CN102617646A - Preparation method of nanoscale metal organic framework materials - Google Patents
Preparation method of nanoscale metal organic framework materials Download PDFInfo
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Abstract
The invention discloses a preparation method of nanoscale metal organic framework materials, which comprises the steps of enabling metal salt and an organic ligand to be placed in a solvent, and obtaining the metal organic framework materials by a reaction in the presence of alkali. The nanoscale/sub-nanoscale metal organic framework materials with different appearances can be obtained. The preparation method is simple, and the nanoscale metal organic framework materials can be obtained, can be used in the fields of gas capture and separation, catalyzing, medicine conveying and the like and have wide application prospect.
Description
Technical field
The present invention relates to metal-organic framework materials, particularly a kind of preparation method of nano level metal organic framework material.
Background technology
Metal-organic framework materials (Metal-Organic Frameworks.MOFs) is the one type of material that is formed, had the infinite network structure by metal and organic ligand coordination, and it is just attracting various countries investigator's interest as a kind of novel potential application of porous material in the fields such as separation of gas adsorption storage, catalysis, pharmaceutical carrier, organic molecule.
MOFs not only has adjustable topological framework and duct, and has the porosity and the specific surface area of super large.With MIL-101 (Science, 2005,30,2040) is example, and its specific surface is up to 4200m
2/ g, the aperture is at 8-30
Between, have carbonic acid gas and hydrogen adsorption ability preferably, and, can be used as the carrier (Nature Material, 2009,172) of medicine owing to its unique porosity and pore size.
The MOFs material is normally synthetic by hydrothermal method or solvent-thermal method.So far, synthesized a variety of MOFs materials in this way, what still obtain usually is micron order or even millimetre-sized MOFs powder granule.Because nanometer materials have some particular performances usually, has good application prospects, for example catalysis, nano composite membrane and gas adsorption field etc. in a lot of fields.
Therefore, this area presses for the preparation method of exploitation nano level or the other metal-organic framework materials MOFs of Subnano-class.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of simple, effective metal-organic framework materials MOFsd.
In first aspect of the present invention, a kind of metal-organic framework materials is provided, said metal-organic framework materials has following one or more characteristic:
(a) specific surface area: 500-5000m
2g
-1
(b) carbonic acid gas adsorptive power: at 0.4 ℃, 25bar adsorptive capacity>=25mmol g
-1
In another preference, said metal-organic framework materials has any characteristic of the group of being selected from down:
(a) microscopic appearance: be wire, bar-shaped, spherical or hexagonal prism;
(b) particle size: 1～600nm.
Said particle size is meant in each angle (x direction, y direction, z direction) measures particle diameter, the particle size values of the minimum that obtains.
In another preference, said metal-organic framework materials has the carbonic acid gas adsorptive power.
In another preference, the particle size of said metal-organic framework materials is 10～500nm, is more preferred from 20～200nm.
In another preference, described specific surface area: 1000-4500m
2g
-1, 1500-4000m preferably
2g
-1
Second aspect of the present invention provides a kind of preparation method of metal-organic framework materials, and said method comprises metal-salt, organic ligand in solvent, and reaction makes the step of said metal-organic framework materials in the presence of alkali.
In another preference, said metal-organic framework materials is the nano level metal organic framework material.
In another preference, said metal-salt is selected from: aluminum nitrate, aluminum nitrate hydrate, aluminum chloride, aluminum chloride hydrate, chromium nitrate, chromium nitrate hydrate, chromium nitrate, chromium nitrate hydrate, zinc chloride, zinc chloride hydrate, cupric nitrate, cupric nitrate hydrate, cupric chloride, cupric chloride hydrate.
In another preference, said metal-salt is selected from: aluminum nitrate, aluminum nitrate hydrate, aluminum chloride, aluminum chloride hydrate, chromium nitrate, chromium nitrate hydrate, chromium nitrate, chromium nitrate hydrate, zinc chloride, zinc chloride hydrate, cupric nitrate, cupric nitrate hydrate, cupric chloride, cupric chloride hydrate.
