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

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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

Nature Nanotechnology, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 18, 2025

Language: 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, Journal Year: 2024, Volume and Issue: 146(29), P. 20230 - 20240

Published: July 10, 2024

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

Language: Английский

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

ACS Nano, Journal Year: 2024, Volume and Issue: 18(33), P. 21623 - 21632

Published: Aug. 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.

Language: Английский

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

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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

Language: Английский

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Spatially Patterned Architectures to Modulate CO₂ Reduction Cascade Catalysis Kinetics

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5894 - 5905

Published: March 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.

Language: Английский

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

Journal of Electroanalytical Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 119097 - 119097

Published: March 1, 2025

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

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Quantitative Assessment for the Disproportionation Reaction of HCHO Formed during CO and CO₂ Electrolysis

Electrochemistry, Journal Year: 2024, Volume and Issue: 92(5), P. 057005 - 057005

Published: May 7, 2024

The electrochemical reduction of carbon dioxide (CO2 electrolysis) is attracting much attention as a promising approach to address environmental challenges.Among the various products CO2 electrolysis, formaldehyde (HCHO) stands out for its potential precursor longer-chain compounds.However, reports on HCHO production are scarce, and comprehensive discussions still lacking.A major obstacle deeper analysis inherent instability HCHO, which tends undergo disproportionation reactions, transforming it into different substances.In this study, we propose quantitative indicator evaluate progression level reaction HCHO.Utilizing indicator, explore how influenced by changes in electrolyte's pH catalyst layer thickness monoxide (CO)  key intermediate electrolysis.Our results showed that impact increases with higher values greater layer.Moreover, insights obtained from CO electrolysis effective managing generation during electrolysis.

Language: Английский

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Realization of a Photoelectrochemical Cascade for the Generation of Methanol: A Liquid Solar Fuel

Energy & Fuels, Journal Year: 2024, Volume and Issue: 39(8), P. 4019 - 4029

Published: Dec. 23, 2024

Biochemical networks use reaction cascades to selectively reduce CO2 using energy from sunlight, but can similar selectivity be achieved by applying a cascade approach an engineered system? Here, we report the design and implementation of two-step photoelectrochemical (PEC) liquid solar fuel: reduction CO subsequent methanol. The potentials required perform reductions were generated custom-made III-V-based three-terminal tandem (3TT) cells. Cobalt phthalocyanine immobilized on multiwalled carbon nanotubes (CoPc/MWCNT) catalyzed both reactions. Multiphysics simulations electrolyte flow nonilluminated electrochemical measurements used narrow operating parameters for CoPc/MWCNT 3TT photocathodes. champion integrated photocathode produced methanol with 3.8 ± 0.4% Faradaic efficiency (FE), tested photocathodes having 0.7-3.8% FE. Products quantified nuclear magnetic resonance spectroscopy gas chromatography. current output was highly stable, production continued over multiple experiments. low yield is attributed insufficient flux to, depletion at, methanol-producing subcell when contacts are active, which supported observation that control photoelectrode slightly outperformed device. Methanol ceased driving deactivated, supporting assignment mechanism. major factors resulting in FE at contact uncertainty potential selection design. Although not yet selective, this work develops basic science principles underlying PEC cascade, demonstrates co-design 3TT-based produce carbon-based fuels, finally discusses routes improving product yields concept, including supply optimization alternative catalyst materials.

Language: Английский

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