Controlling the Polarity of Metal‐Organic Frameworks to Promote Electrochemical CO2 Reduction

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Окт. 11, 2024

The addition of polar functional groups to porous structures is an effective strategy for increasing the ability metal-organic frameworks (MOFs) capture CO

Язык: Английский

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Observation of O₂ Molecules Inserting into Fe–H Bonds in a Ferrous Metal–Organic Framework

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

Опубликована: Янв. 21, 2025

Exploring the interactions between oxygen molecules and metal sites has been a significant topic. Most previous studies concentrated on enzyme-mimicking interacting with O2 to form M-OO species, leaving development of new types O2-activating novel adsorption mechanisms largely overlooked. In this study, we reported an Fe(II)-doped metal-organic framework (MOF) [Fe3Zn2H4(bibtz)3] (MAF-203, H2bibtz = 1H,1'H-5,5'-bibenzo[d][1,2,3]triazole), featuring unprecedented tetrahedral Fe(II)HN3 site. This MOF exhibits selective behavior for from air, achieving O2/N2 separation selectivity up 67.1. Breakthrough experiments confirmed that MAF-203 can effectively capture air even under high relative humidity 60%. X-ray absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectra, ab initio molecular dynamics simulations were utilized monitor loading process Interestingly, could insert into Fe-H bonds FeIIHN3 sites, forming FeIII-OOH species (instead commonly observed Fe-OO species) ultrahigh enthalpy -99.2 kJ mol-1. Consequently, enables efficient electrochemical 2e- reduction production H2O2 as feedstock. Specifically, solid-state electrolyte electrolyzer without any liquid electrolyte, achieved continuous medical-grade (3.2 wt %) solution salts 70 h, performance comparable pure conditions. The activation inaugurate fresh chapter grasping interaction sites.

Язык: Английский

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Cobalt-Cluster-Based Metal–Organic-Framework-Catalyzed Carboxylative Cyclization of Propargylic Amines with CO₂ from Flue Gas

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 27, 2025

The fixation of carbon dioxide (CO2) directly from flue gas into valuable chemicals like 2-oxazolidinones is great significance for economic and environmental benefits, which typically catalyzed by noble-metal catalysts under harsh conditions. Herein, a novel 2-fold interpenetrated framework {[Co3(μ2-O)(TCA)2(HDPTA)2]·2H2O·2DMF}n [Co(II)-based metal-organic (Co-MOF)] containing [Co3] clusters highly dense amino groups (-NH2) dispersed in the channel was prepared, exhibiting high solvent/pH stability CO2 adsorption capacity (24.9 cm3·g-1). Catalytic experiments demonstrated that Co-MOF could catalyze carboxylative cyclization propargylic amines to generate with yields up 98% mild conditions gas. In addition, retained its structure catalytic activity after five-cycle experiments, showing promising practical application. Density functional theory (DFT) calculation suggested centers MOF activated C≡C much more binding energy than Co(NO3)2, partly accounting Co-MOF. This work demonstrates first Co-based material efficient as source, inspiring further rational design porous utilization.

Язык: Английский

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Modulated Multicomponent Reaction Pathway by Pore‐Confinement Effect in MOFs for Highly Efficient Catalysis of Low‐Concentration CO₂

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Abstract The conversion of flue gas CO 2 into high‐value chemicals via multicomponent reactions (MCRs) offers the advantages atom economy, bond‐formation efficiency and product complexity. However, because competition between reaction sequences pathways among substrates, efficient synthesize desired is a great challenge. Herein, porous noble‐metal‐free framework ( Cu‐TCA) was synthesized, which can highly effectively catalyze by modulating pathways. pores with size 6.5 Å×6.5 Å in Cu‐TCA selectively permit entry propargylamine at simulated concentrations, At same time, larger‐sized phosphine oxide hindered outside pores. Control experiments NMR spectroscopy revealed that preferentially reacted to form oxazolidinones, further produce phosphorylated 2‐oxazolidinones. Therefore, sequence substrates were controlled confinement effect . Density functional theory (DFT) calculations supported coordination alkyne, significantly reducing barrier promoting catalytic reaction. This study developed new strategy for regulating promote MCRs MOF.

Язык: Английский

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Integrated Capture and Electrocatalytic Conversion of CO₂: A Molecular Electrocatalysts Perspective

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Апрель 21, 2025

Abstract The ever‐increasing concentration of atmospheric CO 2 , primarily driven by anthropogenic activities, has raised urgent environmental concerns, spurring the development carbon capture and utilization (CCU) technologies. This review focuses on integrated electrochemical conversion (ICECC), a promising approach that combines with its direct electroreduction into value‐added products. By eliminating energy‐intensive steps such as release, compression, transportation, ICECC offers more energy‐efficient cost‐effective alternative to conventional CCU methods. In this review, particular attention is given molecular electrocatalysts, which offer high tunability selectivity in reduction reaction (eCO RR). role capturing agents, including both external dual‐functional systems, critically examined understand their influence binding catalytic efficiency. Whereas significant potential, research area remains underexplored compared discusses mechanistic insights processes, highlighting key challenges potential future directions for improving catalyst design, enhancing efficiency, scaling up These developments can make critical component achieving neutrality addressing climate change.

Язык: Английский

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