US20140294709A1 - Alkylamine functionalized metal-organic frameworks for composite gas separations - Google Patents

Alkylamine functionalized metal-organic frameworks for composite gas separations Download PDF

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US20140294709A1
US20140294709A1 US14/228,532 US201414228532A US2014294709A1 US 20140294709 A1 US20140294709 A1 US 20140294709A1 US 201414228532 A US201414228532 A US 201414228532A US 2014294709 A1 US2014294709 A1 US 2014294709A1
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metal
framework
adsorption
ligand
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Jeffrey R. Long
Thomas M. McDonald
Deanna M. D'Alessandro
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University of California
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Priority to US15/297,114 priority patent/US10722863B2/en
Priority to US15/373,426 priority patent/US9861953B2/en
Priority to US15/820,350 priority patent/US10137430B2/en
Priority to US16/200,988 priority patent/US20190291074A1/en
Priority to US16/912,137 priority patent/US11845058B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/08—Copper compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • This invention pertains to the use of metal-organic frameworks as adsorbents for the separation of composite gasses, and more particularly to adsorbents with a high concentration of alkylamine functionalized sites in a metal organic framework and methods for the separation of a variety of materials based on selective, reversible electron transfer reactions. For example, methods are provided for the separation of individual gases from as stream of combined gases such as CO 2 from N 2 gases or CO 2 from H 2 gases from a stream of combined gases.
  • syngas from the conversion of fossil fuels (natural gas, coal, oil, oil shale, etc) or biomass requires the separation of CO 2 from H 2 and other useful gasses.
  • the coal or other material is converted into syngas (CO and H 2 ) which subsequently undergoes the water-gas shift reaction to generate CO 2 and H 2 .
  • the hydrogen is used to generate electricity after it is separated from CO 2 , which can then be prevented from release into the atmosphere.
  • This strategy, called pre-combustion CO 2 capture is advantageous in comparison to other CO 2 capture technologies that require separation of CO 2 from N 2 , O 2 , or CH 4 because the differences in size and polarizability between CO 2 and H 2 can be exploited.
  • Separation of CO 2 from CH 4 is also relevant to the purification of natural gas, which can have impurity levels of up to 92% CO 2 at its source.
  • Carbon dioxide removal is required for approximately 25% of the natural gas reserves in the United States. Removal of CO 2 , which is most commonly accomplished using amines to reduce CO 2 levels to the required 2% maximum, is conducted at pressures between 20 bar and 70 bar. Carbon dioxide removal is required for approximately 25% of the natural gas reserves in the United States.
  • Gas separations are also important in post-combustion of fossil fuels for energy production.
  • the combustion of fossil fuels is largely responsible for the increase in the global concentration of CO 2 in the Earth's atmosphere, yet fossil fuels will continue to be heavily utilized for energy production during the 21st century.
  • CCS carbon capture and sequestration
  • Aqueous amine solutions are currently the most viable adsorbents for carbon capture and are presently used for the removal of CO 2 from industrial commodities like natural gas. While a variety of advanced amines are available, 30% monoethanolamine (MEA) in water is the benchmark solvent against which competing technologies are generally compared. The low solvent cost and proven effectiveness make MEA an attractive adsorbent for many applications.
  • ammonium carbamate from two MEA molecules and one CO 2 molecule endows the scrubber with extremely high selectivity for CO 2 , but significant energy is required to regenerate the solution.
  • This high regeneration energy cost has two primary components: first, the strong, chemisorptive bond between the carbon dioxide and the amine must be broken; second, a large amount of spectator water solvent must be heated and cooled along with the active amine adsorbent, giving rise to an inefficient system. Because amines are corrosive to plant infrastructure, solutions are typically limited to no more than 30% (w/w) of the amine, and a significant increase in this concentration is not deemed feasible. In addition, solvent boil-off occurs during repeated regeneration cycles consuming the scrubber and increasing costs.
  • the present invention is directed to metal-organic framework materials and methods for use in a variety of gas separation and manipulation applications including the isolation of individual gases from a stream of combined gases, such as carbon dioxide/nitrogen, carbon dioxide/hydrogen, carbon dioxide/methane, carbon dioxide/oxygen, carbon monoxide/nitrogen, carbon monoxide/methane, carbon monoxide/hydrogen, hydrogen sulfide/methane and hydrogen sulfide/nitrogen.
  • gases such as carbon dioxide/nitrogen, carbon dioxide/hydrogen, carbon dioxide/methane, carbon dioxide/oxygen, carbon monoxide/nitrogen, carbon monoxide/methane, carbon monoxide/hydrogen, hydrogen sulfide/methane and hydrogen sulfide/nitrogen.
  • the present invention provides adsorbents that bridge the two approaches through the incorporation of sites that bind CO 2 by chemisorption onto solid materials.
  • the new materials may eliminate the need for aqueous solvents, and may have significantly lower regeneration costs compared with traditional amine scrubbers, yet maintain their exceptional selectivity and high capacity for CO 2 at low pressures.
  • the adsorption materials for gas separations are metal-organic frameworks containing ligands with basic nitrogen groups.
  • Metal-organic frameworks are porous, crystalline solids that are preferably functionalized with the incorporation of alkylamines, which exhibit enhanced basicity over aromatic amines and are capable of strongly adsorbing acid gases.
  • the preferred metal-organic frameworks are a group of porous crystalline materials formed of metal cations or clusters joined by multitopic organic linkers.
  • Ligands of the metal-organic framework may contain other structural elements used to coordinate the ligand to one or more metals of the framework. These include but are not limited to the following functional groups: carboxylate, triazolate, pyrazolate, tetrazolate, pyridines, amines, alkoxide and/or sulfate groups.
