Atomically Dispersed Ga Synergy Lewis Acid‐Base Pairs in F‐doped Mesoporous Cu₂O for Efficient Eletroreduction of CO₂ to C₂₊ Products

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Апрель 22, 2024

Abstract Electroreduction of CO 2 into high‐value chemicals and fuels driven is an effective way to alleviate the environmental crisis, but it suffers from poor activity low selectivity catalyst. Single‐atom catalysts have excellent highest atomic efficiency, are widely used in 2‐electron transfer produce CO. However, electroreduction C 2+ products involves complex processes such as multi‐electron reaction competitive adsorption, so single‐atom catalysis often powerless. Herein, a Ga‐anchored F‐doped Cu O catalyst with dual active sites reported. The Lewis acid‐base pairs Ga single atom promote adsorption/activation dissociation water molecules, respectively, enhance coverage *CO *H, their synergy optimizes path. At high current density 600 mA cm −2 , FE C2+ reached 72.8 ± 3.2% remarkable stability. Experiments theory calculations demonstrate that increase key intermediate transformed *CHO through protonation reaction, which changes path C─C coupling (*OCCO) followed by (*OCCHO) energy barrier, greatly improving for products.

Язык: Английский

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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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Synergistic Effects in the Electrochemical Carbon Dioxide Reduction Reaction for Multi‐Carbon Product Formation

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Abstract The synergistic effects in electrocatalysis can significantly enhance catalyst performance by improving catalytic activity, selectivity, and stability, optimizing reaction mechanisms electron transfer processes. This review summarizes recent advancements the of electrochemical reduction CO 2 (eCO RR) to multi‐carbon (C 2+ ) products. Starting with fundamental principles eCO RR for C product formation, paper outlines producing , 3 4 5 A comprehensive discussion is provided on critical impact structure–performance relationship production Subsequently, observed are classified various electrocatalysts different properties, including single/dual‐atom catalysts, multi‐centric single‐atom alloys, metal‐organic frameworks, heterojunction catalysts. Finally, challenges achieving selective formation through discussed, along corresponding strategies overcome obstacles.

Язык: Английский

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Interstitial carbon induces enriched Cuδ+ sites in Cu2O nanoparticles to facilitate CO2 electroreduction to C2+ products

Nano Research, Год журнала: 2024, Номер 17(8), С. 7013 - 7019

Опубликована: Июнь 26, 2024

Язык: Английский

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Acetylene semi-hydrogenation catalyzed by Pd single atoms sandwiched in zeolitic imidazolate frameworks via hydrogen activation and spillover

Materials Horizons, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Pd single atoms were anchored by zeolitic imidazolate framework to form a Z@Pd@Z sandwich catalyst, over which efficient acetylene semi-hydrogenation could be realized hydrogen activation and spillover.

Язык: Английский

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Cu^δ+ Site-Enhanced Adsorption and Crown Ether-Reconfigured Interfacial D₂O Promote Electrocatalytic Dehalogenative Deuteration

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

Опубликована: Янв. 28, 2025

Electrocatalytic dehalogenative deuteration is a sustainable method for precise deuteration, whereas its Faradaic efficiency (FE) limited by high overpotential and severe D2 evolution reaction (DER). Here, Cuδ+ site-adjusted adsorption crown ether-reconfigured interfacial D2O are reported to cooperatively increase the FE of up 84% at −100 mA cm–2. sites strengthen aryl iodides, promoting mass transfer thus accelerating kinetics toward deuteration. The ethers disrupt hydration effect K·D2O reconstruct hydrogen bond with D2O, lowering content electric double layer hindering interaction between cathode, inhibiting competitive DER. A linear relationship matched sizes alkali metal cations demonstrated universally increasing FEs. This also suitable various halides easily reducible functional group compatibility improved FEs

Язык: Английский

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Quaternary Medium-Entropy Alloy Metallene with Strong Charge Polarization for Highly Selective Urea Electrosynthesis from Carbon Dioxide and Nitrate

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Фев. 14, 2025

Electrochemical urea synthesis via the coreduction of CO2 and NO3- is a sustainable alternative to traditional Bosch-Meiser process. However, sluggish reaction kinetics usually result in low efficiency. Herein, we designed kind quaternary PdCuCoZn medium-entropy alloy (MEA) metallene for highly selective electrosynthesis. The random occupation Cu, Co, Zn with lower electronegativity face-centered cubic lattice Pd-based enables abundant electron donation from transition metals adjacent Pd atoms, leading formation charge-polarized Pdδ--Cu/Co/Znδ+ sites. Considering that pivotal C- N-intermediates, namely, *CO *NH2, are electrophilic nucleophilic, respectively, such strong charge polarization would greatly benefit their respective stabilization. stable adsorption bonded electron-rich sites *NH2 electron-deficient Cu/Co/Zn-based demonstrated by combination situ characterizations theoretical calculations. proof-of-concept MEA achieves maximum yield rate 1840 μg h-1 mg-1 high Faradaic efficiency 70.2%, surpassing most reported state-of-the-arts. Our strategy proposed this work believed enlighten design an effective catalyst used multistep reactions.

Язык: Английский

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Visualization of the Distance-Dependent Synergistic Interaction in Heterogeneous Dual-Site Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(42), С. 29084 - 29093

Опубликована: Окт. 11, 2024

Understanding the characteristics of interfacial hydroxyl (OH) at solid/liquid electrochemical interface is crucial for deciphering synergistic catalysis. However, it remains challenging to elucidate influences spatial distance between OH and neighboring reactants on reaction kinetics atomic level. Herein, we visualize distance-dependent interaction in heterogeneous dual-site catalysis by using ex-situ infrared nanospectroscopy situ spectroscopy techniques. These spectroscopic techniques achieve direct identification distribution species reveal that facilitates reactant deprotonation process depending site distances catalysts. Via modulating Ir-Co pair distances, find dynamic equilibrium generation consumption accounts high-efficiency synergism optimized 7.9 Å. At farther or shorter inaccessibility resistance with intermediates lead accumulation, thereby diminishing effect. Hence, a volcano-shaped curve has been established mass activity formic acid oxidation as probe reaction. This notion could also be extended oxophilic metals, like Ir-Ru pairs, where volcano curves further evidence universal significance distances.

Язык: Английский

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High-selectivity electroreduction of low-concentration CO2 with large concentration fluctuation

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

Язык: Английский

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

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: Английский

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