CN103100372A - Metal-organic framework material for methane adsorption and storage and preparation method thereof - Google Patents
Metal-organic framework material for methane adsorption and storage and preparation method thereof Download PDFInfo
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- CN103100372A CN103100372A CN201310029434XA CN201310029434A CN103100372A CN 103100372 A CN103100372 A CN 103100372A CN 201310029434X A CN201310029434X A CN 201310029434XA CN 201310029434 A CN201310029434 A CN 201310029434A CN 103100372 A CN103100372 A CN 103100372A
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Abstract
The invention discloses a metal-organic framework material for methane adsorption and storage and a preparation method thereof. The metal-organic framework material is of a three-dimensional network structure formed by transition metal ions, an organic ligand, namely, 5,5'-(pyridine-2,5-diyl)-isophthalic acid, and derivatives of the ligand through coordinate bonds or intermolecular forces. The transition metal ions are preferentially selected from bivalent ions of copper, zinc, cobalt, nickel, cadmium and manganese. The metal-organic framework material is higher in specific surface area and pore volume and good in thermal stability. Pyridine, fluorine, methyl, amino, methoxy, hydroxyl, nitro and other functional groups which do not participate in coordination are introduced into the organic ligand used in the material, can effectively improve the capacity of methane adsorption and storage. The metal-organic framework material is simple in preparation process and low in cost, can be used repeatedly, has high capacity of methane adsorption and storage under variable-temperature and variable-pressure conditions, and is expected to be used as a novel high-efficiency methane adsorption and storage material.
Description
Technical field
The present invention relates to a kind of metal organic frame material for methane absorption and storage and preparation method thereof, belong to metal organic frame material technology field.
Background technology
Methane is a kind of hydrocarbon, and chemical formula is CH
4, its distribution in the nature is very wide, is the main component of natural gas, biogas, casing-head gas and coal mine gallery gas, and with other petroleum fuel gas phase ratios, methane gas has higher H/C ratio, so more clean reliable when it uses as combustion gas.Methane gas is also a kind of important industrial chemicals simultaneously, and it is widely used as the raw material of materials such as making hydrogen, carbon black, carbon monoxide, acetylene, hydrogen cyanide and formaldehyde.Yet methane gas storage and transportation problem become the major obstacle that limits its extensive use.The method of storage methane gas mainly contains the several methods such as liquefied methane, high pressure compressed methane and adsorbed methane.The method of hydraulic pressure methane exists: (1) liquefaction critical-temperature is too low, the liquefaction cost is high; (2) aerating technical difficulty is large, and liquefied methane needs continuous cooling in storage and transportation, needs expensive low-temperature storage tank; (3) gas bomb must be special adiabatic material, boils loss with minimizing.Above problem becomes the main cause that the restriction liquefied methane can not the widespread commercial application.The method of high pressure compressed methane must adopt high pressure (20 MPa) to increase the storage density of methane, make compressed methane whole process both expensive, operation easier is large, potential safety hazard is many.Comparatively speaking, the method for adsorbed methane has the advantages such as cost is low, simple to operate, safety, utilization rate height, thereby this method becomes the key that realizes the application of methane gas widespread commercial.Yet, be used at present storage Adsorption of methane agent material, exist adsorbance not high, discharge gas and wait more slowly problem, so development has the significant and application prospect of the porous material of high methane memory space.
