CN103100372B - 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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- CN103100372B CN103100372B CN201310029434.XA CN201310029434A CN103100372B CN 103100372 B CN103100372 B CN 103100372B CN 201310029434 A CN201310029434 A CN 201310029434A CN 103100372 B CN103100372 B CN 103100372B
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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, it is very wide in natural distribution, 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.Simultaneously methane gas is also a kind of important industrial chemicals, and it is widely used as the raw material of materials such as manufacturing hydrogen, carbon black, carbon monoxide, acetylene, hydrogen cyanide and formaldehyde.But 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, 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 to reduce.Above problem become restriction liquefied methane can not widespread commercialization the main cause of 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 commercialization.But, at present for storing the sorbent material of methane, exist adsorbance not high, discharge the problems such as gas is slower, 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, but only have minute quantity to reach practical target, (USDOE, under room temperature 35bar pressure, storage is 180 cm
3/ cm
3).For improving MOFs, the method for methane absorption and memory space is mainly contained at present: (1) improves specific area and the voidage of MOFs material; (2) introduce the undersaturated metal active of coordination unit.(3) while designing organic ligand, introduce the functional group that does not participate in coordination, as pyridine, amino, hydroxyl etc.Comparatively speaking, for adsorbing and store the MOFs material of methane gas, the report of introducing the functional group that does not participate in coordination when 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, introduce and do not participate in after the functional group of coordination, these functional groups can be with interactions such as methanogenesis hydrogen bond or intermolecular active forces and can effectively catch methane molecule, therefore can effectively improve absorption and the memory space of methane.
Summary of the invention
The object 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 consisting of 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 is 1.0 ~ 2.0 cm
3/ g.
Above-mentioned transition metal ions can be Cu
2+, Zn
2+, Cd
2+, Co
2+, Ni
2+or Mn
2+ion.Described organic ligand is 5,5 '-(pyridine-2,5-bis-bases)-M-phthalic acid and derivative thereof, and its structural formula is as follows:
R in formula
1, R
2and R
3for hydrogen, fluorine, methyl, amino, methoxyl group, hydroxyl or nitro.
The preparation method of the metal organic frame material for methane absorption and storage of the present invention, step is as follows:
(1) by the nitrate of copper, zinc, cadmium, cobalt, nickel or manganese, acetate, chlorate, carbonate, sulfate or perchlorate and 5,5 '-(pyridine-2,5-bis-bases)-M-phthalic acid 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 metal organic frame material;
(2) metal organic frame material step (1) being obtained more than ten times, then activates 36 hours by acetone-exchanged under vacuum and 0 ℃ of condition, activates 12 hours at 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:
The preparation technology of the metal organic frame material 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 when organic ligand, by the interaction between these functional groups and methane molecule, can effectively improve absorption and the memory space of metal organic frame material to methane.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 absorption and high, the easy desorption of memory space of methane under alternating temperature, transformation condition.
Accompanying drawing explanation
Fig. 1 is the mono-crystalline structures schematic diagram of the metal organic frame material prepared of the present invention;
Fig. 2 is the TG figure of the metal organic frame material prepared of the present invention;
The nitrogen adsorption isotherm that Fig. 3 is the metal organic frame material that under 77K, 0 ~ 1atm condition prepared by the embodiment of the present invention 1;
Fig. 4 is the methane storage capacity thermoisopleth of the metal organic frame material that under 125K, 150K, 240K, 270K and 300K, 0～65atm condition prepared by the embodiment of the present invention 1;
Fig. 5 is the XRD collection of illustrative plates of the metal organic frame material prepared of the embodiment of the present invention 1.
The specific embodiment
Embodiment 1:
By the Cu (NO of 5,5 ' of 15mg-(pyridine-2,5-bis-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), be then 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 reacts 72 hours, after taking-up, repeatedly cleans with DMF, obtains 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, cell parameter is a=18.8163, 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
3.The mono-crystalline structures figure of the metal organic frame material of preparation is shown in 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 to form { Cu by carboxyl
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 duct in a, b, three directions of c-axis, is a kind of circular duct along c-axis direction, as (c) in Fig. 1, remove after 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 triangle ducts are applied in the circular duct of c-axis direction together.In the duct of a, b, three directions of c-axis, there is unordered object solvent molecule simultaneously.After this material activates, have unsatuated metal site and the spacious micropore without end group water of coordination, porosity can reach 70.5%.Thermogravimetric test shows that this material is stable before 300 ℃, as Fig. 2.
