Atomically Dispersed Metal Catalysts for the Conversion of CO₂ into High‐Value C₂₊ Chemicals

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(37)

Published: May 19, 2024

Abstract The conversion of carbon dioxide (CO 2 ) into value‐added chemicals with two or more carbons (C 2+ is a promising strategy that cannot only mitigate anthropogenic CO emissions but also reduce the excessive dependence on fossil feedstocks. In recent years, atomically dispersed metal catalysts (ADCs), including single‐atom (SACs), dual‐atom (DACs), and single‐cluster (SCCs), emerged as attractive candidates for fixation reactions due to their unique properties, such maximum utilization active sites, tunable electronic structure, efficient elucidation catalytic mechanism, etc. This review provides an overview significant progress in synthesis characterization ADCs utilized photocatalytic, electrocatalytic, thermocatalytic toward high‐value C compounds. To provide insights designing chemical originating from , key factors influence activity selectivity are highlighted. Finally, relevant challenges opportunities discussed inspire new ideas generation ‐based products over ADCs.

Language: Английский

---

Exploring the Performance Improvement for CO₂ Chemical Fixation in Zn/ZnMg-MOFs

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(7), P. 3317 - 3326

Published: Feb. 8, 2024

A new 3D zinc-based metal–organic framework {[Zn7L2(DMF)3(H2O)(OH)2]·5DMF}n (1) (H6L = 5,5′,5″-(methylsilanetriyl) triisophthalic acid) was constructed with an organosilicon-based linker, where H6L is a tetrahedral structure furnished rich −COO– chelating sites for Zn(II) immobilization. Compound 1 exhibited two types of irregular one-dimensional channels and three-dimensional skeleton large specific surface area, making it promising catalytic platform. Moreover, by incorporation the second metal ion into inorganic node 1, isomorphic bimetallic MOF ZnMg-1 successfully synthesized. demonstrated enhanced activity compared to under identical conditions. Contrast experiments theoretical calculations indicate that active play facilitating role in chemical fixation epoxides CO2. It indicated efficient CO2 cyclic carbonates obtained over catalysts ZnMg-1.

Language: Английский

---

Developing a Bifunctional Copper-Organic Framework for Fluorescence Turn-on Hg²⁺ Sensing and Catalyzing CO₂ Cycloaddition Reaction

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(11), P. 4333 - 4341

Published: May 17, 2024

Metal–organic frameworks attract great attention because they show potential for applications such as catalysis and luminescence sensing. Herein, a novel copper–organic framework, [Cu2.5(OH)(nia)2(Bibt)1.5]n, known CuBN, was hydrothermally prepared based on the self-assembly of 4,7-bis(1H-imidazole-1-yl) benzo-[2,1,3]thiadiazole (Bibt), 5-(1,8-naphthalimido)-isophthalic acid (H2nia), CuCl2·2H2O. CuBN exhibited 4, 8-connected sqc 3D porous framework with binuclear copper oxygen cluster unit point symbol {34 48 512 64}{32 42 52}. can work an efficient luminescent sensor Hg2+ via turn-on fluorescence change. Fluorescent data shows that has high selectivity to among various metal ions, detection limit is low, down 9.52 nM. The sensing behavior be mainly attributed Hg2+-promoted collapsing subsequent binding ligand Bibt. In addition, exhibits capability promoting chemical fixation CO2 cyclic carbonates under mild conditions (0.1 mol % catalyst loading, 2 TBAB, 1 atm CO2, 24 h, 80 °C without solvent) up 97% yield good reusability.

Language: Английский

---

A Multivariate 2D Metal–Organic Framework with Open Metal Sites for Catalytic CO₂ Cycloaddition and Cyanosilylation Reactions

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(12), P. 5598 - 5610

Published: March 13, 2024

This work reports the synthesis of a dual functional 2D framework, {[Zn2(4-tpom)2(oxdz)2]·4H2O}n (1), at room temperature, where bent dicarboxylate, oxdz2– (4,4′-(1,3,4-oxadiazole-2,5-diyl)dibenzoate), and neutral flexible N-donor linker, 4-tpom (tetrakis(4-pyridyloxymethylene)methane), are utilized. Its single-crystal X-ray analysis indicated 2-fold interpenetrated framework having tetracoordinated Zn(II) centers dangling pyridyl groups. further characterization was carried out with elemental microanalysis, FTIR spectroscopy, TG analysis, powder diffraction. The as active Lewis acidic sites N atoms basic in 1 explored for its functioning heterogeneous catalyst two important reactions, (i) cycloaddition CO2 various epoxides (ii) cyanosilylation reaction under solvent-free conditions. We could successfully show styrene oxide (99% conversion) balloon pressure low (0.2–0.3 mol %) cocatalyst (0.5–0.75 loadings, which is otherwise difficult to achieve. It observed that all substrates (aromatic aliphatic), irrespective their sizes, showed conversion percentage >99%. In reaction, 96% obtained 1.5 % temperature 12 h. emerged an excellent recyclable both reactions.