In another preference, said organic ligand is selected from: terephthalic acid, amino terephthalic acid, 1,3,5-trimesic acid, biphenyl dicarboxylic acid, 2; 6-naphthalene diacid, 2,5 ,-dihydroxyl-terephthalic acid, 2,2 '-dipyridyl-5; 5 '-dicarboxylicacid, benzene three phenylformic acid, aurin tricarboxylic acid, pentamethylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1; 2-sulfone-3,4,9, the 10-tetracarboxylic acid.
In another preference, said organic ligand is selected from: terephthalic acid, amino terephthalic acid, 1,3,5-trimesic acid, biphenyl dicarboxylic acid, 2,5 ,-dihydroxyl-terephthalic acid, benzene three phenylformic acid.
In another preference, said solvent is selected from: water or N, N, dihexyl methane amide, benzene, azanyl pyrrolidone, DMSO 99.8MIN., pyridine, toluene, ether, formonitrile HCN, methyl alcohol, ethanol, chloroform, propyl alcohol, acetone.
In another preference, said solvent is selected from: water or N.
In another preference,, described alkali is highly basic or weak base; Said weak base is acetate, fluorate, hypochlorite, or carbonate; Said highly basic is sodium hydroxide, Pottasium Hydroxide, calcium hydroxide.
In another preference, said salt is sodium salt, sylvite or calcium salt.
In another preference,, the mol ratio of said metal-salt, organic ligand, solvent is 0.1～1.5: 0.1～1.5: 50～1500; The molar ratio of described alkali and metal-salt is (0.1: 1)～(15: 1).
In another preference, the molar ratio of described alkali and organic ligand is 0.1-8.
In another preference, the mol ratio of said metal-salt, organic ligand, solvent is 0.5～1.5: 0.5～1.5: 300～500; The molar ratio of described alkali and organic ligand is 0.1-6.
In another preference, the mol ratio of said metal-salt, organic ligand, solvent is 0.8～1.2: 0.8～1.2: 350～400.
In another preference, the mol ratio of said metal-salt, organic ligand, solvent is 1: 1: 360.
In another preference, said temperature of reaction is 80-280 ℃
In another preference, said temperature of reaction is 100-250 ℃.
In another preference, said temperature of reaction is 120-220 ℃.
The third aspect of the invention provides the purposes of the described metal-organic framework materials of first aspect, and said purposes is selected from down group:
(a) as catalyzer;
(b) as sorbent material;
(c) as pharmaceutical carrier;
(d) be used to prepare separatory membrane;
(e) be used for gas entrapment, separation;
(f) be used for storage of hydrogen.
In another preference, said gas entrapment is for catching CO
2
Fourth aspect of the present invention provides a kind of film, and this film comprises base material and be coated on the metal-organic framework materials layer of at least one major surfaces of base material, wherein,
Said metal-organic framework materials layer is made up of the described metal-organic framework materials of first aspect.
In another preference, said film is gas separation membrane, liquid separating film or nano thin-film.
Preparing method of the present invention is simple, and can obtain nano level metal-organic framework materials, can be used for fields such as gas entrapment separation, catalysis and delivery of drug, is with a wide range of applications.
Description of drawings
Fig. 1 is the schematic flow sheet of the preferred process of the present invention.
Fig. 2 is the SEM figure of nano wire MOFs material.
Fig. 3 is the SEM figure of nanometer rod MOFs material.
Fig. 4 is the SEM figure of hexagonal prism MOFs material.
Fig. 5 is the adsorption curve of nano grade amino function MOFs material.
Fig. 6 is the adsorption curve of rod-like nano MOFs material.
Embodiment
The present inventor is through extensive and deep research; Find first, at material system (metal-salt, the organic ligand of preparation metal-organic framework materials MOFs; Solvent) in; Add appropriate bases, can increase the solubleness of organic ligand in solvent greatly, obtain nano level MOFs material thereby quicken the MOFs nucleation.On this basis, accomplished the present invention.
Metal-organic framework materials
Metal-organic framework materials (Metal-Organic Frameworks.MOFs); Be the metal-organic framework compound, typically refer to the metal-organic framework crystalline material that organic ligand and metals ion form through self assembling process with periodic network structure.
