A general and facile strategy for precisely controlling the crystal size of monodispersed metal–organic frameworks via separating the nucleation and growth

2018 ◽  
Vol 54 (6) ◽  
pp. 584-587 ◽  
Author(s):  
Xiaocheng Lan ◽  
Ning Huang ◽  
Jinfu Wang ◽  
Tiefeng Wang
Keyword(s):  
Crystal Size ◽  
Metal Organic Frameworks ◽  
Nucleation And Growth ◽  
Metal Organic

Nucleation and growth were separated to precisely control the crystal size of MOFs.

Surviving Under Pressure: The Role of Solvent, Crystal Size, and Morphology During Pelletization of Metal–Organic Frameworks

2021 ◽  
Author(s):  
Timothy C. Wang ◽  
Ashley M. Wright ◽  
William J. Hoover ◽  
Kevin J. Stoffel ◽  
Rachelle K. Richardson ◽  
...  
Keyword(s):  
Crystal Size ◽  
Metal Organic Frameworks ◽  
Metal Organic ◽  
Size And Morphology ◽  
Role Of Solvent

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

2020 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Nucleation And Growth ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rate Determining Step ◽  
Wide Range ◽  
Metal Organic

We report on the results of a thorough <i>in situ</i> synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds <i>in situ</i> in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO<sub>3</sub>) and amount of the coordination modulator acetic acid (AcOH). When only HNO<sub>3</sub> is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO<sub>3</sub>, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO<sub>3</sub> slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO<sub>3</sub> favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO<sub>3</sub>. Based on these <i>in situ</i> results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

From Micro to Nano: A Toolbox for Tuning Crystal Size and Morphology of Benzotriazolate-Based Metal–Organic Frameworks

2016 ◽  
Vol 16 (6) ◽  
pp. 3190-3197 ◽  
Author(s):  
Hana Bunzen ◽  
Maciej Grzywa ◽  
Manuel Hambach ◽  
Sebastian Spirkl ◽  
Dirk Volkmer
Keyword(s):  
Crystal Size ◽  
Metal Organic Frameworks ◽  
Metal Organic ◽  
Size And Morphology

Control of the nucleation and growth processes of metal–organic frameworks using a metal ion-doped polymer substrate for the construction of continuous films

CrystEngComm ◽  
2019 ◽  
Vol 21 (33) ◽  
pp. 4851-4854
Author(s):  
Takashi Ohhashi ◽  
Takaaki Tsuruoka ◽  
Yohei Takashima ◽  
Kensuke Akamatsu
Keyword(s):  
Metal Ion ◽  
Metal Organic Frameworks ◽  
Nucleation And Growth ◽  
Polymer Substrate ◽  
Growth Processes ◽  
Metal Organic ◽  
Doped Polymer

Densely-packed continuous MOF crystal-based films can be prepared by controlling the nucleation and growth processes.

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

2020 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Nucleation And Growth ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rate Determining Step ◽  
Wide Range ◽  
Metal Organic

We report on the results of a thorough <i>in situ</i> synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds <i>in situ</i> in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO<sub>3</sub>) and amount of the coordination modulator acetic acid (AcOH). When only HNO<sub>3</sub> is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO<sub>3</sub>, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO<sub>3</sub> slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO<sub>3</sub> favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO<sub>3</sub>. Based on these <i>in situ</i> results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

scholarly journals Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

2019 ◽  
Vol 7 (37) ◽  
pp. 21459-21475 ◽  
Author(s):  
Sebastian Ehrling ◽  
Irena Senkovska ◽  
Volodymyr Bon ◽  
Jack D. Evans ◽  
Petko Petkov ◽  
...  
Keyword(s):  
Structural Transition ◽  
Crystal Size ◽  
Metal Organic Frameworks ◽  
Paddle Wheel ◽  
Metal Organic

DUT-8(Co) shows a selective structural transition for CH2Cl2vs. CHCl3 and CCl4 at 298 K.

scholarly journals Using Supercritical CO2 in the Preparation of Metal-Organic Frameworks: Investigating Effects on Crystallisation

Crystals ◽  
2019 ◽  
Vol 10 (1) ◽  
pp. 17 ◽  
Author(s):  
Huan Doan ◽  
Fei Cheng ◽  
Thandeka Dyirakumunda ◽  
Mark Elsegood ◽  
Jiamin Chin ◽  
...  
Keyword(s):  
Low Temperatures ◽  
Supercritical Co2 ◽  
Crystal Size ◽  
Solvothermal Method ◽  
Metal Organic Frameworks ◽  
Product Yields ◽  
Metal Organic ◽  
Size And Morphology

In this report, we explore the use of supercritical CO2 (scCO2) in the synthesis of well-known metal-organic frameworks (MOFs) including Zn-MOF-74 and UiO-66, as well as on the preparation of [Cu24(OH-mBDC)24]n metal-organic polyhedra (MOPs) and two new MOF structures {[Zn2(L1)(DPE)]∙4H2O}n and {[Zn3(L1)3(4,4′-azopy)]∙7.5H2O}n, where BTC = benzene-1,3,5-tricarboxylate, BDC = benzene-1,4-dicarboxylate, L1 = 4-carboxy-phenylene-methyleneamino-4-benzoate, DPE = 1,2-di(4-pyridyl)ethylene, 4.4′-azopy = 4,4′- azopyridine, and compare the results versus traditional solvothermal preparations at low temperatures (i.e., 40 °C). The objective of the work was to see if the same or different products would result from the scCO2 route versus the solvothermal method. We were interested to see which method produced the highest yield, the cleanest product and what types of morphology resulted. While there was no evidence of additional meso- or macroporosity in these MOFs/MOPs nor any significant improvements in product yields through the addition of scCO2 to these systems, it was shown that the use of scCO2 can have an effect on crystallinity, crystal size and morphology.

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

2021 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Metal Organic Frameworks ◽  
Nucleation And Growth ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rate Determining Step ◽  
Wide Range ◽  
Metal Organic ◽  
Two Phases

We report on the results of a thorough <i>in situ</i> synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as reagents, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds <i>in situ</i> in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO<sub>3</sub>) and amount of the coordination modulator acetic acid (AcOH). When only HNO<sub>3</sub> is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO<sub>3</sub>, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO<sub>3</sub> slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO<sub>3</sub> favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO<sub>3</sub>. Based on these <i>in situ</i> results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

Layered Metal–Organic Frameworks Based on Octahedral Lanthanides and a Phosphonate Linker: Control of Crystal Size

2014 ◽  
Vol 14 (10) ◽  
pp. 4873-4877 ◽  
Author(s):  
Filipe A. Almeida Paz ◽  
Sérgio M. F. Vilela ◽  
João P. C. Tomé
Keyword(s):  
Crystal Size ◽  
Metal Organic Frameworks ◽  
Metal Organic
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