Post-Synthetic Modification of UiO66 and its Application in Catalytic Reactions

Abstract Because of their unique surface area and adjustable pore size, Metal-Organic Frameworks(MOFs) have been widely used in lots of research fields, such as catalysis, energy storage, sensing, separation. In this paper, as for the Knoevenagel reaction, UiO66 and other UiO series MOFs were synthesized and modified. UiO66 nanoparticles were prepared by one-pot method. 2-aminopyridine, 3-aminopyridine and 4-aminopyridine were used to prepare UiO66-2Py, UiO66-3Py and UiO66-4Py nanoparticles. UiO66-2Py, UiO66-3Py and UiO66-4Py nanoparticles were modified by activated arginine, lysine and glycine to synthesize UiO66-2Py-Arg, UiO66-3Py-Lys and UiO66-4Py-Gly. Finally, the obtained samples were used for the Knoevenagel catalytic condensation reactions of benzaldehyde and ethyl cyanoacetate. In this process, the prepared samples and their intermediates were characterized by infrared spectroscopy (IR) and X-ray diffraction(XRD), which showed that the modification of UiO66 was successful. UiO66-3Py-Lys and UiO66-4Py-Gly showed high catalytic activity in the supernatant determined by fluorescence spectrophotometer, and UiO66-4Py-Gly showed the best catalytic effects at the volume of 0.4mL benzaldehyde.

Download Full-text

FSM-16-SO3H nanoparticles as a novel heterogeneous catalyst: preparation, characterization, and catalytic application in the synthesis of polyhydroquinolines

Main Group Metal Chemistry ◽

10.1515/mgmc-2018-0006 ◽

2018 ◽

Vol 41 (3-4) ◽

pp. 91-101 ◽

Cited By ~ 5

Author(s):

Somayeh Hashemi-Uderji ◽

Mohammad Abdollahi-Alibeik ◽

Reza Ranjbar-Karimi

Keyword(s):

Room Temperature ◽

Ammonium Acetate ◽

Sol Gel ◽

Ethyl Cyanoacetate ◽

Textural Properties ◽

High Catalytic Activity ◽

X Ray Diffraction ◽

One Pot ◽

X Ray ◽

Catalytic Application

Abstract FSM-16-SO3H nanoparticles were prepared using a sol-gel method at room temperature. The prepared FSM-16-SO3H was used to catalyze the synthesis of polyhydroquinolines through a one-pot, four-component reaction of aldehydes, dimedone, ethyl cyanoacetate, and ammonium acetate under reflux condition in EtOH as a green solvent. To investigate the textural properties of the prepared catalyst, various techniques were applied such as X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscope, and Brunauer–Emmett–Teller. High catalytic activity, easy handling, and thermal stability are the superior properties that could be denoted after successive investigations of this catalyst. In addition, the catalyst can be recovered easily and reused effectively for several cycles.

Download Full-text

Revisiting the High-Pressure Properties of the Metal-Organic Frameworks ZIF-8 and ZIF-67

10.26434/chemrxiv.13146278.v1 ◽

2020 ◽

Author(s):

Pia Vervoorts ◽

Stefan Burger ◽

Karina Hemmer ◽

Gregor Kieslich

Keyword(s):

High Pressure ◽

State Of The Art ◽

Energy Landscape ◽

Structural Flexibility ◽

Zeolitic Imidazolate Frameworks ◽

Stimuli Responsive ◽

X Ray Diffraction ◽

X Ray ◽

Open Questions ◽

Metal Organic

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to p = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at p = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).

Download Full-text

Revisiting the High-Pressure Properties of the Metal-Organic Frameworks ZIF-8 and ZIF-67

10.26434/chemrxiv.13146278 ◽

2020 ◽

Author(s):

Pia Vervoorts ◽

Stefan Burger ◽

Karina Hemmer ◽

Gregor Kieslich

Keyword(s):

High Pressure ◽

State Of The Art ◽

Energy Landscape ◽

Structural Flexibility ◽

Zeolitic Imidazolate Frameworks ◽

Stimuli Responsive ◽

X Ray Diffraction ◽

X Ray ◽

Open Questions ◽

Metal Organic

Download Full-text

Synthesis and Structure of a Clathrated Two-Dimensional Metal-Organic Framework: [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2·H2O (L = Bis(1-pyrazinylethylidene)hydrazine)

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20080024 ◽

2008 ◽

Vol 73 (1) ◽

pp. 24-31

Author(s):

Dayu Wu ◽

Genhua Wu ◽

Wei Huang ◽

Zhuqing Wang

Keyword(s):

Metal Organic Framework ◽

Channel Structure ◽

Two Dimensional ◽

X Ray Diffraction ◽

Guest Molecules ◽

X Ray ◽

Square Planar ◽

Metal Organic ◽

Aqueous Meoh ◽

Organic Framework

The compound [Cd(4,4'-bpy)2(H2O)2](ClO4)2·(L)2 was obtained by the reaction of Cd(ClO4)2, bis(1-pyrazinylethylidene)hydrazine (L) and 4,4'-bipyridine in aqueous MeOH. Single-crystal X-ray diffraction has revealed its two-dimensional metal-organic framework. The 2-D layers superpose on each other, giving a channel structure. The square planar grids consist of two pairs of shared edges with Cd(II) ion and a 4,4'-bipyridine molecule each vertex and side, respectively. The square cavity has a dimension of 11.817 × 11.781 Å. Two guest molecules of bis(1-pyrazinylethylidene)hydrazine are clathrated in every hydrophobic host cavity, being further stabilized by π-π stacking and hydrogen bonding. The results suggest that the hydrazine molecules present in the network serve as structure-directing templates in the formation of crystal structures.