In metal-organic framework materials, mainly comprise: (1) metals ion: can be selected from any one of metals ion well known by persons skilled in the art, include but not limited to that transition metal ion (like metallic elements such as zinc, copper, nickel, palladium, platinum, cobalts), lanthanide series metal and other minority boron are metal (like metallic elements such as aluminium).Mostly the valence state that uses is divalence or trivalent.(2) negatively charged ion: can be selected from any one that can exist with the form of metallic compound with the metals ion bonded well known by persons skilled in the art, include but not limited to: nitrate radical, sulfate radical, nitrine acid group etc.(3) organic ligand: can be selected from any one of organic ligand of metallic compound well known by persons skilled in the art, preferably wherein contain a multiple tooth type functional group at least, like CO
2H, CS
2H, NO
2, SO
3H, PO
3H etc., normally used multiple tooth type functional group is CO
2H, like terephthalic acid (BDC), trimesic acid (BTC), oxalic acid, succsinic acid etc. as organic ligand.
Metal-organic framework materials of the present invention has functional group, and wherein, said functional group can be one or more being present in simultaneously on the said organic ligand, also can be that one or more exist simultaneously.Preferably from group is one or more down: amino, carboxyl, hydroxyl, C
1-4Alkyl etc., preferably, said functional group is amino, carboxyl or hydroxyl.
Nano level metal-organic framework material
Metal-organic framework materials provided by the invention has following one or more characteristic:
(a) specific surface area: 500-5000m
2g
-1
(b) carbonic acid gas adsorptive power: at 0.4 ℃, 25bar adsorptive capacity>=25mmol g
-1
In another preference, said metal-organic framework materials has any characteristic of the group of being selected from down:
(a) microscopic appearance: be wire, bar-shaped, spherical or hexagonal prism;
(b) particle size: 1～600nm.
Said particle size is meant in each angle (x direction, y direction, z direction) measures particle diameter, the particle size values of the minimum that obtains.
In another preference, said metal-organic framework materials has the carbonic acid gas adsorptive power, at 0.4 ℃, and 25bar adsorptive capacity>=20mmol g
-1
In another preference, said metal-organic framework materials has the carbonic acid gas adsorptive power, at 0.4 ℃, and 25bar adsorptive capacity>=30mmol g
-1
In another preference, the particle size of said metal-organic framework materials is 10～500nm, is more preferred from 20～200nm, even is 5～100nm.
In another preference, described specific surface area: 1000-4500m
2g
-1, 1500-4000m preferably
2g
-1
Metal-organic framework materials provided by the invention, is reacted in the presence of alkali and makes in solvent by metal-salt, organic ligand.
Used metal base is the metal-salt of the usual preparation metal-organic framework materials that uses in this area; Include, but are not limited to aluminum nitrate, aluminum nitrate hydrate, aluminum chloride, aluminum chloride hydrate, chromium nitrate, chromium nitrate hydrate, chromium nitrate, chromium nitrate hydrate, zinc chloride, zinc chloride hydrate, cupric nitrate, cupric nitrate hydrate, cupric chloride, cupric chloride hydrate.
In another preference, said metal-salt is selected from: aluminum nitrate, aluminum nitrate hydrate, aluminum chloride, aluminum chloride hydrate, chromium nitrate, chromium nitrate hydrate, chromium nitrate, chromium nitrate hydrate, zinc chloride, zinc chloride hydrate, cupric nitrate, cupric nitrate hydrate, cupric chloride, cupric chloride hydrate.
Used organic ligand is the organic ligand of the usual preparation metal-organic framework materials that uses in this area, includes, but are not limited to terephthalic acid, amino terephthalic acid, 1,3,5-trimesic acid, biphenyl dicarboxylic acid, 2; 6-naphthalene diacid, 2,5 ,-dihydroxyl-terephthalic acid, 2,2 '-dipyridyl-5; 5 '-dicarboxylicacid, benzene three phenylformic acid, aurin tricarboxylic acid, pentamethylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1; 2-sulfone-3,4,9, the 10-tetracarboxylic acid.