Language: Английский

---

Heat Treatment of Fe-doped Zr-MOF Catalysts for Dual Lewis Acid Sites Promoted CO₂ Cycloaddition

ACS Applied Nano Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

The activation and transformation of CO2 into high value-added chemicals are very promising for meeting the carbon neutrality. Lewis acids attractive in catalytic due to fact that O atom can be attacked by electrophilic centers. Here, a series single-atom Fe-doped Zr-MOF nanocatalysts, denoted as Fe-ZrMOF-T, prepared. coordination environment Fe single atoms modulated heat treatment, which shows influence on expression acidity affects ability toward cycloaddition. It was found Fe-ZrMOF-5 obtained treatment at 500 °C possesses highest activity. Results show synergistic effect between dual acid sites Fe3+ Zr4+ this catalysis, is prone activate epoxides while prefers react with CO2. corresponding reaction mechanism proposed based these findings.

Language: Английский

---

Imidazole Functionalized and Cobalt-Oxygen Cluster-Based Metal-Organic Framework for Catalytical Conversion of CO2 and Logically Acidic Amino Acid Sensing

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 141543 - 141543

Published: Jan. 1, 2025

Language: Английский

---

Cu(II) Metal–Organic Framework as a Recyclable Heterogeneous Catalyst for Substituted Pyridine Synthesis from Cyclic Ketones with Propargylamine

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The creation of efficient and stable metal-organic framework (MOF) catalysts with coordinatively unsaturated metal sites is critical in modern organic synthesis. Herein, we reported one new Cu(II)-MOF the chemical formula {[Cu(L)(H2O)]·2DMA·H2O}∞ (1) (H2L = 4,4'-((4R,5R)-4,5-diphenylimidazolidine-1,3-diyl)dibenzoic acid) for annulation cyclic ketones propargylamine. Compound 1 possesses a 2-fold interpenetrating 3D kagome net channel opening about 20 Å diameter. Framework 1' exhibits high permanent porosity (778 m2/g, BET) recyclable catalytic activity propargylamine one-pot tandem reaction, affording series substituted pyridines good yield. X-ray photoelectron spectroscopy analysis indicates that Cu(II) reduced to active Cu(I) species reaction system, while selectively activate triple bond promote annulation. successful preparation heterogeneous presents opportunities developing highly Cu or other transformations mediated by Cu.

Language: Английский

---

Exploring the Catalytic Performance of Ligand-Functionalized Cu-BTC Paddlewheels in Carboxylative Cyclization of Propargyl Alcohol with CO2: DFT and SISSO Insights

Journal of Molecular Graphics and Modelling, Journal Year: 2025, Volume and Issue: unknown, P. 109022 - 109022

Published: March 1, 2025

Language: Английский

---

NH₂-MIL-101(Fe) Nanocrystals Synthesized by the Ionic Liquid–Ethanol Interface for Efficient CO₂ Fixation at Mild Conditions

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

In this study, an ionic liquid–ethanol interface strategy is proposed to synthesize NH2-MIL-101(Fe) nanocrystals at room temperature. The as-synthesized exhibit small crystal sizes, abundant ligand defects, and unsaturated metal sites. present superior catalytic activity for the cycloaddition reaction of CO2 mild conditions (room temperature 1 bar pressure), much higher than NH2-MIL-101 (Fe) microcrystals synthesized by conventional solvothermal method. conversion propylene oxide catalyzed achieves a 99% yield within 2.5 h, accompanied generation rate carbonate production per gram catalyst (Rcarbonate) 52.8 mmol g–1 h–1. contrast, system employing shows lower 19.28% 10.28 were further used treatment simulated industrial flue gas with volume ratio N2/CO2 = 85:15. results show efficient ambient pressure, even relatively low concentrations. This work not only offers facile, energy-consumed, environmentally benign method fabrication MOF nanostructures but also provides high-performance systems fixation separation.

Language: Английский

---

Polyoxometalate-Based Ag^I-MOF for Promoting Catalytic Conversion of CO₂ and Propargylic Alcohols under Mild Conditions

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

The conversion of carbon dioxide to high-value chemicals is greatly significant green chemistry. cyclization reaction CO2 with propargyl alcohol form α-alkylidene cyclic carbonates has attracted attention due atomic economy. Silver (AgI) emerged as one the most effective activators for alkynes, attributed its distinctive electronic configuration affording a specific affinity alkynes. Herein, two novel AgI-based metal-organic frameworks containing Keggin PMo12O403- (abbreviated {PMo12}), namely, {Ag3(btap)3[PMo12O40]}·H2O (Ag-1) and {Ag(Hbtap)2[PMo12O40]} (Ag-2, btap 3,5-bis(1',2',4'-triazol-1'-yl)pyridine), were successfully synthesized. Ag-1 exhibits both exceptional thermal solvent stability, along high catalytic activity in various substituted propargylic alcohols into α-alkyl at room temperature atmospheric pressure. highly dispersed AgI {PMo12} sites are beneficial superior performance Ag-1, by activating C≡C bond adsorbing dioxide, respectively. Based on results, structural analysis, classical chemical theory, it speculated that three-coordinated silver higher Lewis acidity compared Ag-2, making easier activate substrate. Notably, catalyst outstanding stability negligible loss over least five successive cycles.

Language: Английский

---