Download Full-text

Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands

Zeitschrift für Naturforschung B ◽

10.1515/znb-2020-0041 ◽

2020 ◽

Vol 75 (8) ◽

pp. 727-732

Author(s):

Chen Zhang ◽

Jian-Qing Tao

Keyword(s):

Crystal Structure ◽

Thermal Analysis ◽

Uv Light ◽

Metal Organic Framework ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Uv Light Irradiation ◽

Photocatalytic Activities ◽

Metal Organic

AbstractA new Cu(II) metal-organic framework, [Cu(L)(OBA)·H2O]n (1) [H2OBA = 4,4′-oxybis(benzoic acid), L = 3,5-di(1H-benzimidazol-1-yl)pyridine] was hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis and single-crystal X-ray diffraction. Complex 1 is a four-connected uni-nodal 2D net with a (44·62) topology which shows an emission centered at λ ∼393 nm upon excitation at λ = 245 nm. Moreover, complex 1 possesses high photocatalytic activities for the decomposition of Rhodamine B (RhB) under UV light irradiation.

Download Full-text

In situ X‐ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)‐based Metal‐Organic Frameworks with UiO‐66 and MIL‐140 architectures

Chemistry - A European Journal ◽

10.1002/chem.202005085 ◽

2021 ◽

Author(s):

Stephen J. I. Shearan ◽

Jannick Jacobsen ◽

Ferdinando Costantino ◽

Roberto D’Amato ◽

Dmitri Novikov ◽

...

Keyword(s):

Metal Organic Frameworks ◽

X Ray Diffraction ◽

X Ray ◽

Metal Organic

Download Full-text

Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes

Catalysts ◽

10.3390/catal11020204 ◽

2021 ◽

Vol 11 (2) ◽

pp. 204

Author(s):

Yu Li ◽

Chumin Liang ◽

Xunzhong Zou ◽

Jinzhong Gu ◽

Marina V. Kirillova ◽

...

Keyword(s):

Coordination Polymers ◽

Polycarboxylic Acid ◽

X Ray Diffraction ◽

X Ray ◽

Trimethylsilyl Cyanide ◽

Effect Of Solvent ◽

Highly Active ◽

Solvent Type ◽

Metal Organic ◽

Chloride Salts

Three 2D coordination polymers, [Cu2(µ4-dpa)(bipy)2(H2O)]n∙6nH2O (1), [Mn2(µ6-dpa)(bipy)2]n (2), and [Zn2(µ4-dpa)(bipy)2(H2O)2]n·2nH2O (3), were prepared by a hydrothermal method using metal(II) chloride salts, 3-(2′,4′-dicarboxylphenoxy)phthalic acid (H4dpa) as a linker, as well as 2,2′-bipyridine (bipy) as a crystallization mediator. Compounds 1–3 were obtained as crystalline solids and fully characterized. The structures of 1–3 were established by single-crystal X-ray diffraction, revealing 2D metal-organic networks of sql, 3,6L66, and hcb topological types. Thermal stability and catalytic behavior of 1–3 were also studied. In particular, zinc(II) coordination polymer 3 functions as a highly active and recoverable heterogeneous catalyst in the mild cyanosilylation of benzaldehydes with trimethylsilyl cyanide to give cyanohydrin derivatives. The influence of various parameters was investigated, including a time of reaction, a loading of catalyst and its recycling, an effect of solvent type, and a substrate scope. As a result, up to 93% product yields were attained in a catalyst recoverable and reusable system when exploring 4-nitrobenzaldehyde as a model substrate. This study contributes to widening the types of multifunctional polycarboxylic acid linkers for the design of novel coordination polymers with notable applications in heterogeneous catalysis.

Download Full-text

A MOF based on a lead(II) 2-oxido-6-methylpyridine-4-carboxylate network

Zeitschrift für Naturforschung B ◽

10.1515/znb-2019-0208 ◽

2020 ◽

Vol 75 (4) ◽

pp. 365-369

Author(s):

Long Tang ◽

Yu Pei Fu ◽

Na Cui ◽

Ji Jiang Wang ◽

Xiang Yang Hou ◽

...

Keyword(s):

Crystal Structure ◽

Solid State ◽

Carboxylic Acid ◽

Thermogravimetric Analysis ◽

Metal Organic Framework ◽

X Ray Diffraction ◽

X Ray ◽

Connected Node ◽

Metal Organic ◽

Solid State Fluorescence

AbstractA new metal-organic framework, [Pb(hmpcaH)2]n (1), has been hydrothermally synthesized from Pb(OAc)2 · 3H2O and 2-hydroxy-6-methylpyridine-4-carboxylic acid (hmpcaH2; 2), and characterized by IR spectroscopy, elemental and thermogravimetric analysis, and single-crystal X-ray diffraction. In complex 1, each hmpcaH− ligand represents a three-connected node to combine with the hexacoordinated Pb(II) ions, generating a 3D binodal (3,6)-connected ant network. The crystal structure of 2 was determined. The solid-state fluorescence properties of 1 and 2 were investigated.

Download Full-text