In another preference, said organic ligand is selected from: terephthalic acid, amino terephthalic acid, 1,3,5-trimesic acid, biphenyl dicarboxylic acid, 2,5 ,-dihydroxyl-terephthalic acid, benzene three phenylformic acid.
Used solvent is the solvent of the usual preparation metal-organic framework materials that uses in this area; Comprise; But be not limited to water or N, N, dihexyl methane amide, benzene, azanyl pyrrolidone, DMSO 99.8MIN., pyridine, toluene, ether; Formonitrile HCN, methyl alcohol, ethanol, chloroform, propyl alcohol, acetone.
In another preference, said solvent is selected from: water or N.
The present invention adds alkali in the reaction system of preparation metal-organic framework materials, described alkali is highly basic or weak base; Said weak base is acetate, fluorate, hypochlorite, or carbonate; Said highly basic is sodium hydroxide, Pottasium Hydroxide, calcium hydroxide.
The mol ratio of said metal-salt, organic ligand, solvent is (0.1～1.5): (0.1～1.5): (50～1500); The molar ratio of described alkali and metal-salt is (0.1: 1)～(15: 1).
In another preference, the mol ratio of said metal-salt, organic ligand, solvent is 0.5～1.2: 0.5～1.2: 300～1000, and more preferably, the mol ratio of said metal-salt, organic ligand, solvent is 0.8～1.0: 0.8～1.0: 350～500.
In another preference, the mol ratio of said metal-salt, organic ligand, solvent is 1: 1: 360.
In another preference, the molar ratio of described alkali and metal-salt is (0.5: 1)～(10: 1).
The preparation method of nano level metal-organic framework material
Because metal-organic framework materials (MOFs material) itself is the title complex of a kind of metal and organic substance, co-ordination bond is easy to interrupted and causes its decomposition under the environment of alkalescence, i.e. alkaline environment synthetic inhibited to MOFs.Therefore, in the synthetic report of MOFs, almost in resulting solution, do not add alkaline matter.
The contriver is unexpected first to find that an amount of alkali of adding can increase the solubleness of organic cpds in reaction soln greatly in the preparation process of MOFs material; Especially insoluble or be insoluble in the organic cpds of reaction solvent for some, obtain small size MOFs material thereby quicken the MOFs nucleation.
The application adds an amount of alkaline matter in the MOFs resulting solution; Increase its solubleness in solution; From formation that promotes the MOFs nucleus and the growth of accelerating MOFs; And through control synthesis condition controlledly synthesis nano level MOFs material, through optimizing the nano level MOFs material that synthesis condition obtains different-shape, pattern is controlled.
The preparation method of nano level metal organic framework material provided by the invention comprises metal-salt, organic ligand in solvent, and reaction makes the step of nano level metal organic framework material in the presence of alkali.
As shown in Figure 1, be preparing method's of the present invention schematic flow sheet.Wherein,
Fig. 1 (A): at first with metal-salt, organic ligand, reactants such as solvent place reaction kettle, and under the situation that does not add alkaline matter, organic ligand is insoluble;
Fig. 1 (B): after adding alkali, organic ligand and OH
-Reaction generates ion and is dissolved in the solvent equably;
Fig. 1 (C): with the reaction kettle heating,, make the nucleus of MOFs generate very soon, obtain MOFs materials such as the nanometer ball shown in Fig. 1 (D), Fig. 1 (E), Fig. 1 (F), nanometer rod, nano wire because a large amount of organic ligand ionic exists.
In another preference, preparation method of the present invention may further comprise the steps:
(a): with metal-salt, organic ligand, solvent places reaction kettle, adds alkali, mixes;
(b): the reacting by heating system generates nano level MOFs material.
In another preference, said metal-salt is selected from: aluminum nitrate, aluminum nitrate hydrate, aluminum chloride, aluminum chloride hydrate, chromium nitrate, chromium nitrate hydrate, chromium nitrate, chromium nitrate hydrate, zinc chloride, zinc chloride hydrate, cupric nitrate, cupric nitrate hydrate, cupric chloride, cupric chloride hydrate.
