scholarly journals Adsorption of Carbon Dioxide, Methane, and Nitrogen on Zn(dcpa) Metal-Organic Framework

Energies ◽  
2021 ◽  
Vol 14 (18) ◽  
pp. 5598
Author(s):  
Rui P. P. L. Ribeiro ◽  
Isabel A. A. C. Esteves ◽  
José P. B. Mota
Keyword(s):  
Carbon Dioxide ◽  
Metal Organic Framework ◽  
Energy Difference ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
Metastable Structures ◽  
Metal Organic ◽  
Pressure Swing ◽  
Adsorption Of Co2 ◽  
Carbon Dioxide Co2

Adsorption-based processes using metal-organic frameworks (MOFs) are a promising option for carbon dioxide (CO2) capture from flue gases and biogas upgrading to biomethane. Here, the adsorption of CO2, methane (CH4), and nitrogen (N2) on Zn(dcpa) MOF (dcpa (2,6-dichlorophenylacetate)) is reported. The characterization of the MOF by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and N2 physisorption at 77 K shows that it is stable up to 650 K, and confirms previous observations suggesting framework flexibility upon exposure to guest molecules. The adsorption equilibrium isotherms of the pure components (CO2, CH4, and N2), measured at 273–323 K, and up to 35 bar, are Langmuirian, except for that of CO2 at 273 K, which exhibits a stepwise shape with hysteresis. The latter is accurately interpreted in terms of the osmotic thermodynamic theory, with further refinement by assuming that the free energy difference between the two metastable structures of Zn(dcpa) is a normally distributed variable due to the existence of different crystal sizes and defects in a real sample. The ideal selectivities of the equimolar mixtures of CO2/N2 and CO2/CH4 at 1 bar and 303 K are 12.8 and 2.9, respectively, which are large enough for Zn(dcpa) to be usable in pressure swing adsorption.

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 A Universal Porous Adsorbent for the Selective Capture of Carbon Dioxide

2019 ◽  
Author(s):  
Omid Taheri Qazvini ◽  
Shane G. Telfer
Keyword(s):  
Carbon Dioxide ◽  
Natural Gas ◽  
Porous Materials ◽  
Noncovalent Interactions ◽  
Metal Organic Framework ◽  
Time Lags ◽  
Guest Molecules ◽  
Energy Penalty ◽  
Carbon Dioxide Co2 ◽  
Short Time

<div>Efficient and sustainable methods for carbon dioxide (CO2) capture are essential. Its atmospheric</div><div>concentration must be reduced to meet climate change targets, and its remediation from chemical</div><div>feedstocks and natural gas is vital. While mature technologies involving chemical reactions that trap the</div><div>CO2 do exist, they have many drawbacks. Porous materials with void spaces that are complementary in</div><div>size and electrostatic potential to CO2 offer an alternative. In these materials, the molecular CO2 guests</div><div>are trapped by noncovalent interactions, hence they can be recycled by releasing the CO2 with a low</div><div>energy penalty. Porous materials that are selective towards CO2 when it is present with an array of</div><div>competing gases are challenging to produce. Here, we show how a metal-organic framework, termed</div><div>MUF-16 (MUF = Massey University Framework), is a ‘universal’ adsorbent for CO2 that sequesters</div><div>CO2 from a broad palette of gas streams with record selectivities over competing gases. The position of</div><div>the CO2 molecules captured in the framework pores was determined crystallographically to illustrate</div><div>how complementary noncovalent interactions envelop the guest molecules. The pore environment has a</div><div>low affinity for all other gases, which underpins the benchmark selectivity of MUF-16 for CO2 over</div><div>methane, hydrogen and acetylene. Breakthrough gas separations under dynamic conditions benefit from</div><div>short time lags in the elution of the weakly-adsorbed component to deliver a repertoire of high-purity</div><div>products. MUF-16 is an inexpensive, robust, easily regernarable and recyclable adsorbent that is</div><div>universally applicable to the removal of CO2 from sources such as natural gas, syngas and chemical</div><div>feedstocks.</div>

Solvent exchange in a metal–organic framework single crystal monitored by dynamicin situX-ray diffraction

