Regulating reconstruction of oxide-derived Cu for electrochemical CO ₂ reduction toward n-propanol

Science Advances, Год журнала: 2023, Номер 9(43)

Опубликована: Окт. 27, 2023

Oxide-derived copper (OD-Cu) is the most efficient and likely practical electrocatalyst for CO 2 reduction toward multicarbon products. However, inevitable but poorly understood reconstruction from pristine state to working of OD-Cu under strong conditions largely hinders rational construction catalysts products, especially C 3 products like n-propanol. Here, we simulate CuO Cu O into their derived by molecular dynamics, revealing that CuO-derived (CuOD-Cu) intrinsically has a richer population undercoordinated sites higher surficial atom density than counterpart O-derived (Cu OD-Cu) because vigorous oxygen removal. In situ spectroscopes disclose coordination number CuOD-Cu considerably lower OD-Cu, enabling fast kinetics reaction strengthened binding *C intermediate(s). Benefiting rich sites, achieves remarkable n-propanol faradaic efficiency up ~17.9%, whereas dominantly generates formate.

Язык: Английский

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Electrocatalytic Waste-Treating-Waste Strategy for Concurrently Upgrading of Polyethylene Terephthalate Plastic and CO₂ into Value-Added Formic Acid

ACS Catalysis, Год журнала: 2023, Номер 13(21), С. 14163 - 14172

Опубликована: Окт. 20, 2023

Polyethylene terephthalate (PET) plastic and CO2 pollution have seriously threatened the ecological environment caused a huge waste of carbon resources. Herein, we report an electrocatalytic waste-treating-waste strategy for concurrently upgrading PET wastes into value-added formic acid (HCOOH), in which both anode (oxygen-vacancy-rich Ni(OH)2-VO) cathode (Bi/Bi2O3 heterostructure) electrocatalysts were elaborately designed from derivatives. Impressively, as-prepared Ni(OH)2-VO Bi/Bi2O3 achieve high selectivity HCOOH (86 91%, respectively) with industrial-level current densities at ultralow potentials (300 mA cm–2 1.6 V −272 −1.4 V, respectively). Further experimental theoretical results reveal that abundant oxygen vacancies will largely facilitate formation Ni3+ species accelerate subsequent processes dehydrogenation C–C bond breakage during upcycling. Meanwhile, interface electron transfer Bi2O3 to Bi benefits keeping valence sites optimizes adsorption OCHO* intermediate, thereby endowing efficient performance toward reduction HCOOH. As proof concept, solar-powered flow reactor real-time monitoring control functions was designed, realized record Faradaic efficiency 181% This work offers opportunities utilization provides constructive guidance design advanced converting valuable chemicals.

Язык: Английский

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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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Porphyrin-based metal–organic frameworks for photo(electro)catalytic CO₂ reduction

Energy & Environmental Science, Год журнала: 2024, Номер 17(15), С. 5311 - 5335

Опубликована: Янв. 1, 2024

The panorama of the latest developments emerging porphyrin-based MOFs for photo(electro)catalytic CO 2 reduction is shown.

Язык: Английский

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Recent Advances in Electrochemical Carboxylation with CO₂

Accounts of Chemical Research, Год журнала: 2024, Номер 57(18), С. 2728 - 2745

Опубликована: Сен. 3, 2024

ConspectusCarbon dioxide (CO

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Covalent Organic Frameworks as Promising Platforms for Efficient Electrochemical Reduction of Carbon Dioxide: A Review

Small Structures, Год журнала: 2024, Номер 5(5)

Опубликована: Фев. 5, 2024

In current research, achieving carbon neutrality has become a primary focus through the utilization of various conversion technologies that transform dioxide (CO 2 ) into valuable chemicals or fuels. Covalent organic frameworks (COFs), as emerging crystalline polymers, offer distinct advantages in CO compared to other materials. These include controllable nanoscale pores, predefined functional units, editable framework structures, and rich conjugated systems. The unique characteristics COFs make them highly promising electrocatalysts for conversion. This review provides comprehensive overview pioneering works recent research on COF‐based materials electrochemical reduction reaction. offers analysis design principles reactive sites, skeleton pore functionalities, 3D frameworks, morphologies, composite COFs, aiming enhance electrocatalysis. Finally, this presents some recommendations material design, reaction mechanisms, theoretical computations understanding mechanisms further facilitate high‐performance electrocatalysts.