In another preference, said metal-salt is selected from: aluminum nitrate, aluminum nitrate hydrate, aluminum chloride, aluminum chloride hydrate, chromium nitrate, chromium nitrate hydrate, chromium nitrate, chromium nitrate hydrate, zinc chloride, zinc chloride hydrate, cupric nitrate, cupric nitrate hydrate, cupric chloride, cupric chloride hydrate.
In another preference, said organic ligand is selected from: terephthalic acid, amino terephthalic acid, 1,3,5-trimesic acid, biphenyl dicarboxylic acid, 2; 6-naphthalene diacid, 2,5 ,-dihydroxyl-terephthalic acid, 2,2 '-dipyridyl-5; 5 '-dicarboxylicacid, benzene three phenylformic acid, aurin tricarboxylic acid, pentamethylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1; 2-sulfone-3,4,9, the 10-tetracarboxylic acid.
In another preference, said organic ligand is selected from: terephthalic acid, amino terephthalic acid, 1,3,5-trimesic acid, biphenyl dicarboxylic acid, 2,5 ,-dihydroxyl-terephthalic acid, benzene three phenylformic acid.
In another preference, said solvent is selected from: water or N, N, dihexyl methane amide, benzene, azanyl pyrrolidone, DMSO 99.8MIN., pyridine, toluene, ether, formonitrile HCN, methyl alcohol, ethanol, chloroform, propyl alcohol, acetone.
In another preference, said solvent is selected from: water or N.
In another preference, described alkali is highly basic or weak base; Said weak base is acetate, fluorate, hypochlorite, or carbonate; Said highly basic is sodium hydroxide, Pottasium Hydroxide, calcium hydroxide.
In another preference, the mol ratio of said metal-salt, organic ligand, solvent is (0.1～1.5): (0.1～1.5): (50～1500); The molar ratio of described alkali and metal-salt is (0.1: 1)～(15: 1).
In another preference, the mol ratio of said metal-salt, organic ligand, solvent is 0.8～1.0: 0.8～1.0: 350～500.
In another preference, the molar ratio of described alkali and metal-salt is (0.5: 1)～(10: 1).
In another preference, the mol ratio of said metal-salt, organic ligand, solvent is 1: 1: 360.
In another preference, the molar ratio of described alkali and organic ligand is 0.1-8.
In another preference, said temperature of reaction is 80-280 ℃, preferably 100-250 ℃, and more preferably 120-220 ℃.
In another preference, the said reaction times is 10～100hr.
In another preference, method of the present invention also comprises following post-processing step:
(a) centrifugally obtain thick product;
(b) organic solvent of thick product with 40～150 ℃ soaked;
(c) remove organic solvent, drying obtains nano level metal-organic framework material.
In another preference, said post-processing step is in the preceding step that thick product is soaked centrifugal removal unreacted reactant through organic solvent that also comprises of step (b), and preferred organic is DMF (N).
In another preference, adopt 50～80 ℃ alcohol-pickled 20-30h or adopt 100～150 ℃ DMF to soak 20-30h.
In another preference, in air atmosphere, carry out drying, drying temperature is 60-100 ℃, is preferably 75-85 ℃.
In another preference, preparation method of the present invention may further comprise the steps:
(a) with metal-salt, organic ligand, solvent places reaction kettle, and the mol ratio of said metal-salt, organic ligand, solvent is 0.8～1.2: 0.8～1.2: 350～400;
(b) add alkali, the molar ratio of described alkali and organic ligand is 0.1-6, organic ligand and OH
-Reaction generates ion and is dissolved in the solvent equably;
(c) reaction system is heated to 100-250 ℃ of reaction 12～72hr;
(d) the thick product of centrifugal acquisition;
(e) adopt N immersion, centrifugal removal unreacted reactant;
(f) handle 20-24h with 50～80 ℃ alcohol or 100～150 ℃ DMF;
(g) drying obtains nano level metal-organic framework material.
The application of nano level metal-organic framework material
The nano level MOFs material of the present invention's preparation is to CO
2Have high adsorptive capacity and adsorption enthalpy, and very little therefore to the adsorptive capacity of other gases such as nitrogen, methane, the MOFs material of preparation separates in gas entrapment by this method, and fields such as catalysis and nano-sized membrane have good application prospects.