2017 ◽  
Vol 73 (4) ◽  
pp. 669-674 ◽  
Author(s):  
Jordan M. Cox ◽  
Ian M. Walton ◽  
Gage Bateman ◽  
Cassidy A. Benson ◽  
Travis Mitchell ◽  
...  
Keyword(s):  
Rational Design ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
Time Resolved ◽  
Ethanol Solvate ◽  
Significant Step ◽  
Metal Organic ◽  
Flexible Metal ◽  
Organic Framework

Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamicin situX-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal–organic framework [Co(AIP)(bpy)0.5(H2O)]·2H2O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.

scholarly journals A Universal Porous Adsorbent for the Selective Capture of Carbon Dioxide

2019 ◽  
Author(s):  
Omid Taheri Qazvini ◽  
Shane G. Telfer
Keyword(s):  
Carbon Dioxide ◽  
Noncovalent Interactions ◽  
Metal Organic Framework ◽  
Time Lags ◽  
Atmospheric Concentration ◽  
Guest Molecules ◽  
Gas Streams ◽  
Energy Penalty ◽  
Metal Organic ◽  
Short Time

<p>Efficient and sustainable methods for carbon dioxide (CO<sub>2</sub>) capture are essential. Its atmospheric concentration must be reduced to meet climate change targets, and its removal from sources such as chemical feedstocks is vital. While mature technologies involving chemical reactions that absorb CO<sub>2</sub> exist, they have many drawbacks. Porous materials with void spaces that are complementary in size and electrostatic potential to CO<sub>2</sub> offer an alternative. In these materials, the molecular CO<sub>2 </sub>guests are trapped by noncovalent interactions, hence they can be recycled by releasing the CO<sub>2</sub> with a low energy penalty. Capacity and selectivity are the twin challenges for such porous adsorbents. Here, we show how a metal-organic framework, termed MUF-16 (MUF = Massey University Framework), is a universal adsorbent for CO<sub>2</sub> that sequesters large quantities of CO<sub>2</sub> from a broad palette of gas streams with record selectivities over competing gases. The crystallographically-determined position of the CO<sub>2</sub> molecules captured in the framework pores illustrate how complementary noncovalent interactions envelop CO<sub>2</sub> while repelling other guest molecules. The low affinity of the pore environment for other gases underpins the strikingly high selectivity of MUF-16 for CO<sub>2</sub> over methane, nitrogen, hydrogen, acetylene, ethylene, ethane, propylene and propane. Breakthrough gas separations under dynamic conditions benefit from short time lags in the elution of the weakly-adsorbed component to deliver a repertoire of high-purity products. MUF-16 is an inexpensive, robust, recyclable adsorbent that is universally applicable to the removal of CO<sub>2 </sub>from sources such as natural gas, syngas, flue gas and chemical feedstocks.</p><br>

scholarly journals A Universal Porous Adsorbent for the Selective Capture of Carbon Dioxide

2019 ◽  
Author(s):  
Omid Taheri Qazvini ◽  
Shane G. Telfer
Keyword(s):  
Carbon Dioxide ◽  
Noncovalent Interactions ◽  
Metal Organic Framework ◽  
Time Lags ◽  
Atmospheric Concentration ◽  
Guest Molecules ◽  
Gas Streams ◽  
Energy Penalty ◽  
Metal Organic ◽  
Short Time

<p>Efficient and sustainable methods for carbon dioxide (CO<sub>2</sub>) capture are essential. Its atmospheric concentration must be reduced to meet climate change targets, and its removal from sources such as chemical feedstocks is vital. While mature technologies involving chemical reactions that absorb CO<sub>2</sub> exist, they have many drawbacks. Porous materials with void spaces that are complementary in size and electrostatic potential to CO<sub>2</sub> offer an alternative. In these materials, the molecular CO<sub>2 </sub>guests are trapped by noncovalent interactions, hence they can be recycled by releasing the CO<sub>2</sub> with a low energy penalty. Capacity and selectivity are the twin challenges for such porous adsorbents. Here, we show how a metal-organic framework, termed MUF-16 (MUF = Massey University Framework), is a universal adsorbent for CO<sub>2</sub> that sequesters large quantities of CO<sub>2</sub> from a broad palette of gas streams with record selectivities over competing gases. The crystallographically-determined position of the CO<sub>2</sub> molecules captured in the framework pores illustrate how complementary noncovalent interactions envelop CO<sub>2</sub> while repelling other guest molecules. The low affinity of the pore environment for other gases underpins the strikingly high selectivity of MUF-16 for CO<sub>2</sub> over methane, nitrogen, hydrogen, acetylene, ethylene, ethane, propylene and propane. Breakthrough gas separations under dynamic conditions benefit from short time lags in the elution of the weakly-adsorbed component to deliver a repertoire of high-purity products. MUF-16 is an inexpensive, robust, recyclable adsorbent that is universally applicable to the removal of CO<sub>2 </sub>from sources such as natural gas, syngas, flue gas and chemical feedstocks.</p><br>