  • the preferred alkylamine ligand is N,N′-dimethylethylenediamine (“mmen”) producing (mmen-Mg 2 -BTTri) or mmen-Mg 2 .(dopbdc) functionalized frameworks.
  • the basic nitrogen groups may be incorporated into the framework on a ligand prior to framework formation, through substitution or modification of a functional group that was bonded to a ligand prior to framework formation, or by substitution of a ligand after framework formation with the ligand with a basic nitrogen group.
  • Another embodiment is a method of separating a mixture stream comprising CO 2 and N 2 .
  • the method includes contacting the mixture stream including CO 2 and N 2 with a material comprising a metal-organic framework, and a ligand with a basic nitrogen group, wherein the material preferably has an isosteric heat of CO 2 adsorption of greater than ⁇ 70 kJ/mol at zero coverage as determined by the Clausius-Clapeyron relation, obtaining a stream richer in CO 2 as compared to the mixture stream, and obtaining a stream richer in N 2 as compared to the mixture stream.
  • a process for attaching polyamine ligands to the surface of metal-organic frameworks with exposed metal cations for use in CO 2 capture.
  • a functionalized metal organic framework that can separate gases at low temperatures and pressures.
  • Yet another aspect of the invention is to provide a material and method for pre-combustion separation of carbon dioxide and hydrogen and methane from a stream of gases.
  • a further aspect of the invention is to provide a material and method for separation of carbon dioxide from a stream of post-combustion flue gases at low pressures and concentrations.
  • Another aspect of the invention is to provide a metal-organic framework that is adaptable to many different separation needs.
  • FIG. 1 is a representation of a portion of the structure of the amine functionalized metal-organic framework mmen-CuBTTri, with incorporation of the diamine N,N′-dimethylethylenediamine onto open metal sites within the pores according to the invention.
  • FIG. 2A is a graph plotting gravimetric gas sorption isotherms for CO 2 (squares) and N 2 (circles) adsorption at 25° C. for mmen-CuBTTri and CuBTTri.
  • the horizontal dashed line in corresponds to 10 wt % CO 2 adsorption.
  • FIG. 2B is a graph plotting volumetric gas sorption isotherms for CO 2 (squares) and N 2 (circles) adsorption at 25° C. for mmen-CuBTTri and CuBTTri for comparison to FIG. 2A .
  • FIG. 3 is a graph of infrared spectra obtained upon exposure of mmen-CuBTTri to a 5% CO 2 /95% He gas mixture in a high-pressure DRIFTS cell.
  • the N—H stretch of mmen is apparent at 3283 cm ⁇ 1 (vertical dashed line) on a fully evacuated sample (28).
  • Dilute CO 2 in He was slowly introduced into the cell (30) up to a dynamic pressure of 1.5 bar (32).
  • the N—H stretch fully disappeared.
  • the N—H stretch reappeared.
  • FIG. 4 is a graph of CO 2 adsorption isotherms at 298 K (squares), 308 K (circles) and 318 K (triangles) for mmen-CuBTTri.
  • FIG. 5 is a graph of N 2 adsorption isotherms at 298 K (squares), 308 K (circles) and 318 K (triangles) for mmen-CuBTTri.
  • FIG. 6 is a graph of Isosteric heats of adsorption for mmen-CuBTTri calculated from the viral method (circles) and the dual-site Langmuir method (squares).
  • FIG. 7 is a graph of % mass change over time with repeated adsorption cycles.
  • the mass of mmen-CuBTTri increased by nearly 7% as measured by thermogravimetric analysis.
  • a N 2 purge flow with a temperature swing to 60° C. fully regenerated the material, with no apparent capacity loss after 72 cycles.
  • MgBr 2 .6H 2 O and H 4 dobpdc Mg 2 (dobpdc) is obtained following evacuation of the as synthesized solid at high temperatures (middle). Addition of an excess of mmen to the evacuated framework yields the amine-appended CO 2 adsorbent Mg 2 (dobpdc)(mmen) 1.6 (H 2 O) 0.4 .
  • FIG. 9 is a graph of the adsorption of CO 2 in mmen-Mg 2 -(dobpdc) at 25° C. (squares), 50° C. (triangles), and 75° C. (circles).
  • Inset The isotherms at very low pressures exhibit a step that shifts to higher pressures at higher temperatures.
  • the dashed, vertical line marks the current partial pressure of CO 2 in air (390 ppm).
  • FIG. 1 through FIG. 9 for illustrative purposes several embodiments of the metal-organic framework adsorbents of the present invention are depicted generally in FIG. 1 through FIG. 9 and the associated methods for using and producing the alkylamine functionalized frameworks. It will be appreciated that the methods may vary as to the specific steps and sequence and the metal-organic framework architecture may vary as to structural details, without departing from the basic concepts as disclosed herein. The method steps are merely exemplary of the order that these steps may occur. The steps may occur in any order that is desired, such that it still performs the goals of the claimed invention.
  • Metal-organic frameworks are a class of porous, crystalline adsorbents that enables greater functionality with reduced adsorbent mass and volume compared to traditional solid adsorbents. These metal-organic frameworks are preferred because of the presence of coordinatively unsaturated metal centers (open metal sites) along the pore surfaces. These coordinate metal cations are known to behave as Lewis acids that strongly polarize gas adsorbents and are further amenable to post-synthetic functionalization. In these frameworks with well separated open metal sites, one amine of a diamine ligand molecule can bind to a metal cation as a Lewis base while the second amine remains available as a chemically reactive adsorption site.
  • the metals in the framework can be individual metal atoms bridged by a set of ligands or metal clusters (a collection of metal atoms that as a group interact with a set of ligands.