Nano level metal organic framework material of the present invention, its purposes is selected from down group:
(a) as catalyzer;
(b) as sorbent material;
(c) as pharmaceutical carrier;
(d) be used to prepare separatory membrane;
(e) be used for gas entrapment, separation;
(f) be used for storage of hydrogen.
Nano level metal organic framework material of the present invention can be used to process film, and said film can be used as gas separation membrane, liquid separating film or nano thin-film.
The preparation method of film can adopt the usual method of using in this area, comprises step:
(i) on base material, introduce the crystal seed of metal-organic framework materials, thereby form the base material that the surface is connected with the crystal seed of the metal-organic framework materials with functional group with functional group; With,
The base material that the surface that (ii) step (i) is obtained is connected with the crystal seed of the metal-organic framework materials with functional group places reaction system, carries out the two-step film forming reaction, thereby forms metal-organic framework materials film of the present invention.
Preferably, comprise step:
(i-1) the metal-organic framework materials that provides an employing the inventive method to prepare with functional group;
(i-2) will contain said seed-solution and coat at least one major surfaces of base material with metal-organic framework materials of functional group after; Carry out dry activation treatment, thereby form the base material that the surface is connected with the crystal seed of the metal-organic framework materials with functional group.
Wherein, said seed-solution is said metal-organic framework materials with functional group to be dissolved in inert solvent process; Said inert solvent can be selected from any one of inert solvent well known by persons skilled in the art; The solvent that is liquid under the preferred normal temperature and can the said metal-organic framework materials of well dispersed; Preferably, be selected from down group: zero(ppm) water, ethanol, DMF, methyl alcohol or acetone etc.
(ii-1) provide a preparation to have the reaction system of the metal-organic framework materials of functional group;
Configuration when the configuration of said reaction system can prepare the metal-organic framework materials with functional group with step (i-1) is middle (comprise used metallic compound, organic ligand, solvent, alkali, and the molar ratio of raw material etc.) unanimity.
(ii-2) base material that said surface is connected with the crystal seed of the metal-organic framework materials with functional group places the reaction system of step (ii-1), carries out the two-step film forming reaction, thereby forms metal-organic framework materials film of the present invention.
Said film formation reaction condition can to have the condition (comprising temperature of reaction, time etc.) of metal-organic framework materials of functional group consistent with preparation in the step (i-1).
Said film can pass through aftertreatment subsequently, comprises cleaning, high temperature drying, vacuumizes processes such as activation, removes the guest molecule (like H2O, DMF, ethanol etc.) that remains in MOF fenestra road.
The present invention has following advantage:
(1) the invention provides a kind of novel method for preparing metal-organic framework materials.
(2) method of the present invention is simple, easy to operate.
(3) the present invention adds alkali in reaction system, can make nano level metal-organic framework material
(4) nano level metal-organic framework material of the present invention has preferable carbon dioxide capture ability.
Below in conjunction with practical implementation, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
Embodiment 1
The preparation of nano grade amino functionalization MOF
At first, in the tetrafluoroethylene reaction kettle, add chromium nitrate (800mg), amino terephthalic acid (360mg), Pottasium Hydroxide (280mg) and deionized water (25ml), be stirred to evenly.Put into baking oven then and rise to 130～170 ℃, and after keeping 12h, from baking oven, take out, naturally cool to room temperature with the speed of 10 ℃ of PMs; Open reaction kettle, at first through centrifugal acquisition green product, and then through organic solvent (DMF; N) soak, centrifugal removing unreacted reactant, and then move in the reaction kettle, with 50～80 ℃ alcohol processing 24h; Drying obtains green powder in 80 ℃ of air atmosphere at last; Through electron microscopic observation, particle size≤50nm obtains nano grade amino functionalization MOFs material.
