon cycle and contributing neutrality, particularly when renewable electricity is used power reaction. However, lack of efficient durable electrocatalysts with high selectivity for multicarbons severely hinders practical application this promising technology. Herein, nanoporous defective Au1Cu single-atom alloy (De-Au1Cu SAA) catalyst developed through facile low-temperature thermal in hydrogen subsequent dealloying process, which shows toward ethylene (C2H4), Faradaic efficiency 52% at current density 252 mA cm–2 under potential −1.1 V versus reversible electrode (RHE). In situ spectroscopy measurements functional theory (DFT) calculations reveal that C2H4 product results from synergistic effect between Au single atoms Cu sites on surface catalysts, where promote *CO generation defects stabilize key intermediate *OCCO, altogether enhances C–C coupling kinetics. This work provides important insights design electrochemical products.

Язык: Английский

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Selective C–C coupling via copper atom reconfiguration in CO2 electroreduction

Frontiers of Chemical Science and Engineering, Год журнала: 2025, Номер 19(4)

Опубликована: Фев. 21, 2025

Язык: Английский

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Development of catalysts and reactor designs for CO₂ electroreduction towards C₂₊ products

Energy Materials, Год журнала: 2025, Номер 5(5)

Опубликована: Фев. 25, 2025

Recent research on the electrocatalytic CO2 reduction reaction (eCO2RR) has garnered significant attention given its capability to address environmental issues associated with emissions while harnessing clean energy produce high-value-added products. Compared C1 products, C2+ products provide greater densities and are highly sought after as chemical feedstocks. However, formation of C-C bond is challenging due competition H-H C-H bonds. Therefore, elevate selectivity yield fuels, it essential develop more advanced electrocatalysts optimize design electrochemical cell configurations. Of materials investigated for CO2RR, Cu-based stand out their wide availability, affordability, compatibility. Moreover, catalysts exhibit promising capabilities in adsorption activation, facilitating compounds via coupling. This review examines recent both cells electroreduction compounds, introducing core principles eCO2RR pathways involved generating A key focus categorization catalyst designs, including defect engineering, surface modification, nanostructure tandem catalysis. By analyzing studies catalysts, we aim elucidate mechanisms behind enhanced compounds. Additionally, various types electrolytic discussed. Lastly, prospects limitations utilizing highlighted future research.

Язык: Английский

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Rational Construction of Cu Active Sites for CO₂ Electrolysis to C₂₊ Product

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Abstract Electrocatalytic CO 2 reduction reaction (CO RR) has emerged as a promising approach in advancing towards carbon neutrality and addressing renewable energy intermittency. Copper‐based catalysts have received much attention due to their high catalytic activity convert into value‐added C 2+ products. However, RR exhibits diversity of products unavoidable hydrogen precipitation side reactions the moderate adsorption strength *CO on copper surface fact that electrode potential for is very close reduction. Here, we summarize recent advances structural design active site construction copper‐based RR, investigate effects improvement performance, with aim deepening understanding catalyst structure sites, thereby facilitating more efficient sustainable production chemicals.

Язык: Английский

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Single-Molecule Fluorescence Imaging of Energy-Related Catalytic Reactions

Chemical & Biomedical Imaging, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Язык: Английский

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A Review on Single Site Catalysts for Electrochemical CO₂ Reduction

Advanced Energy Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Abstract Single site catalysts (SSCs), characterized by high atomic utilization and well‐defined active sites, exhibit significant potential in the field of CO 2 electroreduction (CO RR). Typically, SSCs tend to a 2‐electron transfer reaction RR, there remain challenges achieving efficient conversion above 2‐electrons (methane (CH 4 ) multicarbon products(C 2+ ). Therefore, systematic review is crucial summarize recent advancements single electrocatalysts their structure‐activity relationship. The discussion begins with state‐of‐the‐art characterization techniques SSCs. Then influence central atoms, coordination environments, support metal‐support interactions on catalytic performance discussed detail. Subsequently, regulation strategies improve activity selectivity CH C products are discussed. Furthermore, dynamic evolution metal sites true nature during RR also addressed. Finally, associated for product formation analyzed.

Язык: Английский

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