  • the preferred metal-organic frameworks are a group of porous crystalline materials formed of metal cations or clusters joined by multitopic organic linkers. These are frequently frameworks that are described as having “open metal sites” (also called coordinatively unsaturated metal centers).
  • the ligands of the metal-organic frameworks preferably contain basic nitrogen groups.
  • These basic nitrogen ligands may include, for example, alkyl amines or imines, but not aromatic amines (i.e. aniline derivatives).
  • the reactive chemical atom contains a lone pair of electrons including nitrogen, oxygen, sulfur, and phosphorous. More preferably, it is a basic amine. More preferably, the lone pair or pairs of the reactive atom are not in resonance with an aromatic ring.
  • the functional group is a primary, secondary, or tertiary alkylamine (an aliphatic amine).
  • Ligands of the metal-organic framework may contain other structural elements used to coordinate the ligand to one or more metals of the framework. These include but are not limited to the following functional groups: carboxylate, triazolate, pyrazolate, tetrazolate, pyridines, amines, alkoxide and/or sulfate groups.
  • the preferred alkylamine ligand is N,N′-dimethylethylenediamine (“mmen”) producing (mmen-Mg 2 -BTTri) or mmen-Mg 2 .(dopbdc) functionalized frameworks.
  • Some or all ligands of the metal organic framework may contain one or more aromatic rings that contain carbon and may contain other atoms including boron, nitrogen, and oxygen. This is most preferably five and six membered rings. These rings may provide structural rigidity to the material and/or provide spatial separation of other functional groups contained within ligands as to provide porosity to the adsorbent.
  • the structure of the basic ligands may include three distinct components: 1) A backbone that provides structural rigidity to the material. This may be, for example, an aromatic group such as a phenyl group. 2) At least one functional group that binds the ligands to the metal such as nitrogen or oxygen atoms. Specific examples include a carboxylate group, a triazolate group (as in this case for Cu-BTTri), pyrazolates, tetrazolates, pyridines, and sulfates. 3) A functional group that contains a nitrogen atom that is not integral to the structural rigidity of the material and is not bound to a metal that is available to interact with gases.
  • the functional group that contains a nitrogen atom and interacts with the CO 2 molecule is preferably a basic organic group.
  • Preferred functional groups include primary amines, secondary amines, tertiary amines, primary imines, and secondary imines, and similar compounds. Although these groups all contain nitrogen, in alternative embodiments, these groups could include other atoms as well, especially atoms having an available lone pair of electrons.
  • These basic nitrogen functional groups can be incorporated into the metal-organic framework in one of three preferable ways: 1) attached as a functional group on a ligand prior to framework formation; 2) as a substitution or modification of a functional group that was bonded to a ligand prior to framework formation; and 3) as a substitution of a ligand after framework formation for a new ligand that contains the desired functional group.
  • the nitrogen is preferably not directly bonded to an aromatic carbon atom. This is because the nitrogen would be bonded to an alkylcarbon (a methylene), giving rise to an alkylamine groups, which is preferred. Accordingly, it is preferred that at least one atom of any type separates the amine that interacts with CO 2 from the aromatic backbone.
  • the basic nitrogen groups are incorporated into the framework through a substitution or modification of a functional group that was bonded to a ligand prior to framework formation and the ligands are not exchanged. Rather, functional groups within the ligands may be exchanged for the desired functionality.
  • Other potential reactions could also be used that modify ligands to include alkylamines or imines after framework synthesis.
  • the new ligand preferably has at least two functional groups: 1) A functional group used to bind CO 2 and 2) a functional group used to bind to the metal.
  • the second functional group that binds the metal can also be an amine. It is possible to use other functional groups such as oxygen containing groups like alcohols, ethers or alkoxides, carbon groups like carbenes or unsaturated bonds like alkenes or alkynes, or sulfur atoms.
  • Preferable characteristic for the end that binds the metal include the following: 1) strongly bonded to the metal so the functional groups are not removed upon framework activation by vacuum; 2) capable of being grafted at nearly all metal sites within the pores for nearly complete functionalization.
  • the ligand itself may contain one or more amines that bind CO 2 .
  • the ligand could have 3 carboxylate groups for binding metals and 1, 2, or 3 (or more) alkylamine groups on each ligand.
  • Examples may include Tris(2-aminoethyl)amine (primary and tertiary amines) or Tris[2(methylamino)ethyl]amine (secondary and tertiary amines), which would be capable of binding a metal-site with one amine and adsorbing CO 2 with 3 other amines. These examples are branched.
  • Amines do not necessarily simply polarize CO 2 ; rather, they strongly and selectively bind it through chemisorptive interactions. Amines tethered to solid surfaces within porous materials also have considerable advantages over aqueous alkanolamines. It has also been found that the incorporation of alkylamine groups at higher loadings can further polarize the overall surface area of a metal-organic framework, thereby increasing the capacity for CO 2 capture. Other functional groups are similarly capable of polarizing framework surfaces, but many are not capable of undergoing the chemisorptive type process. Higher order amines, in particular secondary amines, have more favorable adsorption characteristics in solutions as well as on solid adsorbents. It has been found that the incorporation of N,N′-dimethylethylenediamine (mmen) at high loadings within CuBTTri affords a material with exceptional CO 2 capture characteristics.
  • mmen N,N′-dimethylethylenediamine
  • the stream of mixed gases is directed across a bed of adsorbent and the molecules of the first gas are adsorbed onto the metal-organic framework so that the resulting stream is richer in the second gas as compared to the mixture stream that is collected.
  • the adsorbed first gas is released from the metal-organic framework to obtain a stream richer in the first chemical as compared to the mixture stream that is also collected.