The preparation of wire nanometer MOFs material
At first, in the tetrafluoroethylene reaction kettle, add nine water aluminum nitrates (375mg), trimesic acid (280mg), sodium hydroxide (200mg) and deionized water (10ml), be stirred to evenly.Put into baking oven then and rise to 130～170 ℃ baking oven with the speed of 10 ℃ of PMs and react, from baking oven, take out behind the question response to 3 day, naturally cool to room temperature, afterwards through centrifugal acquisition reaction product.Again through DMF soak, centrifugal back moves in the reaction kettle, with 100～150 ℃ DMF processing 24h, drying obtains white powder in 80 ℃ of air atmosphere at last.
In the present embodiment, the reaction mole proportioning of sodium hydroxide and aluminum nitrate is 5: 1, and the MOFs material granule pattern that obtains is nano wire, and is as shown in Figure 2, and the mean length of nanometer wire MOFs material reaches about 2 microns mean diameter＜20nm.
Embodiment 3
The preparation of rod-like nano MOFs material
At first, in the tetrafluoroethylene reaction kettle, add nine water aluminum nitrates (1500mg), trimesic acid (280mg), sodium hydroxide (200mg) and deionized water (10ml), be stirred to evenly.Put into baking oven then and rise to 130～170 ℃ baking oven with the speed of 10 ℃ of PMs and react, from baking oven, take out behind the question response to 3 day, naturally cool to room temperature, afterwards through centrifugal acquisition reaction product.Again through DMF soak, centrifugal back moves in the reaction kettle, with 100～150 ℃ DMF processing 24h, drying obtains white powder in 80 ℃ of air atmosphere at last.
Individual in the present embodiment, the reaction mole proportioning of the alkali sodium hydroxide of employing and aluminum nitrate is 1.25: 1, and is as shown in Figure 3, and the MOFs material granule pattern that obtains is a nanometer rod, and the mean length of the MOFs material of nano bar-shape is about 200nm.
Embodiment 4
The preparation of hexagonal prism MOFs material
At first, in the tetrafluoroethylene reaction kettle, add nine water aluminum nitrates (375mg), trimesic acid (280mg), sodium hydroxide (100mg) and deionized water (10ml), be stirred to evenly.Put into baking oven then and rise to 130～170 ℃ baking oven with the speed of 10 ℃ of PMs and react, from baking oven, take out behind the question response to 3 day, naturally cool to room temperature, afterwards through centrifugal acquisition reaction product.Again through DMF soak, centrifugal back moves in the reaction kettle, with 100～150 ℃ DMF processing 24h, drying obtains white powder in 80 ℃ of air atmosphere at last.
The reaction mole proportioning of sodium hydroxide and aluminum nitrate is 2.5: 1, and is as shown in Figure 4, and the cross section pattern of the MOFs material granule that obtains is a sexangle, and the MOFs material granule is a hexagonal prism, mean length＜500nm.
The preparation of nanometer MOFs material
At first, in the tetrafluoroethylene reaction kettle, add nine water chromium nitrates (800mg), terephthalic acid (332mg), Lithium Acetate (100mg) and deionized water (25ml), be stirred to evenly.Put into baking oven then and rise to 180～220 ℃ baking oven with the speed of 10 ℃ of PMs and react, from baking oven, take out behind the question response to 16 hour, naturally cool to room temperature, afterwards through centrifugal acquisition reaction product.Handle 24h through ethanol down at 80 ℃ again, drying obtains green powder in 80 ℃ of air atmosphere at last, and the MOFs material that microscopic examination obtains is a nano particle, and particle size is 90～100nm, and through test, specific surface reaches 3000m
2g
-1
Embodiment 6
The performance test of MOFs material
Nano grade amino functionalization MOFs material with embodiment 1 preparation is an example, adopts ASAP-2020 absorption appearance (U.S. Micromeritics company) that its performance is tested, and the result is as shown in Figure 5.
The specific surface of nano grade amino functionalization MOFs material is up to 1675m
2g
-1Shown in Fig. 5 a, nano grade amino functionalization MOFs material has very excellent CO
2Acquisition performance, at 0.4 ℃, under the 25bar up to 25mmol g
-1, have high adsorptive power, shown in Fig. 5 b, at 25 ℃ of nano grade amino functionalization MOFs materials to N
2And CH
4Adsorptive capacity seldom, at 25 ℃, under the 25bar to CH
4Adsorptive capacity be about 5mmol g
-1, to N
2Adsorptive capacity be about 3mmol g
-1, have good selectivity.
