scholarly journals The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal–organic framework DUT-98

2019 ◽  
Vol 10 ◽  
pp. 1737-1744 ◽  
Author(s):  
Simon Krause ◽  
Volodymyr Bon ◽  
Hongchu Du ◽  
Rafal E Dunin-Borkowski ◽  
Ulrich Stoeck ◽  
...  
Keyword(s):  
Crystal Size ◽  
Metal Organic Framework ◽  
Adsorption Behavior ◽  
Switching Behavior ◽  
Type I ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic ◽  
The Impact ◽  
Organic Framework

In this contribution we analyze the influence of adsorption cycling, crystal size, and temperature on the switching behavior of the flexible Zr-based metal–organic framework DUT-98. We observe a shift in the gate-opening pressure upon cycling of adsorption experiments for micrometer-sized crystals and assign this to a fragmentation of the crystals. In a series of samples, the average crystal size of DUT-98 crystals was varied from 120 µm to 50 nm and the obtained solids were characterized by X-ray diffraction, infrared spectroscopy, as well as scanning and transmission electron microscopy. We analyzed the adsorption behavior by nitrogen and water adsorption at 77 K and 298 K, respectively, and show that adsorption-induced flexibility is only observed for micrometer-sized crystals. Nanometer-sized crystals were found to exhibit reversible type I adsorption behavior upon adsorption of nitrogen and exhibit a crystal-size-dependent steep water uptake of up to 20 mmol g−1 at 0.5 p/p 0 with potential for water harvesting and heat pump applications. We furthermore investigate the temperature-induced structural transition by in situ powder X-ray diffraction. At temperatures beyond 110 °C, the open-pore state of the nanometer-sized DUT-98 crystals is found to irreversibly transform to a closed-pore state. The connection of crystal fragmentation upon adsorption cycling and the crystal size dependence of the adsorption-induced flexibility is an important finding for evaluation of these materials in future adsorption-based applications. This work thus extends the limited amount of studies on crystal size effects in flexible MOFs and hopefully motivates further investigations in this field.

scholarly journals The impact of crystal size and temperature on the adsorption-induced flexibility of the Zr-based metal-organic framework DUT-98

2019 ◽  
Author(s):  
Simon Krause ◽  
Volodymyr Bon ◽  
Hongchu Du ◽  
Rafal E Dunin-Borkowski ◽  
Ulrich Stoeck ◽  
...  
Keyword(s):  
Crystal Size ◽  
Metal Organic Framework ◽  
Type I ◽  
Adsorption Behaviour ◽  
X Ray Diffraction ◽  
Transmission Electron ◽  
Adsorption Of Nitrogen ◽  
Metal Organic ◽  
The Impact ◽  
Organic Framework

In this contribution we analyse the influence of adsorption cycling, crystal size, and temperature on the switching behaviour of the flexible Zr-based metal-organic framework DUT-98. We observe a shift in the gate opening pressure upon cycling of adsorption experiments of micro meter-sized crystals and assign this to a fragmentation of the crystals. In a series of modulated syntheses we downsize the average crystal size of DUT-98 crystals from 120 µm to 50 nm and characterize the obtained solids by X-ray diffraction, infrared spectroscopy, as well as scanning and transmission electron microscopy. We analyse the adsorption behaviour by nitrogen and water adsorption at 77 K and 298 K, respectively and show that adsorption-induced flexibility is only observed for micro meter-sized crystals. Nanometer-sized crystals were found to exhibit reversible type I adsorption behaviour upon adsorption of nitrogen and exhibit a crystal-size dependent steep water uptake of up to 20 mmol g-1 at 0.5 p/p 0 with potential for water harvesting and heat pump applications. We furthermore investigate the temperature-induced structural transition by in situ PXRD. At temperatures beyond 110 °C the open pore state of nano meter-sized DUT-98 crystals are found to irreversibly transform in a closed pore state. The connection of crystal fragmentation upon adsorption cycling and the crystal size-dependence of the adsorption-induced flexibility is an important finding for evaluation of these materials in future adsorption-based applications. This work thus extends the limited amount of studies on crystal size effects in flexible MOFs and hopefully motivates further investigations into this field.

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)

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.