  • the adsorbed chemical is typically released by a change in temperature or pressure.
  • a purge gas may also be used to move the released gas through the bed for collection.
  • M 2 (dobpdc) and CuBTTri functionalized with alkylamines are frameworks that are particularly suited for carbon dioxide/nitrogen gas separations at CO 2 partial pressures between 1 and 1000 mbar.
  • mmen-CuBTTri shown in FIG. 1 and mmen-Mg 2 (dobpdc) shown in FIG. 8B are used to illustrate the M-BTTri and M 2 (dobpdc) framework families and the methods of use for gas separations.
  • FIG. 1 an embodiment of a portion of a metal-organic framework crystal structure of a mmen-CuBTTri, a water stable, triazolate-bridged framework of the invention is schematically shown.
  • the incorporation of the N,N′-dimethylethylenediamine (mmen) ligand into the (CuBTTri) framework was shown to drastically enhance CO 2 adsorption.
  • the attachment of the mmen alkylamine at the metal centers of the framework is shown with arrows. Because the diamines are shorter than the distance between two adjacent metal sites one amine from each molecule is bound to a single metal site, while the other amine is free to interact with guest gas molecules upon framework activation.
  • mmen-CuBTTri adsorbs 2.38 mmol CO 2 /g (9.5 wt %) with a selectivity of 327, as determined using Ideal Adsorbed Solution Theory (IAST).
  • IAST Ideal Adsorbed Solution Theory
  • a mmen-CuBTTri framework as shown in FIG. 1 was constructed and tested.
  • the grafted material, mmen-CuBTTri was then activated by heating at 50° C. for 24 hours under a dynamic vacuum prior to gas adsorption. Nitrogen adsorption isotherms collected at 77 K indicate a BET surface area of 870 m 2 /g, while powder x-ray diffraction data show the structure of the CuBTTri framework to be intact. Overall, the characterization data are most consistent with a chemical formula of H 3 [(CU 4 Cl) 3 (BTTri) 8 (mmen) 12 ], with approximately one mmen molecule for each available metal site.
  • mmen-CuBTTri is thought to possess a high concentration of surface-appended mmen molecules, where one of the amine groups is bound to a Cu 2+ center, while the other dangles within the pore, as depicted in FIG. 1 .
  • a mmen-CuBTTri framework as shown in FIG. 1 was constructed and tested.
  • the mmen-CuBTTri and men-CuBTTri adsorbents were initially tested in the context of separating a mixture stream including CO 2 and N 2 to obtain a stream richer in N 2 as compared to the mixture stream, with the adsorption of CO 2 in the frameworks at low pressures.
  • Gas adsorption isotherms for pressures in the range 0-1.1 bar were measured by a volumetric method using a Micromeritics ASAP2020 instrument.
  • a sample was transferred in an N 2 filled glovebag to a pre-weighed analysis tube, which was capped with a transeal and evacuated by heating (50° C. for mmen-CuBTTri, 100° C. for men-CuBTTri) under dynamic vacuum for 24 hours.
  • the evacuated analysis tube containing the degassed sample was then carefully transferred to an electronic balance and weighed again to determine the mass of sample (108.5 mg for mmen-, 69.2 mg for men-CuBTTri). The tube was then transferred back to the analysis port of the gas adsorption instrument.
  • mmen-CuBTTri displays significantly enhanced CO 2 adsorption at all pressures between 0 and 1.1 bar relative to the unappended framework.
  • Thermogravimetric analyses were carried out at a ramp rate of 1° C./min under a nitrogen flow with a TA Instruments TGA Q5000 V3.1 Build 246.
  • CO 2 cycling experiments were performed using 15% CO 2 /N 2 (Praxair Certified standard NI-CD15C-K) and N 2 (Praxair, 99.99%). A flow rate of 25 mL/min was employed for both gases.
  • Prior to cycling the sample was activated by heating at 60° C. for 1 hour, followed by cooling to 25° C. under an N 2 atmosphere. Sample mass was normalized to be 0% at 25° C. under an N 2 atmosphere. Masses were uncorrected for buoyancy effects, which were small compared to mass changes realized from gas adsorption.
  • FIG. 2A plots the gravimetric gas adsorption isotherm
  • FIG. 2B plots the crystallite volumetric gas adsorption isotherm for the two materials.
  • FIG. 2A is a graph plotting gravimetric gas sorption isotherms for CO 2 (squares) 12 and N 2 (circles) 16 adsorption at 25° C. for mmen-CuBTTri. Gravimetric gas sorption isotherms for CO 2 (squares) 14 and N 2 (circles) 18 for adsorption at 25° C. for CuBTTri alone is also plotted for comparison. The horizontal dashed line in corresponds to 10 wt % CO 2 adsorption.
  • FIG. 2B is a graph plotting volumetric gas sorption isotherms for CO 2 (squares) 20 and N 2 (circles) 24 adsorption at 25° C. for mmen-CuBTTri. Volumetric gas sorption isotherms for CO 2 (squares) 22 and N 2 (circles) 26 adsorption at 25° C. for CuBTTri alone is also plotted for comparison for comparison to FIG. 3A .
  • volumetric capacity for an actual adsorber unit is dependent upon how crystallites pack together and the fraction of void space within the occupied volume. Yet, gravimetric capacity alone does not provide a complete measure of the performance of a material being proposed for stationary applications, such as post-combustion CO 2 capture. Here, infrastructure costs are linked more directly to the volume the adsorbent would occupy than to its mass. Because incorporation of mmen into CuBTTri increases the framework density by 34% with no significant change in volume, this system is a good candidate for comparisons between gravimetric and volumetric capacities.
