Steering CO₂ Electroreduction Selectivity U-Turn to Ethylene by Cu–Si Bonded Interface

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 289 - 297

Published: Dec. 22, 2023

Copper (Cu), with the advantage of producing a deep reduction product, is unique catalyst for electrochemical CO2 (CO2RR). Designing Cu-based to trigger CO2RR multicarbon product and understanding accurate structure–activity relationship elucidating reaction mechanisms still remain challenge. Herein, we demonstrate rational design core–shell structured silica-copper (p-Cu@m-SiO2) through Cu–Si direct bonding efficient selective CO2RR. The interface fulfills inversion in selectivity. ratio C2H4/CH4 changes from 0.6 14.4 after silica modification, current density reaches high up 450 mA cm–2. kinetic isotopic effect, situ attenuated total reflection Fourier-transform infrared spectra, functional theory were applied elucidate mechanism. SiO2 shell stabilizes *H intermediate by forming Si–O–H inhibits hydrogen evolution effectively. Moreover, direct-bonded makes bare Cu sites larger charge density. Such stabilized *CHO activated *CO, promoting coupling *CO intermediates form C2H4. This work provides promising strategy designing catalysts C2H4 catalytic activity.

Language: Английский

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Photocoupled Electroreduction of CO₂ over Photosensitizer-Decorated Covalent Organic Frameworks

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19856 - 19865

Published: Aug. 31, 2023

Introducing an external visible-light field would be a promising strategy to improve the activity of electrocatalytic CO2 reduction reaction (CO2RR), but it still remains challenge due short excited-state lifetime active sites. Herein, Ru(bpy)3Cl2 struts as powerful photosensitive donors were immobilized into backbones Co-porphyrin-based covalent organic frameworks (named Co-Bpy-COF-Rux, x is molar ratio Ru and Co species, = 1/2 2/3) via coordination bonds, for photo-coupled CO2RR produce CO. The optimal Co-Bpy-COF-Ru1/2 displays high CO Faradaic efficiency 96.7% at -0.7 V vs reversible hydrogen electrode (RHE) partial current density 16.27 mA cm-2 -1.1 RHE under assistance light, both which far surpassing values observed in dark. significantly enhanced mainly attributed incorporation donor with long concomitantly giant built-in electric Co-Bpy-COF-Ru1/2, efficiently accelerate photo-induced electron transfer from cobalt-porphyrin light. Thus, sites have longer lower rate-determining steps' energy occurring during actual process. This first work porphyrin-based COFs CO2RR, opening new frontier construction efficient electrocatalysts.

Language: Английский

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Tuning Coordination Structures of Zn Sites Through Symmetry‐Breaking Accelerates Electrocatalysis

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(4)

Published: Aug. 31, 2023

Manipulating the coordination environment of individual active sites in a precise manner remains an important challenge electrocatalytic reactions. Herein, inspired by theoretical predictions, facile procedure to synthesize series symmetry-breaking zinc metal-organic framework (Zn-MOF) catalysts with well-defined structures is presented. Benefiting from optimized microenvironment regulated symmetry-breaking, Zn-N

Language: Английский

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MOF-based materials for electrochemical reduction of carbon dioxide

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 494, P. 215333 - 215333

Published: July 28, 2023

Language: Английский

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Trimetallic-organic framework/MXene composite as an oxygen evolution reaction electrocatalyst with elevated intrinsic activity

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(8), P. 4826 - 4834

Published: Jan. 1, 2024

A composite of trimetallic Fe 2.1 Ni 0.2 Co 0.7 -MIL-88A grown on Ti 3 C 2 T x MXene nanosheets was successfully synthesized and employed as a high-performance OER electrocatalyst with low overpotential 231 mV at 10 mA cm −2 current density in alkaline media.

Language: Английский

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Iron Active Center Coordination Reconstruction in Iron Carbide Modified on Porous Carbon for Superior Overall Water Splitting

Advanced Science, Journal Year: 2024, Volume and Issue: 11(25)

Published: April 24, 2024

Abstract In this work, a novel liquid nitrogen quenching strategy is engineered to fulfill iron active center coordination reconstruction within carbide (Fe 3 C) modified on biomass‐derived nitrogen‐doped porous carbon (NC) for initiating rapid hydrogen and oxygen evolution, where the chrysanthemum tea (elm seeds, corn leaves, shaddock peel, etc.) treated as biomass source Fe C NC. Moreover, original thermodynamic stability changed through corresponding force generated by phase transformation induced with rich vacancies increasing instantaneous temperature drop amplitude. Noteworthy, optimizing intermediate absorption/desorption achieved new phases, coordination, vacancies. The C/NC‐550 (550 refers temperature) demonstrates outstanding overpotential evolution reaction (26.3 mV at −10 mA cm −2 ) (281.4 10 ), favorable overall water splitting activity (1.57 V ). Density functional theory (DFT) calculations further confirm that treatment can enhance intrinsic electrocatalytic efficiently adsorption free energy of intermediates. Overall, above results authenticate open up possibilities obtaining highly electrocatalysts generation green conversion systems.