Embodiment 7
The performance test of MOFs material
Rod-like nano MOFs material with embodiment 3 preparations is an example, and its performance is tested, and its specific surface area reaches 1043m
2g
-1Has very excellent CO
2Acquisition performance, as shown in Figure 6, at 0.4 ℃, surpass 15mmolg under the 30bar adsorptive capacity
-1, have high adsorptive power, and to N
2And CH
4Have good selectivity, at 0.4 ℃, the adsorptive capacity to CH4 under the 30bar is about 5mmolg
-1, to N
2Adsorptive capacity be about 3mmolg
-1
All documents in that the present invention mentions are all quoted as a reference in this application, are just quoted such as a reference separately as each piece document.Should be understood that in addition after having read above-mentioned teachings of the present invention, those skilled in the art can do various changes or modification to the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. a metal-organic framework materials is characterized in that, said metal-organic framework materials has following one or more characteristic:
(a) specific surface area: 500-5000m
2g
-1
(b) carbonic acid gas adsorptive power: at 0.4 ℃, 25bar adsorptive capacity>=25mmol g
-1
2. metal-organic framework materials as claimed in claim 1 is characterized in that, said metal-organic framework materials has any characteristic of the group of being selected from down:
(a) microscopic appearance: be wire, bar-shaped, spherical or hexagonal prism;
(b) particle size: 1～600nm.
3. the preparation method of a metal-organic framework materials is characterized in that being, said method comprises metal-salt, organic ligand in solvent, and reaction makes the step of said metal-organic framework materials in the presence of alkali.
4. preparation method as claimed in claim 3; It is characterized in that said metal-salt is selected from: aluminum nitrate, aluminum nitrate hydrate, aluminum chloride, aluminum chloride hydrate, chromium nitrate, chromium nitrate hydrate, chromium nitrate, chromium nitrate hydrate, zinc chloride, zinc chloride hydrate, cupric nitrate, cupric nitrate hydrate, cupric chloride, cupric chloride hydrate.
5. preparation method as claimed in claim 3 is characterized in that, said organic ligand is selected from: terephthalic acid, amino terephthalic acid, 1,3,5-trimesic acid, biphenyl dicarboxylic acid, 2; 6-naphthalene diacid, 2,5 ,-dihydroxyl-terephthalic acid, 2,2 '-dipyridyl-5; 5 '-dicarboxylicacid, benzene three phenylformic acid, aurin tricarboxylic acid, pentamethylene tetracarboxylic acid, perylene-3,4,9,10-tetracarboxylic acid, perylene-1; 2-sulfone-3,4,9, the 10-tetracarboxylic acid.
6. preparation method as claimed in claim 3; It is characterized in that; Said solvent is selected from: water or N, N, dihexyl methane amide, benzene, azanyl pyrrolidone, DMSO 99.8MIN., pyridine, toluene, ether; Formonitrile HCN, methyl alcohol, ethanol, chloroform, propyl alcohol, acetone.
7. preparation method as claimed in claim 3 is characterized in that, described alkali is highly basic or weak base; Said weak base is acetate, fluorate, hypochlorite, or carbonate; Said highly basic is sodium hydroxide, Pottasium Hydroxide, calcium hydroxide.
8. preparation method as claimed in claim 3 is characterized in that, the mol ratio of said metal-salt, organic ligand, solvent is 0.1～1.5: 0.1～1.5: 50～1500; The molar ratio of described alkali and metal-salt is (0.1: 1)～(15: 1).
9. the purposes of the described metal-organic framework materials of claim 1 is characterized in that, said purposes is selected from down group:
(a) as catalyzer;
(b) as sorbent material;
(c) as pharmaceutical carrier;
(d) be used to prepare separatory membrane;
(e) be used for gas entrapment, separation;
(f) be used for storage of hydrogen.
10. a film is characterized in that, comprises base material and is coated on the metal-organic framework materials layer of at least one major surfaces of base material, and said metal-organic framework materials layer is made up of the described metal-organic framework materials of claim 1.
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