  • Framework volumes are based upon powder pattern unit cell optimizations, and framework compositions are based upon elemental and thermogravimetric analyses.
  • mmen-CuBTTri adsorbs 4.2 mmol/g of CO 2 (15.4 wt %), representing a 15% improvement in gravimetric capacity compared to the unmodified CuBTTri framework.
  • CO 2 comprises at most 15% of coal fired power station flue gas and the effluent is released into the environment at total pressures near 1 bar.
  • the more important criterion for CO 2 capacity is that of the framework at a pressure near 0.15 bar.
  • mmen-CuBTTri adsorbs 2.38 mmol/g (9.5 wt %).
  • mmen-CuBTTri adsorbs less N 2 than CuBTTri at all pressures between 0.0 and 1.1 bar. This is due to the reduction in specific surface area upon incorporation of mmen, with the BET surface area of 870 m 2 /g for mmen-CuBTTri being roughly half of the 1770 m 2 /g observed for CuBTTri.
  • the additional polarizing sites in mmen-CuBTTri enhance N 2 adsorption less than the decreased surface area diminishes N 2 adsorption. The opposite trend was observed for CO 2 adsorption. Enhanced adsorption of only one gas is a defining characteristic of chemisorption.
  • frameworks replete with open metal cation sites can be expected to polarize all gases more effectively, including N 2 , accounting for the substantially greater N 2 adsorption in Mg 2 (dobdc) relative to mmen-CuBTTri.
  • the selectivity (S) for adsorption of CO 2 over N 2 in mmen-CuBTTri was estimated from the single-component isotherm data. For CO 2 capture, this value typically reports the ratio of the adsorbed amount of CO 2 at 0.15 bar to the adsorbed amount of N 2 at 0.75 bar; the value is normalized for the pressures chosen. The values are derived from an approximate flue gas composition of 15% CO 2 , 75% N 2 , and 10% other gases, at a total pressure of 1 bar. Pure-component isotherm selectivities, which frequently are calculated from the excess adsorption data directly measured by gas adsorption, can be misleading.
  • the adsorption selectivity, S IAST was therefore modeled by applying the Ideal Adsorbed Solution Theory (IAST) to the calculated absolute adsorption isotherms.
  • IAST Ideal Adsorbed Solution Theory
  • the accuracy of the IAST procedure has been established for the adsorption of a wide variety of gas mixtures in different zeolites, as well as CO 2 capture in metal-organic frameworks.
  • SIAST values were calculated to be 327, 200, and 123 at 25° C., 35° C., and 45° C., respectively.
  • the selectivity that was observed at 25° C. is one of the highest values reported for a metal-organic framework.
  • the isosteric heat of adsorption and working capacity of the materials were analyzed. Utilizing a dual-site Langmuir adsorption model, isosteric heats of adsorption were calculated for CO 2 in mmen-CuBTTri and compared to those obtained from data for bare CuBTTri, which were fit using a single-site Langmuir model to give a value of ⁇ 24 kJ/mol. The N 2 adsorption isotherm for mmen-CuBTTri was also fit to a single-site Langmuir model, resulting in a calculated isosteric heat of adsorption of ⁇ 15 kJ/mol.
  • the isosteric heat of CO 2 adsorption in mmen-CuBTTri approaches ⁇ 96 kJ/mol at zero coverage, corresponding to the largest value yet reported for CO 2 adsorption in a metal-organic framework.
  • the heat of adsorption for en-CuBTTri was recalculated with the same dual-site Langmuir model. Because this model incorporates absolute adsorption, direct comparisons between the two different models are not possible.
  • the isosteric heat of CO 2 adsorption in en-CuBTTri was calculated to be ⁇ 78 kJ/mol at zero coverage, nearly 20 kJ/mol lower in magnitude than the heat calculated for mmen-CuBTTri.
  • the isosteric heat of CO 2 adsorption of the material is greater than ⁇ 70 kJ/mol at zero coverage as determined by the Clausius-Clapeyron relation.
  • mmen-CuBTTri has a significantly larger number of free amines available to bind guest CO 2 molecules. Because isosteric heats correspond to the average of all adsorption sites potentially populated at a specific coverage level, at zero coverage there is a higher probability of the CO 2 molecule adsorbing onto an amine in mmen-CuBTTri compared with en-CuBTTri.
  • adsorbents with high heats of adsorption may prove to be better candidates than materials with moderate heats of adsorption. This is because the capacities of adsorbents with high heats of adsorption are more dependent on temperature than materials with smaller heats of adsorption.
  • the cyclability of the mmen-CuBTTri material as a CO 2 adsorbent was evaluated using a combined temperature swing and nitrogen purge approach. Utilizing a thermogravimetric analyzer, a mixture of 15% CO 2 in N 2 was introduced into the furnace for 5 minutes at 25° C. It was observed that the sample mass increased by nearly 7% upon introduction of the mixed gas, due to strong adsorption of CO 2 , even in the dilute mixture. The adsorbent was then regenerated by changing the flow to a pure N 2 stream followed by rapid ramping of the furnace at 5° C./min to 60° C. The sample was held for 2 minutes at 60° C., and then cooled at 5° C./min to 25° C.
  • Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) measurements were performed on mmen-CuBTTri using a high-pressure (0-3 bar) gas cell to confirm and characterize the proposed chemisorptive process.
  • Infrared spectra were collected on a Perkin Elmer Spectrum 400 FTIR spectrometer equipped with an attenuated total reflectance accessory (ATR).
  • ATR attenuated total reflectance accessory
  • the FTIR spectrometer was equipped a Barrick Praying Mantis Diffuse Reflectance accessory and a high-pressure gas cell with temperature control.