Metal organic frame material (Metal Organic Frameworks, be called for short MOFs) as a kind of novel porous material, have high permeability, specific area large, synthetic convenient, hole size is variable and can make the advantages such as chemical modification, structure be abundant according to target call, and potential fields such as gas absorption, catalysis, photoelectric material that are applied to.At present, had a considerable amount of MOFs to be applied to storing methane gas, (USDOE, under room temperature 35bar pressure, storage is 180 cm yet only have minute quantity to reach practical target
3/ cm
3).Mainly contain for improving the method for MOFs to methane absorption and memory space at present: (1) improves specific area and the voidage of MOFs material; (2) the introducing undersaturated metal active of coordination unit.Introduce the functional group that does not participate in coordination when (3) designing organic ligand, as pyridine, amino, hydroxyl etc.Comparatively speaking, be used for the MOFs material of absorption and storage methane gas, the report of introducing the functional group that does not participate in coordination during the design organic ligand is also more rare.Guaranteeing higher specific area and the voidage of MOF material, and under the condition of the undersaturated metal active of coordination unit, after introducing does not participate in the functional group of coordination, these functional groups can effectively catch methane molecule with the interaction such as methanogenesis hydrogen bond or intermolecular active force, therefore can effectively improve Adsorption of methane and memory space.
Summary of the invention
The purpose of this invention is to provide a kind of metal organic frame material with higher methane absorption and memory space and preparation method thereof.
For achieving the above object, metal organic frame material for methane absorption and storage of the present invention, be the three-dimensional net structure that is made of by coordinate bond or intermolecular force transition metal ions and organic ligand, this three-dimensional net structure specific area is 2000 ~ 3000 m
2/ g, its pore volume are 1.0 ~ 2.0 cm
3/ g.
Above-mentioned transition metal ions can be Cu
2+, Zn
2+, Cd
2+, Co
2+, Ni
2+Perhaps Mn
2+Ion.Described organic ligand is 5,5 '-(pyridine-2,5-two bases)-M-phthalic acid and derivative thereof, and its structural formula is as follows:
R in formula
1, R
2And R
3Be hydrogen, fluorine, methyl, amino, methoxyl group, hydroxyl or nitro.
Metal organic frame material preparation method for methane absorption and storage of the present invention, step is as follows:
(1) with nitrate, acetate, chlorate, carbonate, sulfate or the perchlorate and 5 of copper, zinc, cadmium, cobalt, nickel or manganese, 5 '-(pyridine-2,5-two bases)-M-phthalic acid is 2:1 together in the mixed solvent of water-soluble, organic solvent or water and organic solvent in mass ratio, in 40 ~ 120 ℃ of fully reactions, obtain the metal organic frame material;
(2) the metal organic frame material that step (1) is obtained more than ten times, then activates 36 hours with acetone-exchanged under vacuum and 0 ℃ of condition, activation is 12 hours under 100 ℃, obtains the metal organic frame material for methane absorption and storage.
In preparation process of the present invention, the said organic solvent of step (1) is N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMA), dioxane, dimethyl sulfoxide (DMSO) (DMSO), N, any one or the arbitrarily mixing of several any ratios in N-diethyl acetamide (DEF), acetonitrile, methyl alcohol, ethanol, oxolane and carrene.
The invention has the advantages that:
Metal organic frame material preparation technique for methane absorption and storage of the present invention is simple, reaction condition is gentle, effective, cost is low.The functional groups such as the pyridine radicals that do not participate in coordination, fluorine, methyl, amino, methoxyl group, hydroxyl, nitro have been introduced in design during organic ligand, by the interaction between these functional groups and methane molecule, can effectively improve the metal organic frame material to Adsorption of methane and memory space.And this metal organic frame material has higher specific area and higher pore volume content, has good heat endurance, can reuse.Under room temperature and 35bar condition, the storage capacity of the methane of this metal organic frame material reaches target (180 cm of USDOE (DOE)
3/ cm
3), and Adsorption of methane and memory space is high, easy desorption under alternating temperature, transformation condition.
Description of drawings
Fig. 1 is the mono-crystalline structures schematic diagram of the metal organic frame material for preparing of the present invention;
Fig. 2 is the TG figure of the metal organic frame material for preparing of the present invention;
Fig. 3 is the nitrogen adsorption isotherm of the metal organic frame material of the embodiment of the present invention 1 preparation under 77K, 0 ~ 1atm condition;
Fig. 4 is the methane storage capacity thermoisopleth of the metal organic frame material of the embodiment of the present invention 1 preparation under 125K, 150K, 240K, 270K and 300K, 0～65atm condition;
Fig. 5 is the XRD collection of illustrative plates of the metal organic frame material of the embodiment of the present invention 1 preparation.
