A Universal Porous Adsorbent for the Selective Capture of Carbon Dioxide

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>

A Universal Porous Adsorbent for the Selective Capture of Carbon Dioxide

10.26434/chemrxiv.9729665.v4 ◽

2020 ◽

Author(s):

Omid Taheri Qazvini ◽

Shane G. Telfer

Keyword(s):

Carbon Dioxide ◽

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>

A Universal Porous Adsorbent for the Selective Capture of Carbon Dioxide

10.26434/chemrxiv.9729665.v1 ◽

2019 ◽

Author(s):

Omid Taheri Qazvini ◽

Shane G. Telfer

Keyword(s):

Carbon Dioxide ◽

Natural Gas ◽

Porous Materials ◽

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>

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

10.26434/chemrxiv.9729665.v5 ◽

2020 ◽

Author(s):

Omid Taheri Qazvini ◽

Shane G. Telfer

Keyword(s):

Carbon Dioxide ◽

Natural Gas ◽

Metal Organic Framework ◽

Time Lags ◽

Guest Molecules ◽

X Ray Crystallography ◽

Metal Organic ◽

Short Time ◽

<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>

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

10.26434/chemrxiv.9729665 ◽

2020 ◽

Cited By ~ 1

Author(s):

Omid Taheri Qazvini ◽

Shane G. Telfer

Keyword(s):

Carbon Dioxide ◽

Natural Gas ◽

Metal Organic Framework ◽

Time Lags ◽

Guest Molecules ◽

X Ray Crystallography ◽

Metal Organic ◽

Short Time ◽

<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>

Selective capture of carbon dioxide from hydrocarbons using a metal-organic framework

Nature Communications ◽

10.1038/s41467-020-20489-2 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Omid T. Qazvini ◽

Ravichandar Babarao ◽

Shane G. Telfer

Keyword(s):

Carbon Dioxide ◽

Density Functional ◽

Metal Organic Framework ◽

Density Functional Theory Calculations ◽

Time Lags ◽

X Ray Crystallography ◽

Metal Organic ◽

Adsorption Of Co ◽

Short Time ◽

AbstractEfficient and sustainable methods for carbon dioxide capture are highly sought after. Mature technologies involve chemical reactions that absorb CO2, but they have many drawbacks. Energy-efficient alternatives may be realised by porous physisorbents with void spaces that are complementary in size and electrostatic potential to molecular CO2. Here, we present a robust, recyclable and inexpensive adsorbent termed MUF-16. This metal-organic framework captures CO2 with a high affinity in its one-dimensional channels, as determined by adsorption isotherms, X-ray crystallography and density-functional theory calculations. Its low affinity for other competing gases delivers high selectivity for the adsorption of CO2 over methane, acetylene, ethylene, ethane, propylene and propane. For equimolar mixtures of CO2/CH4 and CO2/C2H2, the selectivity is 6690 and 510, respectively. 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, including pure methane and acetylene.

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

Energies ◽

10.3390/en14185598 ◽

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.

Alkylamine-Integrated Metal–Organic Framework-Based Waveguide Sensors for Efficient Detection of Carbon Dioxide from Humid Gas Streams

ACS Applied Materials & Interfaces ◽

10.1021/acsami.9b12052 ◽

2019 ◽

Vol 11 (36) ◽

pp. 33489-33496 ◽

Cited By ~ 3

Author(s):

Ki-Joong Kim ◽

Jeffrey T. Culp ◽

Paul R. Ohodnicki ◽

Patricia C. Cvetic ◽

Sean Sanguinito ◽

...

Keyword(s):

Carbon Dioxide ◽

Metal Organic Framework ◽

Gas Streams ◽

Efficient Detection ◽

Metal Organic ◽

Waveguide Sensors ◽

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 ◽

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.