  • FIG. 3 plots the infrared absorbance of mmen-CuBTTri under various pressures of CO 2 in a 5% CO 2 /95% He gas mixture in the high-pressure DRIFTS cell.
  • the N—H stretch of mmen is apparent at 3283 cm ⁇ 1 (vertical dashed line) on a fully evacuated sample is shown at plot 28.
  • the reported frequency for the N—H stretch in free mmen is 3279 cm ⁇ 1 .
  • Dilute CO 2 in He was slowly introduced into the cell at plot 30 up to a dynamic pressure of 1.5 bar at plot 32.
  • Upon saturation, a total disappearance of the N—H band at 3283 cm ⁇ 1 is clearly observed with the introduction of 5% CO 2 in He in the cell at increasing pressures.
  • the framework CuBTTri was additionally modified with N methylethylenediamine (men), an asymmetric diamine with one primary and one secondary amine.
  • the adsorption isotherms of mmen-CuBTTri for CO 2 at 298 K (squares), 308 K (circles) and 318 K (triangles) is shown in FIG. 4 as a baseline for comparison.
  • FIG. 5 shows N 2 adsorption isotherms at 298 K (squares), 308 K (circles) and 318 K (triangles) temperatures for mmen-CuBTTri.
  • men-CuBTTri performs more similarly to en-CuBTTri, for which only a small enhancement in CO 2 uptake was observed at very low pressures. A small improvement in performance was, however, realized through the use of men over en.
  • the significantly greater adsorption of CO 2 in mmen-CuBTTri is attributable to the larger number of amines that are accessible to guest CO 2 molecules.
  • the best fits to the elemental analysis data indicate at least two times as many diamine molecules were incorporated into mmen-CuBTTri versus the en- and men-analogues.
  • a reasonable explanation for the higher incorporation of mmen into the framework is the formation of a weaker coordinate bond between the secondary amine on mmen and a framework Cu 2+ ion compared with the relatively stronger coordinate bond formed between a primary amine and a Cu 2+ ion.
  • FIG. 6 is a graph of isosteric heats of adsorption for mmen-CuBTTri calculated from the virial method (circles) and the dual-site Langmuir method (squares).
  • FIG. 6 overlays the isosteric heats of adsorption calculated for mmen-CuBTTri using both the dual-site Langmuir and the Virial methods. At zero coverage, the Virial method gives a significantly lower magnitude for the heat of adsorption: ⁇ 66 kJ/mol.
  • the isosteric heat of adsorption was calculated to be about ⁇ 45 kJ/mol by both the dual-site Langmuir and Virial models.
  • the average enthalpy of adsorption for CO 2 would be significantly less than the ⁇ 96 kJ/mol value calculated for very low coverage levels. This has important implications for adsorbent regeneration.
  • the pore volume of mmen used for this purpose was 0.363 cm 3 /g, based on the N 2 adsorption data at 77 K.
  • the pore volume obtained was 51% that of bare CuBTTri.
  • the absolute component loadings were fitted with either a single-site Langmuir model or a dual-site Langmuir model.
  • a single-site Langmuir model was used for isotherm fitting.
  • the single-site Langmuir model is also adequate for fitting the isotherm data for CO 2 in “bare” CuBTTri.
  • the dual-site Langmuir model was employed.
  • the framework was used for the separation of CO 2 from mixed nitrogen gases.
  • the M 2 (dobpdc) structure type features approximately 18 ⁇ -wide channels and exhibits exceptional CO 2 adsorption properties upon functionalization with mmen.
  • Several different metal organic frameworks were prepared for comparison testing.
  • FIG. 8A and FIG. 8B one synthesis scheme for the mmen-M 2 -(dobpdc) functionalized framework is illustrated.
  • the initial framework is produced from H 4 dobpdc (4,4′-Dihydroxy-(1,1′-biphenyl)-3,3′-dicarboxylic Acid).
  • H 4 dobpdc was produced by adding 4,4′′-dihydroxybiphenyl (1.16 g, 6.24 mmol), KHCO 3 (2.00 g, 20.0 mmol), dry ice (4 g), and 1,2,4-trichlorobenzene (3 mL) to a PTFE insert within a steel acid digestion bomb (23 mL) and heated at 255° C. for 17 hours. After cooling to room temperature, the mixture was collected via vacuum filtration and washed with diethyl ether. The solid was suspended in 300 mL of distilled water, and filtered again. To the filtrate, neat HCl was slowly added until a pH between 1 and 2 was reached. The resulting crude product was collected via filtration. Recrystallization using 50 mL of acetone and 50 mL of water per gram of crude material afforded 0.68 g (40%) of pure product as a white powder.
  • DEF-2 was produced by loading H 4 dobpdc (24 mg, 0.088 mmol), MgBr 2 .6H 2 O (60 mg, 0.21 mmol), and 3 mL of solvent (1:1 DEF:EtOH) into a 10 ml Pyrex cell and sealed with a PTFE cap. The mixture was irradiated in a microwave reactor (CEM Discover) for 30 minutes at 120° C. After 30 minutes, the solution was cooled and the resulting solid was collected via filtration and washed with hot DEF. The solid was dried under vacuum to yield 57.5 mg (95%) of product as a white powder.
  • CEM Discover microwave reactor
  • each Zn 2+ is bonded to each Zn 2+ ion in a distorted octahedral geometry.
  • the equatorial plane of each Zn 2+ is composed of two trans-disposed O1 ligands from different linkers, one O3 donor atom, and one O2 donor atom.
  • An O2 donor atom occupies one axial coordination site, while the other axial site is occupied by an O donor atom from DEF, the reaction solvent.