The metal organic frame material of acquisition is carried out to exchange of solvent with acetone, every a solvent of exchange in 15 minutes, exchange ten times, then under 0 ℃ of vacuum condition, activate 36 hours, under 100 ℃ of vacuum conditions, activate 12 hours again, 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, under 0～1atm, recording nitrogen adsorption isotherm 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
-1.Shown in Fig. 4, the metal organic frame material obtaining after activation is recorded under 125K, 150K, 240K, 270K and 300K, 0～65bar condition to the storage capacity of methane, the maximum storage of methane reduces along with the rising of temperature, and adsorption desorption curve overlaps completely, the memory space that can control methane by controlled pressure and temperature is described, 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).Meanwhile, as shown in Figure 5, after absorption test, XRD collection of illustrative plates fits like a glove with the XRD collection of illustrative plates going out by monocrystalline digital simulation, and the crystal structure of illustrative material does not have destroyed, can reuse.
Embodiment 2:
By the ZnCl of 5,5 ' of 20mg-(4-picoline-2,5-bis-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 reacts 72 hours, after taking-up, repeatedly cleans with DMA, obtains metal organic frame material after oven dry.
The metal organic frame material of acquisition is carried out to exchange of solvent with acetone, every a solvent of exchange in 15 minutes, exchange ten times, then under 0 ℃ of vacuum condition, activate 36 hours, under 100 ℃ of vacuum conditions, activate 12 hours again, 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 exceed respectively 2200 m
2g
-1with 3300 m
2g
-1, pore volume is greater than 1.300 cm
3g
-1.Be 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), exceed the target of USDOE (DOE).
Embodiment 3:
By the Cd (ClO of 5,5 ' of 25mg-(3,4,6-trifluoromethyl pyridine-2,5-bis-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 reacts 24 hours, after taking-up, repeatedly cleans with DEF, obtains metal organic frame material after oven dry.
The metal organic frame material of acquisition is carried out to exchange of solvent with acetone, every a solvent of exchange in 15 minutes, exchange ten times, then under 0 ℃ of vacuum condition, activate 36 hours, under 100 ℃ of vacuum conditions, activate 12 hours again, 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 exceed respectively 2500m
2g
-1with 3500 m
2g
-1, pore volume is greater than 1.500cm
3g
-1.Be 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), exceed the target of USDOE (DOE).
Embodiment 4:
By the Cd (CH of 5,5 ' of 15mg-(3,4-diamino-pyridine-2,5-bis-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 reacts 48 hours, after taking-up, repeatedly cleans with DMSO, obtains the crystal of diamond shaped after oven dry.
The metal organic frame material of acquisition is carried out to exchange of solvent with acetone, every a solvent of exchange in 15 minutes, exchange ten times, then under 0 ℃ of vacuum condition, activate 36 hours, under 100 ℃ of vacuum conditions, activate 12 hours again, 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 exceed respectively 2100 m
2g
-1and 3100m
2g
-1, pore volume is greater than 1.250cm
3g
-1.Be 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:
By the MnCO of 5,5 ' of 15mg-(4-pyridone-2,5-bis-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 reacts 48 hours, after taking-up, repeatedly cleans with DMSO, obtains metal organic frame material after oven dry.
The metal organic frame material of acquisition is carried out to exchange of solvent with acetone, every a solvent of exchange in 15 minutes, exchange ten times, then under 0 ℃ of vacuum condition, activate 36 hours, under 100 ℃ of vacuum conditions, activate 12 hours again, 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 exceed respectively 2300 m
2g
-1and 3300m
2g
-1, pore volume is greater than 1.200cm
3g
-1.Be 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), exceed the target of 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.Every do not depart under spirit disclosed by the invention, complete equivalence or revise, all fall into protection domain of the present invention.
Claims (1)
1. the preparation method for the metal organic frame material of methane absorption and storage, this metal organic frame material is the three-dimensional net structure consisting of coordinate bond or intermolecular force transition metal ions and organic ligand, and three-dimensional net structure specific area is 2000 ~ 3000 m
2/ g, its pore volume is 1.0 ~ 2.0 cm
3/ g, described transition metal ions is Cu
2+, Zn
2+, Cd
2+, Co
2+, Ni
2+or Mn
2+ion, described organic ligand is 5,5 '-(pyridine-2,5-bis-bases)-M-phthalic acid and derivative thereof, its structural formula is as follows:
R in formula
1, R
2and R
3for hydrogen, fluorine, methyl, amino, methoxyl group, hydroxyl or nitro;
It is characterized in that preparation process is as follows:
(1) by the nitrate of copper, zinc, cadmium, cobalt, nickel or manganese, acetate, chlorate, carbonate, sulfate or perchlorate and 5,5 '-(pyridine-2,5-bis-bases)-M-phthalic acid 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 metal organic frame material;
(2) metal organic frame material step (1) being obtained more than ten times, then activates 36 hours by acetone-exchanged under vacuum and 0 ℃ of condition, activates 12 hours at 100 ℃, obtains the metal organic frame material for methane absorption and storage.
2. the preparation method of the metal organic frame material for methane absorption and storage according to claim 1, 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108219159A (en) * | 2018-02-02 | 2018-06-29 | 西北大学 | Flexible metal organic framework materials and preparation method and application |
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