The specific embodiment
Embodiment 1:
Cu (NO with 5,5 ' of 15mg-(pyridine-2,5-two bases)-M-phthalic acid and 30mg
3)
2(H
2O)
2.5Be dissolved in DMF (DMF), acetonitrile, H
2In the mixed solvent of O (8mL, volume ratio 6:1:1), then be added dropwise to the concentrated hydrochloric acid of 50 μ L, be placed in the seed bottle of 25 milliliters, sealing is placed in 80 ℃ of baking ovens reacted 72 hours, repeatedly cleaned with DMF after taking out, and obtained the metal organic frame material after oven dry.Determine its structure by Oxford Xcalibur Gemini Ultra single crystal diffractometer, result shows: the structural formula of this metal organic frame material is [Cu
2(C
21H
9NO
8) (H
2O)
2] (DMF)
4(H
2O)
6, molecular formula is C
33H
53N
5O
20Cu
2, belonging to hexagonal crystal system, space group is R-3m, and cell parameter is a=18.8163, and b=18. 8163, c=38.079, α=β=90 °, γ=120 °, unit cell volume is 11675.7
3, Z=3, D
c=0.725g/cm
3The mono-crystalline structures figure of the metal organic frame material of preparation sees Fig. 1, this material is three-dimensional net structure, wherein each copper ion and five oxygen atom ligands, these five oxygen atoms come from respectively a hydrone and four ligand moleculars, and a pair of copper atom is connected by carboxyl and forms { Cu
2(O
2CR)
4Double-spiral structure, each { Cu
2(O
2CR)
4Be connected with four parts and each part and four { Cu
2(O
2CR)
4Be connected, as (a) in Fig. 1 and (b), hydrone is along double-stranded axial and copper ion coordination, and this metal organic frame thing has the duct in a, b, three directions of c-axis, is a kind of circular duct along the c-axis direction, as (c) in Fig. 1, after removing the van der Waals radius of atom, the size in duct is about 5.0, is a kind of triangle duct along a, b direction of principal axis, as (d) in Fig. 1, these triangles ducts is applied in the circular duct of c-axis direction together.There is simultaneously unordered object solvent molecule in the duct of a, b, three directions of c-axis.Have unsatuated metal site and the spacious micropore without the end group water of coordination after this material activates, porosity can reach 70.5%.The thermogravimetric test shows that this material is stable before 300 ℃, as Fig. 2.
The metal organic frame material that obtains is carried out exchange of solvent with acetone, every solvent of exchange in 15 minutes, exchange ten times, then activate 36 hours under 0 ℃ of vacuum condition, activate 12 hours again under 100 ℃ of vacuum conditions, obtain having the metal organic frame material in unsatuated metal site and spacious duct.Utilize Micromeritics ASAP 2020 specific surface area measuring instruments to carry out the collection of gas absorption data, test shows: at 77K, recording nitrogen adsorption isotherm under 0～1atm is I-type thermoisopleth (see figure 3), and specific area and Langmuir adsorption surface area are respectively 2103.05 m
2G
-1With 3118.28 m
2G
-1, pore volume is 1.1917 cm
3G
-1, the saturated extent of adsorption of nitrogen is 770.43 cm
3g
-1Shown in Figure 4, the metal organic frame material that obtains after activation is recorded the storage capacity of methane under 125K, 150K, 240K, 270K and 300K, 0～65bar condition, the maximum storage of methane reduces along with the rising of temperature, and the adsorption desorption curve overlaps fully, explanation can be controlled the memory space of methane by controlled pressure and temperature, accomplishes that adsorption desorption freely.Be issued to saturatedly at room temperature and 35bar, the storage capacity of the methane of this metal organic frame material can reach 189.4cm
3/ cm
3(abs), reach target (180 cm of USDOE (DOE)
3/ cm
3).Simultaneously, as shown in Figure 5, after the absorption test, the XRD collection of illustrative plates fits like a glove with the XRD collection of illustrative plates that goes out by the monocrystalline digital simulation, and the crystal structure of illustrative material does not have destroyed, can reuse.
