A Porous Copper–Organic Framework Assembled by [Cu₁₂] Nanocages: Highly Efficient CO₂ Capture and Chemical Fixation and Theoretical DFT Calculations

Abstract

A new porous copper–organic framework assembled from 12-nuclear [Cu12] nanocages {[Cu2(L4–)­(H2O)2]·4DMA·2H2O} n (1) (H4L = 5,5′-(butane-1,4-diyl)-bis­(oxy)-diisophthalic acid) was successfully prepared and structurally characterized. Compound 1 feathering of a 3D framework with two types of 1D nanotubular channels and a large specific surface area can effectively enrich various harmful dyes. Additionally, due to the carbon dioxide (CO2) interactions with open Cu­(II) sites and the electron-rich ether oxygen atoms of ligand in 1, it exhibits a highly selective CO2 uptake. Interestingly, 1 can effectively catalyze the cycloaddition reaction of CO2 with various epoxides under mild conditions, which is ascribed to the Lewis acid Cu­(II) sites in the framework of 1. Importantly, 1 acting as a heterogeneous catalyst can be recycled at least 10 times without an obvious loss of catalytic activity, and the CO2 cycloaddition mechanism was further uncovered by density functional theory (DFT) calculations. This study can greatly enrich the MOF catalysts system of CO2 conversion and also provide a valuable guidance for the design of efficient MOFs catalysts.

Soft Metal–Organic Frameworks Based on {Na@Ln6} as a Secondary Building Unit Featuring a Magnetocaloric Effect and Fluorescent Sensing for Cyclohexane and Fe3+

“…Metal–organic frameworks (MOFs) containing two-dimensional and three-dimensional porous coordination polymers have been rapidly developed in the past two decades, − not only because of their rich and fascinating topological structures, − but also because of their various potential applications in nonlinear optics, , biomedicine, − sensors, , catalysis, − gas adsorption and separation, etc. − As a large branch of the MOF family, lanthanide metal–organic frameworks (Ln-MOFs) exhibit special and interesting topologies due to the high coordination numbers and flexible coordination modes of the Ln 3+ ions. − Compared with transition MOFs, − Ln-MOFs have unique magnetic properties and sensitive luminescence properties based on the special 4f electronic configuration of Ln 3+ ions. − …”

Topologically Driven Pore/Surface Engineering in a Recyclable Microporous Metal–Organic Vessel Decorated with Hydrogen-Bond Acceptors for Solvent-Free Heterogeneous Catalysis

“…The CO 2 fixation reaction in the presence of 1 proceeds effectively under ambient temperature conditions compared to the MOFs reported in the literature (Table S3). ,,− For example, VPI-100 MOFs, FJI-C10, Cd-MOF, MOF-Zn-1, TMU-73, [Cu 12 ] nanocage MOF, NUC-5, NUC-21, In-MOF, etc., require high temperatures ranging from 40 to 80 °C. Furthermore, the MOFs, which catalyze the fixation reaction at lower temperatures, such as In-MOF, Cu-MOF, Sr-MOF, and Zn-MOFs, ,, require either longer time durations ranging from 24 to 60 h or higher pressures of CO 2 gas of 10–20 atm; 1 works effectively under 1 atm CO 2 pressure and in a lesser time of reaction.…”

Highly Efficient Conversion of Propargylic Alcohols and Propargylic Amines with CO2 Activated by Noble‐Metal‐Free Catalyst Cu2O@ZIF‐8

“…[1] Therefore, the capture and conversion of CO 2 to produce high-value products has become one of the hotspots in green chemistry, which can not only reduce the CO 2 emissions but also provide a green route for efficient utilization of CO 2 as a low cost and renewable C1-building block. [2] To date, various valuable chemicals have been obtained by constructing CÀ C, CÀ O and CÀ N bonds between substrates and CO 2 , such as carboxylic acids, [3] carboxylic esters, [4] cyclic carbonates, [5] benzimidazoles, [6] N,N'-disubstituted ureas, [7] etc. [8] Among them, the cyclization of propargylic alcohols and propargylic amines with CO 2 are environmentally friendly and atom-economic reactions, [9] and the resulting products α-alkylidene cyclic carbonates and oxazolidinones with alkene functionality are important building blocks in organic polymer synthesis and the pharmaceutical chemistry.…”