  • This coordination mode results in the formation of helical chains of Zn 2+ atoms running along the c axis of the crystal.
  • the resulting framework consists of a honeycomb lattice of hexagonal, one-dimensional channels approximately 18 ⁇ in width.
  • Bound DEF molecules occupy the Zn 2+ coordination sites along the corners of hexagonal channel walls.
  • Powder X-ray diffraction (PXRD) data indicate DEF-2 to be isostructural with DEF-1.
  • Heating DEF-1 or DEF-2 at 420° C. for 65 minutes in vacuo yielded the fully activated adsorbent Mg 2 (dobpdc) or Zn 2 (dobpdc) respectively.
  • Heating DEF-2 at 420° C. for 65 min under dynamic vacuum removed the DEF molecules bound to the metal atoms, completely activating the material and generating open Mg 2+ coordination sites.
  • Such extreme thermal treatment was necessary because soaking in methanol at 100° C. for 20 hours did not lead to exchange of the bound DEF molecules.
  • the porosity of activated DEF-2 was confirmed via N 2 adsorption at 77 K, resulting in a BET surface area of 3270 m 2 /g. Note that, in line with the expanded structure, this is significantly greater than the BET surface area of 1495 m 2 /g reported for Mg 2 (dobdc).
  • mmen-Mg 2 (dobpdc) or mmen-2 is depicted schematically at the right of FIG. 8A and FIG. 8B .
  • An activated sample of DEF-1 of DEF-2 was suspended in hexanes and an excess of mmen was added. Specifically, a 77 mg, 0.24 mmol sample of activated DEF-2 was immersed in anhydrous hexane, and 20 equivalents of N,N′-dimethylethylenediamine (mmen, 0.53 mL, 4.8 mmol) was added. The suspension was stirred for one day, filtered, and rinsed copiously with hexanes. The solid was then evacuated of residual solvents at 100° C. for 24 h to afford 87 mg (77%) of product as a gray-white powder.
  • framework crystallinity was not significantly affected by activation or subsequent amine functionalization.
  • a much reduced BET surface area of 70 m 2 /g was calculated for mmen-2, while DFT pore size distributions indicated a reduction in average pore size.
  • the adsorption capacity of Mg 2 (dobpdc) at 25° C. is 4.85 mmol/g (13.8 wt %) and 6.42 mmol/g (20.0 wt %) at 0.15 and 1 bar, respectively.
  • the capacity of Mg 2 (dobpdc) for CO 2 at 0.15 bar exceeds the capacity of most metal-organic frameworks.
  • the alkylamine-functionalized metal-organic framework mmen-2 displayed an extremely high affinity for CO 2 at extraordinarily low pressures.
  • the CO 2 adsorption isotherms obtained at 25, 50, and 75° C. are presented in FIG. 9 .
  • the compound adsorbed 2.0 mmol/g (8.1 wt %), which is 15 times the capacity of Mg 2 (dobpdc).
  • the median partial pressure of CO 2 within the International Space Station the framework adsorbed 2.6 mmol/g (10.3 wt %).
  • zeolite 5A which is currently used aboard the station to adsorb CO 2 , adsorbs 0.85 mmol/g (3.6 wt %, crystallographic volumetric capacity 1.3 mmol/cm 3 ) at 5 mbar.
  • the CO 2 adsorption in mmen-2 reaches 3.14 mmol/g (12.1 wt %) at 0.15 bar and 3.86 mmol/g (14.5 wt %) at 1 bar.
  • its CO 2 uptake at 1 bar and 25° C. exceeds the amount of N 2 adsorbed at 77 K.
  • the low surface area measured at 77 K does not appear to accurately reflect the surface area accessible to CO 2 .
  • the amine-functionalized framework adsorbed less CO 2 than Mg 2 (dobpdc) at pressures higher than ca. 0.1 bar.
  • mmen-2 While the decreased surface area of mmen-2 may limit its capacity at super-atmospheric pressures, the large density difference between the two frameworks is primarily responsible for the lower gravimetric capacity of mmen-2. Crystallographic densities of 0.58 and 0.86 g/cm 3 were calculated for Mg 2 (dobpdc) and mmen-2, respectively. For adsorbents of the same structure and widely different densities, volumetric capacities better represent CO 2 adsorption performance. At 0.15 bar, Mg 2 (dobpdc) and mmen-2 adsorb 2.1 and 2.7 mmol/cm 3 , respectively, while at 1 bar, the capacities of both adsorbents are 3.3 mmol/cm 3 .
  • mmen-2 For stationary applications like CCS, the greater volumetric capacity of mmen-2 makes it the superior adsorbent. Based upon the calculated number of dangling amine groups in mmen-2, a loading of 3.4 mmol/g would correspond to one CO 2 per amine, yet uptake of only ca. 2.2 mmol/g was observed. Here, pore blockages, hydrogen bonded amines, or cooperative binding mechanisms between two amines and one CO 2 may be limiting the accessible stoichiometry of mmen-2. Thus, significant additional capacity improvements might be realized in the material if conditions can be identified for appending one mmen per magnesium and binding one CO 2 molecule per dangling amine.
  • Isosteric heat of adsorption calculations were hindered by the presence of a prominent step in the isotherms at low pressures and convex to the pressure axis.
  • continuous mathematical functions are used to model experimental isotherms, which then become the input parameters for the Clausius-Clapeyron relation. Since mathematical modeling of the CO 2 isotherms of mmen-2 with continuous equations over the entire pressure range were unavailable, each isotherm was modeled with two Langmuir-Freurium equations. Data sets corresponding to the adsorption regions before and after the steps were compiled and then modeled individually. Isosteric heats of adsorption for mmen-2 were calculated from the 25, 50, and 75° C. isotherm models.
