Yan-An Li

Bifunctional Imidazolium-Based Ionic Liquid Decorated UiO-67 Type MOF for Selective CO2 Adsorption and Catalytic Property for CO2 Cycloaddition with Epoxides

A bifunctional robust and highly porous imidazolium-based ionic liquid decorated UiO-67 type MOF (UiO-67-IL, 1) was successfully constructed via solvothermal assembly of the imidazolium-based ligand and Zr(IV) ions. It exhibits a highly selective adsorption for CO2 over CH4 and N2. Furthermore, 1 herein can be used as a highly active heterogeneous catalyst for CO2 cycloaddition with epoxides under atmospheric pressure with or without cocatalyst TBAB (n-Bu4NBr).

Pd@Cu(II)-MOF-Catalyzed Aerobic Oxidation of Benzylic Alcohols in Air with High Conversion and Selectivity

A new 3D porous Cu(II)-MOF (1) was synthesized based on a ditopic pyridyl substituted diketonate ligand and Cu(OAc)2 in solution, and it features a 3D NbO motif which is determined by the X-ray crystallography. Furthermore, the Pd NPs-loaded hybrid material Pd@Cu(II)-MOF (2) was prepared based on 1 via solution impregnation, and its structure was confirmed by HRTEM, SEM, XRPD, gas adsorption-desorption, and ICP measurement. 2 exhibits excellent catalytic activity (conversion, 93% to >99%) and selectivity (>99% to benzaldehydes) for various benzyl alcohol substrates (benzyl alcohol and its derivatives with electron-withdrawing and electron-donating groups) oxidation reactions in air. In addition, 2 is a typical heterogeneous catalyst, which was confirmed by hot solution leaching experiment, and it can be recycled at least six times without significant loss of its catalytic activity and selectivity.

A porous Cd(II)-MOF-coated quartz fiber for solid-phase microextraction of BTEX

The utilization of a porous Cd(II)-MOF ([Cd(L)2(ClO4)2]·H2O) (L = 4-amino-3,5-bis(4-pyridyl-3-phenyl)-1,2,4-triazole) with good thermal/chemical stability for solid-phase micro-extraction (SPME) is reported. The Cd(II)-MOF thin films are expediently in situ grown on quartz fiber in solution, exhibiting high sensitivity and selectivity towards volatile benzene, toluene, o-, m-, p-xylene, and ethylbenzene (termed as BTEX) aromatics. The limits of detection for BTEX are 0.01–0.001 μg L−1.

Cd(II)-MOF: adsorption, separation, and guest-dependent luminescence for monohalobenzenes.

A series of isostructural 2-fold interpenetrating 2D Cd(II)-MOFs, namely G⊂CdL2(OTs)2 (G = THF (1), PhF (2), PhCl (3), PhBr (4), PhI (5), L = 1,2-bis[(3-(pyridin-4-yl)phenoxy]ethane, and OTs(-) = p-toluenesulfonate anion), have been successfully synthesized from the flexible ethylene glycol ether-bridging ligand L and Cd(OTs)2 in solution. The CdL2(OTs)2 framework contains squarelike nonpolar channels, and the encapsulated guest molecules can be removed by heating (150 °C) to generate a guest-free host framework which is able to reversibly adsorb monohalobenzenes PhX (X = F, Cl, Br, I) in the liquid phase under ambient conditions without loss of framework integrity. Furthermore, it can effectively separate these monohalobenzenes and exhibits a clear affinity for monohalobenzenes according to the following order: PhI > PhBr > PhCl > PhF. In addition, PhX⊂CdL2(OTs)2 exhibits guest-dependent luminescence properties.