Embodiment 2:
ZnCl with 5,5 ' of 20mg-(4-picoline-2,5-two bases)-M-phthalic acid and 40mg
2(H
2O)
2Be dissolved in DMA (DMA) solution of 8mL, be placed in the seed bottle of 25 milliliters, sealing is placed in 65 ℃ of baking ovens reacted 72 hours, repeatedly cleaned with DMA after taking out, and obtained the metal organic frame material after oven dry.
The metal organic frame material that obtains is carried out exchange of solvent with acetone, every solvent of exchange in 15 minutes, exchange ten times, then activate 36 hours under 0 ℃ of vacuum condition, activate 12 hours again under 100 ℃ of vacuum conditions, obtain having the metal organic frame material in unsatuated metal site and spacious duct.Utilize Micromeritics ASAP 2020 specific surface area measuring instruments to carry out the collection of gas absorption data, its specific area and Langmuir adsorption surface area surpass respectively 2200 m
2G
-1With 3300 m
2G
-1, pore volume is greater than 1.300 cm
3G
-1Be issued to saturatedly at room temperature and 35bar, the storage capacity of the methane of this metal organic frame material is greater than 200 cm
3/ cm
3(abs), the target that surpasses USDOE (DOE).
Embodiment 3:
Cd (ClO with 5,5 ' of 25mg-(3,4,6-trifluoromethyl pyridine-2,5-two bases)-M-phthalic acid and 50mg
4)
2(H
2O)
6Be dissolved in N, in the mixed solvent of N-diethyl acetamide (DEF), acetonitrile (8mL, volume ratio 6:2), be placed in the seed bottle of 25 milliliters, sealing is placed in 90 ℃ of baking ovens reacted 24 hours, repeatedly cleaned with DEF after taking out, and obtained the metal organic frame material after oven dry.
The metal organic frame material that obtains is carried out exchange of solvent with acetone, every solvent of exchange in 15 minutes, exchange ten times, then activate 36 hours under 0 ℃ of vacuum condition, activate 12 hours again under 100 ℃ of vacuum conditions, obtain having the metal organic frame material in unsatuated metal site and spacious duct.Utilize Micromeritics ASAP 2020 specific surface area measuring instrument testers to carry out the collection of gas absorption data, its specific area and Langmuir adsorption surface area surpass respectively 2500m
2G
-1With 3500 m
2G
-1, pore volume is greater than 1.500cm
3G
-1Be issued to saturatedly at room temperature and 35bar, the storage capacity of the methane of this metal organic frame material is greater than 220 cm
3/ cm
3(abs), the target that surpasses USDOE (DOE).
Embodiment 4:
Cd (CH with 5,5 ' of 15mg-(3,4-diamino-pyridine-2,5-two bases)-M-phthalic acid and 30mg
3COO)
2(H
2O)
6Be dissolved in dimethyl sulfoxide (DMSO) (DMSO), ethanol, H
2In the mixed solvent of O (8mL, volume ratio 6:2:1), be placed in the seed bottle of 25 milliliters, sealing is placed in 80 ℃ of baking ovens reacted 48 hours, repeatedly cleaned with DMSO after taking out, and obtained the crystal of diamond shaped after oven dry.
The metal organic frame material that obtains is carried out exchange of solvent with acetone, every solvent of exchange in 15 minutes, exchange ten times, then activate 36 hours under 0 ℃ of vacuum condition, activate 12 hours again under 100 ℃ of vacuum conditions, obtain having the metal organic frame material in unsatuated metal site and spacious duct.Utilize Micromeritics ASAP 2020 specific surface area measuring instrument testers to carry out the collection of gas absorption data, its specific area and Langmuir adsorption surface area surpass respectively 2100 m
2G
-1And 3100m
2G
-1, pore volume is greater than 1.250cm
3G
-1Be issued to saturatedly at room temperature and 35bar, the storage capacity of the methane of this metal organic frame material is greater than 195cm
3/ cm
3(abs), reach the target of USDOE (DOE).