Single Crystal X-ray Diffraction Studies of Carbon Dioxide and Fuel-Related Gases Adsorbed on the Small Pore Scandium Terephthalate Metal Organic Framework, Sc2(O2CC6H4CO2)3

Langmuir ◽  
2009 ◽  
Vol 25 (6) ◽  
pp. 3618-3626 ◽  
Author(s):  
Stuart R. Miller ◽  
Paul A. Wright ◽  
Thomas Devic ◽  
Christian Serre ◽  
Gérard Férey ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Single Crystal ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Small Pore ◽  
Metal Organic ◽  
Organic Framework

scholarly journals Exceptional adsorption-induced cluster and network deformation in the flexible metal–organic framework DUT-8(Ni) observed by in situ X-ray diffraction and EXAFS

2015 ◽  
Vol 17 (26) ◽  
pp. 17471-17479 ◽  
Author(s):  
Volodymyr Bon ◽  
Nicole Klein ◽  
Irena Senkovska ◽  
Andreas Heerwig ◽  
Jürgen Getzschmann ◽  
...  
Keyword(s):  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Gate Opening ◽  
Metal Organic ◽  
Flexible Metal ◽  
Organic Framework

The “gate opening” mechanism in flexible MOF Ni2(2,6-ndc)2dabco was elucidated in detail.

A Mn(II) Metal-Organic Framework Constructed from a Tetrahedral Silicon-Cored Ligand

2013 ◽  
Vol 275-277 ◽  
pp. 2367-2370
Author(s):  
Qing Yu Ma ◽  
Rui Fang Guan ◽  
Guo Zhong Li ◽  
Deng Xu Wang
Keyword(s):  
Single Crystal ◽  
Metal Organic Framework ◽  
Diffusion Method ◽  
X Ray Diffraction ◽  
X Ray ◽  
Slow Diffusion ◽  
Sheet Structure ◽  
Metal Organic ◽  
1D Chains ◽  
Organic Framework

A novel metal-organic framework, MnCl2(BIPS)2•2CH3OH•2H2O (1) were synthesized from MnCl2 and a tetrahedral silicon-cored ligand, Me2Si(p-C6H4-imdazol-1-yl)2 (BIPS) under the slow diffusion method. The structure was determined by single-crystal X-ray diffraction. Complex 1 is a 2D sheet structure constructed from 1D chains with 34-atom metallamacrocycles.

Rapid Recognition of Fatal Cyanide in Water in a Wide pH Range by a Trifluoroacetamido Based Metal-Organic Framework

2021 ◽  
Author(s):  
Abhijeet Rana ◽  
Chiranjib Gogoi ◽  
Subhrajyoti Ghosh ◽  
Soutick Nandi ◽  
Saurav Kumar ◽  
...  
Keyword(s):  
Thermogravimetric Analysis ◽  
Terephthalic Acid ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Acid Ligand ◽  
Wide Ph Range ◽  
Metal Organic ◽  
Ph Range ◽  
Organic Framework

A new metal-organic-framework (MOF) called UiO-66-NH-COCF3 was prepared using trifluoroacetamido functionalized terephthalic acid ligand. Powder X-ray diffraction (PXRD), infrared (IR) spectroscopy, thermogravimetric analysis (TGA) and Brunauer Emmett-Teller (BET) experiment were...

scholarly journals Twinning in Zr-Based Metal-Organic Framework Crystals

Chemistry ◽  
2020 ◽  
Vol 2 (3) ◽  
pp. 777-786
Author(s):  
Sigurd Øien-Ødegaard ◽  
Karl Lillerud
Keyword(s):  
Crystal Structures ◽  
Metal Organic Framework ◽  
Special Importance ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic ◽  
Ab Initio Structure ◽  
Crystal Twinning ◽  
Organic Framework

Ab initio structure determination of new metal-organic framework (MOF) compounds is generally done by single crystal X-ray diffraction, but this technique can yield incorrect crystal structures if crystal twinning is overlooked. Herein, the crystal structures of three Zirconium-based MOFs, that are especially prone to twinning, have been determined from twinned crystals. These twin laws (and others) could potentially occur in many MOFs or related network structures, and the methods and tools described herein to detect and treat twinning could be useful to resolve the structures of affected crystals. Our results highlight the prevalence (and sometimes inevitability) of twinning in certain Zr-MOFs. Of special importance are the works of Howard Flack which, in addition to fundamental advances in crystallography, provide accessible tools for inexperienced crystallographers to take twinning into account in structure elucidation.

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