A self-assembled Pd6L8 nanoball for Suzuki–Miyaura coupling reactions in both homogeneous and heterogeneous formats

A self-assembled nano-sized Pd6L8 (L = 1,3,5-tris(4′-pyridyloxadiazole)-2,4,6-triethylbenzene) ball was constructed based on a new oxadiazole-containing tripod. In H2O–EtOH mixed-solvent system, Pd(II)-ball displays excellent performance in Suzuki–Miyaura cross-coupling reactions at low catalyst loading under ambient conditions in a homogeneous fashion. Furthermore, it shows heterogeneous catalyst nature in o-xylene and can be reused without loss of catalytic activity.

A drug-loaded nanoscale metal–organic framework with a tumor targeting agent for highly effective hepatoma therapy

Drug delivery systems with targeting agents for precise drug release in cancer therapy are very significant and important. Herein, we report the rational design and synthesis of a DOX (doxorubicin) loaded UiO-68-type of nanoscale metal-organic framework (NMOF) with a tumor targeting agent (folic acid, FA), DOX@UiO-68-FA (3), as a multifunctional drug delivery system for hepatoma (Hep G2) therapy via tail-vein injection. Compared to free DOX, FA-unloaded DOX@Mi-UiO-68 (2), 3 exhibits a much higher antitumor efficacy, which was confirmed by cell imaging, standard 3-(4,5-dimethylthiahiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) proliferation and in vivo experiments.

Micro-Cu4I4-MOF: reversible iodine adsorption and catalytic properties for tandem reaction of Friedel–Crafts alkylation of indoles with acetals

We report a convenient approach, the first of its kind, to construct a microscale non-metal@MOF composite catalytic host-guest system for an organic tandem reaction. The reported porous Cu4I4-MOF is able to reversibly adsorb molecular iodine at room temperature. The obtained I2@Cu4I4-MOF host-guest system can be a highly heterogeneous catalyst to promote the Friedel-Crafts alkylation of indoles with acetals in a one-pot two-step fashion under solvent-free conditions at room temperature.

Fabrication of Cd(II)-MOF-based ternary photocatalytic composite materials for H2 production via a gel-to-crystal approach.

Cd(II)-MOF-based ternary composite materials of CdS@Cd(II)-MOF@TiO2 were prepared by a unique TiO2 induced gel-to-crystal approach. CdS@Cd(II)-MOF@TiO2 was demonstrated to be a highly active photocatalyst for hydrogen production under visible light based on water photolysis.

Reversible adsorption and separation of chlorocarbons and BTEX based on Cu(II)-metal organic framework

A new non-interpenetrating 2D Cu(II)-metal organic framework has been successfully synthesized from the carbazole-bridging organic ligand L and Cu(NO3)2 in solution. The CuL2(NO3)2 framework contains square-like channels and the n-butyl groups on L face toward the channel center to form the typical hydrophobic pores. In addition, the reported CuL2(NO3)2 host can reversibly upload various VOCs such as CH2Cl2, CHCl3 and BTEX (benzene, toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene) under ambient conditions without loss of framework integrity. Furthermore, it is able to effectively separate CH2Cl2 from CHCl3, benzene from toluene/ethylbenzene/xylene and toluene from ethylbenzene/xylene in the liquid phase. The selectivity for chlorocarbons is derived from the substrate polarity, while the host–guest hydrophobic interaction might be the dominating factor for BTEX affinity.

A MOF-membrane based on the covalent bonding driven assembly of a NMOF with an organic oligomer and its application in membrane reactors

A UiO-66-MOF-based membrane UiO-66-TEM (1) was prepared by the assembly of methacrylamide-decorated UiO-66-NH-Met with a thiol side chain-attached polysiloxane (PSI-SH) via a photoinduced thiol-ene click reaction. The obtained membrane 1 can be a platform to support Au nanoparticles (Au NPs) to generate an Au-MOF-polymer composite membrane Au@UiO-66-TEM (2). 1 and 2 can be used to build highly efficient continuous flow-through membrane reactors for Knoevenagel condensation of 4-nitrobenzaldehyde with malononitrile and 4-nitrophenol (4-NP) reduction at ambient temperature, respectively.