Switching CO₂ Electroreduction toward Ethanol by Delocalization State-Tuned Bond Cleavage

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(20), С. 14260 - 14266

Опубликована: Май 7, 2024

The electrochemical CO2 reduction reaction by copper-based catalysts features a promising approach to generate value-added multicarbon (C2+) products. However, due the unfavored formation of oxygenate intermediates on catalyst surface, selectivity C2+ alcohols like ethanol remains unsatisfactory compared that ethylene. bifurcation point (i.e., CH2═CHO* intermediate adsorbed Cu via Cu–O–C linkage) is critical product selectivity, whereas subsequent cleavage Cu–O or O–C bond determines ethylene pathway. Inspired hard–soft acid–base theory, in this work, we demonstrate an electron delocalization tuning strategy nitrene surface functionalization approach, which allows weakening and cleaving CH2═CHO*, as well accelerating hydrogenation C═C along As result, nitrene-functionalized exhibited much-enhanced Faradaic efficiency 45% with peak partial current density 406 mA·cm–2, substantially exceeding unmodified amide-functionalized Cu. When assembled membrane electrode assembly electrolyzer, presented stable CO2-to-ethanol conversion for >300 h at industrial 400 mA·cm–2.

Язык: Английский

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Inverse design of promising electrocatalysts for CO2 reduction via generative models and bird swarm algorithm

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 26, 2025

Directly generating material structures with optimal properties is a long-standing goal in design. Traditional generative models often struggle to efficiently explore the global chemical space, limiting their utility localized space. Here, we present framework named Material Generation Efficient Global Chemical Space Search (MAGECS) that addresses this challenge by integrating bird swarm algorithm and supervised graph neural networks, enabling effective navigation of immense space towards materials target properties. Applied design alloy electrocatalysts for CO2 reduction (CO2RR), MAGECS generates over 250,000 structures, achieving 2.5-fold increase high-activity (35%) compared random generation. Five predicted alloys— CuAl, AlPd, Sn2Pd5, Sn9Pd7, CuAlSe2 are synthesized characterized, two showing around 90% Faraday efficiency CO2RR. This work highlights potential revolutionize functional development, paving way fully automated, artificial intelligence-driven Designing longstanding challenge, as current methods vast effectively. authors combine model optimization novel highly active electroreduction.

Язык: Английский

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Isolating and stabilizing active copper species in layered double hydroxide to enhance electrocatalytic CO2 reduction to CH4

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 115959 - 115959

Опубликована: Янв. 1, 2025

Язык: Английский

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Unveiling the role of heteroatom doping and strain in Core-Shell catalysts for CO2RR

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 160155 - 160155

Опубликована: Фев. 1, 2025

Язык: Английский

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Brass Phase Determining Selectivity in Urea Electrosynthesis from CO₂ and Nitrate

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3276 - 3283

Опубликована: Фев. 7, 2025

Язык: Английский

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Electrocatalytic CO2 hydrogenation to C2+ alcohols catalysed by Pr–Cu oxide heterointerfaces

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

Язык: Английский

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Tuning electronic structure of cobaltous nitride-manganous oxide heterojunction by N-vacancy engineering for optimizing oxygen electrocatalysis activity

Nano Energy, Год журнала: 2024, Номер unknown, С. 110294 - 110294

Опубликована: Сен. 1, 2024

Язык: Английский

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Topologically Close‐Packed Frank‐Kasper C15 Phase Intermetallic Ir Alloy Electrocatalysts Enables High‐Performance Proton Exchange Membrane Water Electrolyzer

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 30, 2024

Abstract Chemical synthesis of unconventional topologically close‐packed intermetallic nanocrystals (NCs) remains a considerable challenge due to the limitation large volume asymmetry between components. Here, series Frank‐Kasper C15 phase Ir 2 M (M = rare earth metals La, Ce, Gd, Tb, Tm) NCs is successfully prepared via molten‐salt assisted reduction method as efficient electrocatalysts for hydrogen evolution reaction (HER). Compared disordered counterpart (A1‐Ir Ce), C15‐Ir Ce features higher Ir‐Ce coordination number that leads an electron‐rich environment sites. The catalyst exhibits excellent and pH‐universal HER activity requires only 9, 16, 27 mV overpotentials attain 10 mA cm −2 in acidic, alkaline, neutral electrolytes, respectively, representing one best ever reported. In proton exchange membrane water electrolyzer, cathode achieves industrial‐scale current density 1 A with remarkably low cell voltage 1.7 V at 80 °C can operate stably 1000 h sluggish decay rate 50 µV −1 . Theoretical investigations reveal sites intensify polarization *H O intermediate on thus lowering energy barrier dissociation facilitating kinetics.

Язык: Английский

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Solid Electrolytes for Low-Temperature Carbon Dioxide Valorization: A Review

Environmental Science & Technology, Год журнала: 2024, Номер 58(25), С. 10881 - 10896

Опубликована: Июнь 11, 2024

One of the most promising approaches to address global challenge climate change is electrochemical carbon capture and utilization. Solid electrolytes can play a crucial role in establishing chemical-free pathway for CO2. Furthermore, they be applied electrocatalytic CO2 reduction reactions (CO2RR) increase utilization, produce high-purity liquid chemicals, advance hybrid electro-biosystems. This review article begins by covering fundamentals processes capture, emphasizing advantages utilizing solid electrolytes. Additionally, it highlights recent advancements use polymer electrolyte or layer CO2RR with multiple functions. The also explores avenues future research fully harness potential electrolytes, including integration performance assessment under realistic conditions. Finally, this discusses opportunities challenges, aiming contribute establishment green sustainable society through valorization.

Язык: Английский

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Regulating Asymmetric C–C Coupling with Interfacial Alkalinity for Efficient CO₂ to C₂₊ Electroconversion

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Abstract The electrocatalytic reduction of CO 2 in neutral electrolytes is a promising avenue to minimize energy losses linked carbonate formation. However, selectivity for multi‐carbon (C 2+ ) products hampered by kinetic barriers C–C coupling. Here, the regulation asymmetric coupling achieved with interfacial alkalinity, facilitating efficient C electroconversion. This realized co‐engineering copper electrodes ZrO sites and CeO x enable favorable microenvironment that greatly boosts intrinsic catalytic activity. In situ spectroscopic results theoretical analyses demonstrates facilitates dissociation H O into *H *OH, effectively regulating coverage at interface promoting protonation *CO *COH. Meanwhile, significantly enhance adsorption situ‐produced optimize local pH on Cu surface, formation via low‐energy *OC–COH pathway. A notable electroconversion 1.0 M KCl electrolyte, Faraday efficiency 67.2 ± 2.1% partial current density 413.0 9.9 mA cm −2 achieved. synergistic enhancement hydroxyl stabilization interface, driven activation O, crucial boosting overall performance system.

Язык: Английский

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