Carbon Dioxide (CO2) Fixation: Linearly Bridged Zn2 Paddlewheel Nodes by CO2 in a Metal–Organic Framework

2019 ◽  
Vol 58 (23) ◽  
pp. 16040-16046 ◽  
Author(s):  
Wenqing Wang ◽  
Yaping Wen ◽  
Jian Su ◽  
Haibo Ma ◽  
Hai-Ying Wang ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Co2 Fixation ◽  
Metal Organic Framework ◽  
Metal Organic ◽  
Carbon Dioxide Co2 ◽  
Organic Framework

scholarly journals Reversible switching between positive and negative thermal expansion in a metal–organic framework DUT-49

2020 ◽  
Vol 8 (39) ◽  
pp. 20420-20428
Author(s):  
Bikash Garai ◽  
Volodymyr Bon ◽  
Anastasia Efimova ◽  
Martin Gerlach ◽  
Irena Senkovska ◽  
...  
Keyword(s):  
Thermal Expansion ◽  
Single Crystal ◽  
Metal Organic Framework ◽  
Negative Thermal Expansion ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Metal Organic ◽  
Mesoporous Metal ◽  
Organic Framework

Reversible switching between positive and negative thermal expansion of a mesoporous metal-organic framework DUT-49 has been demonstrated and studied by synchrotron single-crystal X-ray diffraction with different guest molecules in the pores.

scholarly journals Selective Capture of Carbon Dioxide from Hydrocarbons Using a Metal-Organic Framework: Relevance to the Purification of Natural Gas and Acetylene

2020 ◽  
Author(s):  
Omid Taheri Qazvini ◽  
Shane G. Telfer
Keyword(s):  
Carbon Dioxide ◽  
Natural Gas ◽  
Noncovalent Interactions ◽  
Metal Organic Framework ◽  
Time Lags ◽  
Guest Molecules ◽  
X Ray Crystallography ◽  
Metal Organic ◽  
Short Time ◽  
Organic Framework

<p>Efficient and sustainable methods for carbon dioxide (CO<sub>2</sub>) capture are highly sought after. Mature technologies involve chemical reactions that absorb CO<sub>2, </sub>but they have many drawbacks. Energy-efficient alternatives may be realized by porous physisorbents with void spaces that are complementary in size and electrostatic potential to molecular CO<sub>2</sub>. Here, we present a robust, recyclable and inexpensive adsorbent termed MUF-16 (MUF = Massey University Framework). This metal-organic framework captures CO<sub>2</sub> with a high affinity in its one-dimensional channels. The position of the CO<sub>2</sub> molecules sequestered in the framework pores, as determined by X-ray crystallography, illustrate how complementary noncovalent interactions envelop the CO<sub>2</sub> while repelling other guest molecules. The low affinity of the MUF-16 pores for these competing gases underpins new benchmarks for the adsorption of CO<sub>2</sub> over methane, acetylene, ethylene, ethane, propylene and propane. IAST calculations show that for 50/50 mixtures at 293 K and 1 bar, the CO<sub>2</sub>/CH<sub>4</sub> selectivity is 6690 and the CO<sub>2</sub>/C<sub>2</sub>H<sub>2</sub> selectivity is 510, for example. Breakthrough gas separations under dynamic conditions benefit from short time lags in the elution of the weakly-adsorbed component to deliver high-purity hydrocarbon products. Ultimately, MUF-16 may be applicable to the removal of CO<sub>2 </sub>from sources such as natural gas and chemical feedstocks.<br></p>

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