Language: Английский

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Bifunctional Catalysts with Core–Shell Distributed ZrO₂ and Co Nanoparticles Derived from MOF-on-MOF Heterostructures for Economical One-Pot Tandem CO₂ Fixation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8372 - 8383

Published: June 8, 2023

The N-formylation of aryl amines with CO2 is an emerging strategy to simultaneously reduce carbon emission and produce high-value formamides. Considering that are usually produced from the hydrogenation their corresponding nitroarenes in chemical industry, one-pot tandem hydrogenation–formylation formamides obviously a much more economical but still unexploited for efficient fixation. Herein, we report rational synthesis bifunctional catalysts core–shell distributed ZrO2 Co nanoparticles (NPs) controlled pyrolysis ZIF-67-on-UiO-66 heterostructure this reaction. To fabricate such MOF-on-MOF heterostructures, develop facile surfactant-assisted seed ZIF-8 nuclei on UiO-66 surface, followed by successful growth thickness-controlled ZIF-67 shell UIO-66 core. Based further pyrolysis, highly mesoporous derivants NPs can be obtained, which reductive Lewis basic serve as active sites CO2, respectively, due favorable electronic structures good mass diffusion reactants/intermediates. Impressively, optimized catalyst achieves higher yield N-(4-methoxyphenyl)formamide (99.5%) than its ZrO2/C (0%), Co-NC (14.1%), physically mixed counterparts (52.3%) between 4-nitroanisole recyclability broad substrate scope, shedding light design fixation

Language: Английский

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Self‐Accelerating Effect in a Covalent–Organic Framework with Imidazole Groups Boosts Electroreduction of CO₂ to CO

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Sept. 1, 2023

Solvent effect plays an important role in catalytic reaction, but there is little research and attention on it electrochemical CO2 reduction reaction (eCO2 RR). Herein, we report a stable covalent-organic framework (denoted as PcNi-im) with imidazole groups new electrocatalyst for eCO2 RR to CO. Interestingly, compared neutral conditions, PcNi-im not only showed high Faraday efficiency of CO product (≈100 %) under acidic conditions (pH ≈ 1), also the partial current density was increased from 258 320 mA cm-2 . No obvious degradation observed over 10 hours continuous operation at 250 The mechanism study shows that group can be protonated form cation media, hence reducing surface work function charge active metal center. As result, poisoning weakened key intermediate *COOH stabilized, thus accelerating rate.

Language: Английский

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Ag⁺‐Doped InSe Nanosheets for Membrane Electrode Assembly Electrolyzer toward Large‐Current Electroreduction of CO₂ to Ethanol

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Oct. 16, 2023

It is an appealing approach to CO2 utilization through electroreduction (CO2 ER) ethanol at high current density; however, the commonly used Cu-based catalysts cannot sustain large during ER despite their capability for production. Herein, we report that Ag+ -doped InSe nanosheets with Se vacancies can address this grand challenge in a membrane electrode assembly (MEA) electrolyzer. As revealed by our experimental characterization and theoretical calculation, doping, which tailor electronic structure of while diversifying catalytically active sites, enables formation key reaction intermediates sequential evolution into ethanol. More importantly, such material well work large-current conditions MEA electrolyzers In2+ species stabilized via electron transfer from Ag Se. Remarkably, electrolyzer coupling cathodic anodic oxygen (OER), optimal catalyst exhibits Faradaic efficiency 68.7 % partial density 186.6 mA cm-2 on cathode full-cell energy 26.1 3.0 V. This opens avenue production selectivity rationally designing electrocatalysts.

Language: Английский

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A benzimidazole-linked bimetallic phthalocyanine–porphyrin covalent organic framework synergistically promotes CO₂electroreduction

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(29), P. 15732 - 15738

Published: Jan. 1, 2023

A bimetallic phthalocyanine–porphyrin covalent organic framework with benzimidazole linkage was developed as an efficient CO 2 electrocatalyst. Mechanistic studies clarified that a synergistic effect in the reduction thermodynamic pathway.

Language: Английский

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