Язык: Английский

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Conjugated Microporous Polymers for Catalytic CO₂ Conversion

Advanced Science, Год журнала: 2024, Номер 11(14)

Опубликована: Фев. 7, 2024

Abstract Rising carbon dioxide (CO 2 ) levels in the atmosphere are recognized as a threat to atmospheric stability and life. Although this greenhouse gas is being produced on large scale, there solutions reduction indeed utilization of gas. Many these involve costly or unstable technologies, such air‐sensitive metal–organic frameworks (MOFs) for CO capture “non‐green” systems amine scrubbing. Conjugated microporous polymers (CMPs) represent simpler, cheaper, greener solution utilization. They often easy synthesize at scale (a one pot reaction many cases), chemically thermally stable (especially comparison with their MOF covalent organic framework (COF) counterparts, owing amorphous nature), and, result, cheap manufacture. Furthermore, surface areas, tunable porous chemical structures mean they reported highly efficient motifs. In addition, provide dual pathway utilize captured via conversion electrochemical into industrially valuable products. Recent studies show that all attractive properties can be realized metal‐free CMPs, presenting truly green option. The promising results two fields CMP applications reviewed explored here.

Язык: Английский

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Progress and Perspective for “Green” Strategies of Catalytic Plastics Conversion into Fuels by Regulating Half-Reactions

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(25), С. 16950 - 16962

Опубликована: Июнь 4, 2024

Nowadays, plastic waste threatens public health and the natural ecosystems of our lives. It is highly beneficial to recycle in order maximize reuse its contained carbon sources for development other valuable products. Unfortunately, traditional techniques usually require significant energy consumption result generation hazardous waste. Herein, up-to-date developments on "green" strategies under mild conditions including electrocatalysis, photocatalysis, photoelectrocatalysis wastes are presented. During oxidation plastics these strategies, corresponding reduction reactions exist, which affect property catalytic conversion. Particularly, we mainly focus how design half reactions, such as water reduction, dioxide nitrate reduction. Finally, provide forward-looking insight into enhancement extension more organic catalysis, a comprehensive exploration underlying mechanisms through situ studies theoretical analysis problems practical applications that needs be solved.

Язык: Английский

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Boosting Electrochemical CO₂ Reduction on Copper‐Based Metal‐Organic Frameworks via Valence and Coordination Environment Modulation

Small, Год журнала: 2024, Номер 20(27)

Опубликована: Янв. 29, 2024

Abstract Cu‐based metal‐organic frameworks (MOFs) have attracted much attention for electrocatalytic CO 2 reduction to high value‐added chemicals, but they still suffer from low selectivity and instability. Here, an associative design strategy the valence coordination environment of metal node in MOFs is employed regulate CO2 electroreduction ethylene. A novel “reduction‐cleavage‐recrystallization” method developed modulate Cu(II)‐Trimesic acid (BTC) framework form a Cu(I)‐BTC structure enriched with free carboxyl groups secondary (SCE). In contrast Cu(II)‐BTC, shows higher catalytic activity better ethylene (≈2.2‐fold) electroreduction, which further enhanced by increasing content groups, resulting Faraday efficiency up 57% durability catalyst could last 38 h without performance decline. It indicates that synergistic effect between Cu(I)‐O coordinated considerably enhances dimerization *CO intermediates hinders hydrogenation these competitive pathways. This work unravels strong dependence on Cu state provides platform designing highly selective catalysts.

Язык: Английский

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Recent Advances and Challenges in Efficient Selective Photocatalytic CO₂ Methanation

Small, Год журнала: 2024, Номер 20(32)

Опубликована: Март 15, 2024

Abstract Solar‐driven carbon dioxide (CO 2 ) methanation holds significant research value in the context of emission reduction and energy crisis. However, this eight‐electron catalytic reaction presents substantial challenges activity selectivity. In regard, researchers have conducted extensive exploration achieved developments. This review provides an overview recent advances efficient selective photocatalytic CO methanation. It begins by discussing fundamental principles detail, analyzing strategies for improving efficiency conversion to CH 4 comprehensively. Subsequently, it outlines applications advanced characterization methods Finally, highlights prospects opportunities area, aiming inspire into high‐value shed light on mechanisms.

Язык: Английский

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