  • DRIFTS In situ diffuse reflectance infrared Fourier transform spectroscopy
  • the step observed in each isotherm marks the pressure at which CO 2 adsorption becomes dominated by chemisorption. Interestingly, the step moves to significantly higher pressures as the adsorption temperature increases.
  • the location of the step is modeled well by a simple Clausius-Clapeyron relation, which predicts how isotherms move as a function of temperature.
  • the existence of the step is unexpected in a strongly adsorbing material with large pores, and can best be explained by the surprising conclusion that weaker adsorption sites are energetically favored over amine adsorption sites at low coverage.
  • Thermogravimetric analyses were carried out at ramp rates between 5 and 10° C./min under a nitrogen flow with a TA Instruments TGA Q5000 (Ver. 3.1 Build 246) or a Scinco TGA N-1000.
  • Carbon dioxide cycling experiments were performed using a 15% CO 2 in N 2 (Praxair NI-CD15C-K), 390 ppm CO 2 in air (Praxair AI-CD-390C-K; 390 ppm CO 2 , 21% O 2 , balance N2), CO 2 (Praxair 99.998%) and N 2 (Praxair, 99.9%).
  • a flow rate of 25 mL/minute was employed for all gases. Prior to cycling, the sample was activated by heating at 150° C. for 1 hour.
  • sample mass was normalized to be 0% at the adsorption temperature (25° C. for 390 ppm CO 2 and 40° C. for 15% CO 2 ) under flowing N 2 and sample mass was normalized to be 0% at 150° C. under flowing 100% CO 2 .
  • the adsorbent was then regenerated under flowing N 2 at 150° C. for 30 minutes and the cycle repeated ten times with no apparent loss of capacity.
  • the equilibrium capacity (2.0 mmol/g, 1.72 mmol/cm 3 ) of mmen-2 is similar to the capacities of the very best amine-grafted silica and alumina adsorbents reported to date. However, the kinetics of adsorption appear to be significantly faster in mmen-2 than for amines deposited via evaporation or polymerization methodologies.
  • mmen-2 as an adsorbent for removing CO 2 from the flue gas of coal-fired power stations were also investigated.
  • An adsorption material comprising: a porous metal-organic framework; and a plurality of ligands within the pores of the metal-organic framework, each ligand having at least one basic nitrogen group; wherein the basic nitrogen groups are configured to selectively adsorb CO 2 from a stream of mixed gases at pressures below approximately 3 bar and CO 2 partial pressures between approximately 1 and 1000 mbar.
  • ligand comprises a first functional group reactive to metal atoms in the metal-organic framework and a second functional group reactive with carbon dioxide.
  • the first functional group of the ligand comprises a carboxylate group, a triazolate group, a pyrazolate, a tetrazolates, a pyridine, or a sulfate.
  • the ligand comprises a primary alkylamine, a secondary alkylamine, a tertiary alkylamine, a primary imine, or a secondary imine.
  • metal-organic framework comprises open metal sites and ligand occupied metal sites.
  • adsorption material of any previous embodiment wherein the adsorption material has an isosteric heat of CO 2 adsorption of greater than ⁇ 60 kJ/mol at zero coverage using a dual-site Langmuir model.
  • a method of separating a mixture stream comprising CO 2 and N 2 comprising: contacting the mixture stream comprising CO 2 and N 2 with a material comprising a metal-organic framework, and a ligand with a basic nitrogen group; wherein the material has an isosteric heat of CO 2 adsorption of greater than ⁇ 60 kJ/mol at zero coverage using a dual-site Langmuir model; obtaining a stream richer in CO 2 as compared to the mixture stream; and obtaining a stream richer in N 2 as compared to the mixture stream.
  • the ligand is selected from the group of ligands consisting essentially of a carboxylate group, a triazolate group, a pyrazolate, a tetrazolates, a pyridine, or a sulfate.
  • the ligand comprises a primary alkylamine, a secondary alkylamine, a tertiary alkylamine, a primary imine, or a secondary imine.
  • a method of separating a mixture stream comprising CO 2 and other combustion gases comprising: contacting the mixture stream comprising CO 2 and N 2 with a material comprising a metal-organic framework and a plurality of ligands that have at least one basic nitrogen group; obtaining a stream richer in CO 2 as compared to the mixture stream; and obtaining a stream richer in N 2 as compared to the mixture stream.
  • metal-organic framework and plurality of ligands comprises mmen-CuBTTri.
  • An adsorption material comprising: a metal-organic framework; and a ligand with a basic nitrogen group, wherein the adsorption material has an isosteric heat of CO 2 adsorption of greater than ⁇ 80 kJ/mol at zero coverage using a dual-site Langmuir model.
  • ligand comprises a carboxylate group, a triazolate group, a pyrazolate, a tetrazolates, a pyridine, or a sulfate.
  • the ligand comprises a primary amine, a secondary amine, a tertiary amine, a primary imine, or a secondary imine.
  • adsorption material of claim 1 wherein the adsorption material has an isosteric heat of CO 2 adsorption of greater than ⁇ 95 kJ/mol at zero coverage using a dual-site Langmuir model.
  • a method of separating a mixture stream comprising CO 2 and N 2 comprising: contacting the mixture stream comprising CO 2 and N 2 with a material comprising a metal-organic framework, and a ligand with a basic nitrogen group, wherein the material has an isosteric heat of CO 2 adsorption of greater than ⁇ 80 kJ/mol at zero coverage using a dual-site Langmuir model; obtaining a stream richer in CO 2 as compared to the mixture stream; and obtaining a stream richer in N 2 as compared to the mixture stream.
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