Molecular-scale CO spillover on a dual-site electrocatalyst enhances methanol production from CO2 reduction

Nature Nanotechnology, Год журнала: 2025, Номер unknown

Опубликована: Фев. 18, 2025

Язык: Английский

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Atomically Dispersed Cu Active Centers: Local Structure and Mechanism Modulation for Carbon Dioxide Reduction

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

Abstract Reducing carbon dioxide （CO 2 ）to high‐value products using green renewable energy is a promising approach for addressing and greenhouse effect issues. Consequently, electrocatalytic CO reduction reaction (CO RR) technology has become current research hotspot. Since the discovery of high activity selectivity copper in RR, atomically dispersed Cu catalysts have garnered widespread attention due to their efficient atom utilization, unique electronic structure, outstanding catalytic performance. However, great challenge remains providing rational catalyst design principles achieve regulation product distribution. A clear understanding materials an in‐depth interpretation mechanism as well elucidation strategy progress toward different are keys building solving above problem. Therefore, this review starts with introduction advanced characterization techniques reveal structure mechanisms. Then, various optimization strategies applications producing targeted summarized discussed. Finally, perspectives on RR field future development offered.

Язык: Английский

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Proton-Coupled Electron Transfer Mechanisms for CO₂ Reduction to Methanol Catalyzed by Surface-Immobilized Cobalt Phthalocyanine

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(29), С. 20230 - 20240

Опубликована: Июль 10, 2024

Immobilized cobalt phthalocyanine (CoPc) is a highly promising architecture for the six-proton, six-electron reduction of CO

Язык: Английский

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Unlocking the Potential for Methanol Synthesis via Electrochemical CO₂ Reduction Using CoPc-Based Molecular Catalysts

ACS Nano, Год журнала: 2024, Номер 18(33), С. 21623 - 21632

Опубликована: Авг. 8, 2024

The electrochemical CO2 reduction reaction (CO2RR) to produce methanol (CH3OH) is an attractive yet challenging approach due a lack of selective electrocatalysts. An immobilized cobalt phthalocyanine (CoPc) molecular catalyst has emerged as promising electrocatalyst for CH3OH synthesis, demonstrating decent activity and selectivity through CO2–CO–CH3OH cascade reaction. However, CoPc's performance limited by its weak binding strength toward the CO intermediate. Recent advancements in modification aimed at enhancing intermediate have shown great promise improving CO2-to-CH3OH performance. In this Perspective, we discuss competitive mechanism between that hinders formation summarize effective strategies can enhance both conversion activity. Finally, offer future perspectives on optimization inspire further research efforts fully unlock potential synthesis via CO2RR using catalysts.

Язык: Английский

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Tuning the microenvironment of immobilized molecular catalyst for selective electrochemical CO₂ reduction

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The electrochemical CO2 reduction reaction (CO2RR), as a novel technology, holds great promise for carbon neutrality. Immobilized molecular catalysts are considered efficient CO2RR due to their high selectivity and fast electron transfer rates. However, at current densities, changes in the microenvironment of result decrease local concentration, leading suboptimal catalytic performance. This work describes an effective strategy control concentration by manipulating hydrophobicity. obtained catalyst exhibits CO with Faradaic efficiency (FE) 96% membrane electrode assembly. Moreover, consistent FE exceeding 85% could be achieved total 0.8 A. Diffusion impedance testing interface characterization confirm that enhanced hydrophobicity layer leads increase thickness Nernst diffusion expansion three-phase interface, thereby accelerating adsorption enhance

Язык: Английский

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Spatially Patterned Architectures to Modulate CO₂ Reduction Cascade Catalysis Kinetics

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5894 - 5905

Опубликована: Март 26, 2025

Electrochemical CO2 reduction using renewable sources of electrical energy holds promise for converting into fuels and chemicals. The complex interactions among chemical/electrochemical reactions mass transport make it difficult to analyze the effect an individual process on electrode performance based only experimental methods. Here, we developed a generalized steady-state simulation describe surface in which sequential cascade catalysts are patterned periodic trench design. If appropriately constructed, this geometry is hypothesized be able yield higher net current density (CO2R) reaction. We have used realistic reaction kinetics investigate role transport, local microenvironments, selectivity model CO2R considers concentration gradients bicarbonate species at quasi-equilibrium catalytic concentration-dependent Butler–Volmer kinetics. Our results suggest that varying spatial distribution active sites plays significant facilitating effective between sites, modulating reaction, enhancing desirable products. Moreover, observe significantly alters rate by affecting pH, can cause inadvertent depletion available aqueous limit modest suppression hydrogen evolution (HER). highlight trade-offs become apparent when considering coupled physics all processes surface. This thus serve as primary tool build more selective efficient architectures catalysis.

Язык: Английский

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Nuclear magnetic resonance spectroscopy: A comprehensive tool for analyzing liquid products in electrochemical CO2 reduction

Journal of Electroanalytical Chemistry, Год журнала: 2025, Номер unknown, С. 119097 - 119097

Опубликована: Март 1, 2025

Язык: Английский

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Revealing Substituent Effects in CO to CH₃OH Conversion on a Cobalt Phthalocyanine Catalyst Using DFT Method

The Journal of Physical Chemistry C, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Язык: Английский

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Design Principles of Metal Phthalocyanine for Electrochemical CO₂ Reduction: From Targeted Molecular Structures to Atomic‐Level Active Sites

Small, Год журнала: 2025, Номер unknown

Опубликована: Май 26, 2025

Abstract The electrocatalytic reduction of carbon dioxide (CO 2 RR) to valuable chemical feedstocks using renewable electricity is a promising approach circumventing climate change due the overuse fossil energy. However, most critical mission design high active and economical electrocatalysts. Metal phthalocyanine (MPc)‐based electrocatalysts have attracted extensive research their well‐defined sites flexible structural tunability. Specifically, features MPcs are first introduced then summarize different catalytic mechanisms for CO RR products. Importantly, two main modification strategies axial horizontal modulation MPc‐based highlighted systematically summarized. Furthermore, selectivity products Finally, challenges expectations electrocatalyst selection proposed. This article aims present comprehensive overview electrocatalysts, expecting further inspire development provide new ideas rational efficient

Язык: Английский

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Dual Molecular Catalyst-Based Tandem That Enables Electrocatalytic CO₂−Formaldehyde−Methanol Cascade Conversion

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

Опубликована: Июнь 3, 2025

Electrocatalytic CO2 reduction into multielectron products is a promising approach for carbon capture and utilization. Recently, cobalt phthalocyanine (CoPc)-based molecular catalysts have shown potential competence toward electrochemical conversion of to methanol, 6e-/6H+ product. Yet, despite the recent advancements, CoPc's tendency aggregate weak CO-intermediate binding generally limit its electrocatalytic activity selectivity. Herein, we demonstrate that metal-organic framework (MOF) could be used construct tandem system via immobilization 2 types (CoPc Fe-porphyrin). Notably, MOF-based achieves 3-fold increase in CO2-to-methanol selectivity compared CoPc-only catalyst (up 18% methanol faradaic efficiency at 25 mA/cm2). Additionally, operando spectroscopy analysis show unlike typical systems, operates uniquely by using reactive intermediate different from CO (i.e., formaldehyde). Hence, this proof-of-concept offers new means design schemes capable driving complex proton-coupled electron transfer reactions.

Язык: Английский

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