Embodiment 5:
MnCO with 5,5 ' of 15mg-(4-pyridone-2,5-two bases)-M-phthalic acid and 30mg
3Be dissolved in dimethyl sulfoxide (DMSO) (DMSO), H
2In the mixed solvent of O (8mL, volume ratio 6:2), be placed in the seed bottle of 25 milliliters, sealing is placed in 100 ℃ of baking ovens reacted 48 hours, repeatedly cleaned with DMSO after taking out, and obtained the metal organic frame material after oven dry.
The metal organic frame material that obtains is carried out exchange of solvent with acetone, every solvent of exchange in 15 minutes, exchange ten times, then activate 36 hours under 0 ℃ of vacuum condition, activate 12 hours again under 100 ℃ of vacuum conditions, obtain having the metal organic frame material in unsatuated metal site and spacious duct.Utilize Micromeritics ASAP 2020 specific surface area measuring instrument testers to carry out the collection of gas absorption data, its specific area and Langmuir adsorption surface area surpass respectively 2300 m
2G
-1And 3300m
2G
-1, pore volume is greater than 1.200cm
3G
-1Be issued to saturatedly at room temperature and 35bar, the storage capacity of the methane of this metal organic frame material is greater than 200 cm
3/ cm
3(abs), the target that surpasses USDOE (DOE).
The above-mentioned specific embodiment is used for the present invention that explains, but the present invention is not limited to this embodiment and the disclosed content of accompanying drawing.Everyly do not break away from the equivalence of completing under spirit disclosed by the invention or revise, all falling into protection domain of the present invention.
Claims (5)
1. one kind is used for the metal organic frame material that methane adsorbs and stores, it is characterized in that, the metal organic frame material is the three-dimensional net structure that is made of by coordinate bond or intermolecular force transition metal ions and organic ligand, and this three-dimensional net structure specific area is 2000 ~ 3000 m
2/ g, its pore volume are 1.0 ~ 2.0 cm
3/ g.
2. the metal organic frame material for methane absorption and storage according to claim 1, is characterized in that, described transition metal ions is Cu
2+, Zn
2+, Cd
2+, Co
2+, Ni
2+Perhaps Mn
2+Ion.
3. the metal organic frame material for methane absorption and storage according to claim 1, is characterized in that, described organic ligand is 5,5 '-(pyridine-2,5-two bases)-M-phthalic acid and derivative thereof, and its structural formula is as follows:
R in formula
1, R
2And R
3Be hydrogen, fluorine, methyl, amino, methoxyl group, hydroxyl or nitro.
4. prepare the method for the metal organic frame material for methane absorption and storage claimed in claim 1, it is characterized in that step is as follows:
(1) with nitrate, acetate, chlorate, carbonate, sulfate or the perchlorate and 5 of copper, zinc, cadmium, cobalt, nickel or manganese, 5 '-(pyridine-2,5-two bases)-M-phthalic acid is 2:1 together in the mixed solvent of water-soluble, organic solvent or water and organic solvent in mass ratio, in 40 ~ 120 ℃ of fully reactions, obtain the metal organic frame material;
(2) the metal organic frame material that step (1) is obtained more than ten times, then activates 36 hours with acetone-exchanged under vacuum and 0 ℃ of condition, activation is 12 hours under 100 ℃, obtains the metal organic frame material for methane absorption and storage.
5. the metal organic frame material preparation method for methane absorption and storage according to claim 4, it is characterized in that the said organic solvent of step (1) is N, dinethylformamide, N, N-dimethylacetylamide, dioxane, dimethyl sulfoxide (DMSO), N, any one or the arbitrarily mixing of several any ratios in N-diethyl acetamide, acetonitrile, methyl alcohol, ethanol, oxolane and carrene.
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