CN104151336A - Preparation method of metal-organic framework compound with hierarchical pore structure - Google Patents
Preparation method of metal-organic framework compound with hierarchical pore structure Download PDFInfo
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Abstract
The invention belongs to the technical field of nanocomposite materials and in particular relates to a preparation method of a metal-organic framework compound with a hierarchical pore structure. The preparation method comprises the following steps: firstly, self-assembling a diblock copolymer in a solvent to form a flexible polymer nanowire with a core-shell structure, and cross-linking cores to obtain a polymer nanowire with a stable solvent; adding metal ions and organic ligands into a nanowire solution to form a mixed solution; crystallizing at the room temperature to obtain a metal-organic framework/core-shell structure polymer nanowire compound; calcining to remove the polymer nanowire to obtain a hierarchical pore material with MOFs (metal-organic frameworks) micropores, small mesopores formed after calcination of a shell layer of the polymer nanowire and large mesopores formed after calcinations of a core layer. According to the MOFs material with the hierarchical pore structure, the advantages of the micropores and the micropores are combined, the mass transfer speed of the MOFs material is improved, relatively large molecules can conveniently enter the MOFs material, and the application potential of the MOFs material in the field of catalysis, adsorption and the like is improved.
Description
Technical field
The invention belongs to nano composite material technical field, be specifically related to the preparation method of the metal organic frame compound of hierarchical porous structure.
Background technology
Porous material, if molecular sieve, mesoporous silicon and gac etc. are the very important materials of a class.Due to they huge specific surface areas, it is all widely used at aspects such as catalysis, gas adsorption, ion-exchanges.The porous material of emerging a kind of organic-inorganic combination in recent years---metal organic frame compound (MOFs), due to its excellent performance, and the Modulatory character of structure and function has been subject to paying close attention to widely.MOFs is the crystalline material that a class is made up of metal ion and organic ligand.The structure and function of MOsF can obtain according to the selection of metal ion and synthetic different organic ligand.The fields such as it can be employed with gas storage, separate, detection and catalysis.
The aperture of most of MOFs is micropore (being less than 2nm), make it have large specific surface area, but be but unfavorable for that larger molecule enters, and its inner mass transfer is also restricted, and this has just limited its application at aspects such as catalysis, storage, separation, medicament transport.Therefore preparing mesoporous MOFs had particularly not only had mesoporous but also to have the multi-stage porous MOFs of micropore just very meaningful.The report (J. Am. Chem. Soc. 2012,134,126-129.) of such as Zhou Hongcai etc., uses surfactivity as producing mesoporous pore-creating agent.Report (the Crystal Growth & Design of Bai Junfeng etc., 2010,10,2451-2454.) with nanometer MOF particle by Van der Waals force gather together form crystal grain gap mesoporous, report (the J. Am. Chem. Soc. 2011 of Yaghi etc., 133,11920-11923.) thus mesoporous or macropore etc. produced by adding the part of single functionality to make crystal produce defect.But removing of tensio-active agent often causes integrally-built caving in, and utilizes Van der Waals force and special part method to have specificity.Therefore, develop the MOFs that a kind of method with universality is prepared hierarchical porous structure, and the stability of the crystal grain of maintenance MOFs is just very meaningful.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the multi-stage porous metal organic frame compound (MOFs) that can guarantee hierarchical porous structure good stability.
The preparation method of multi-stage porous metal organic frame compound provided by the invention (MOFs), concrete steps are:
(1) first, di-block copolymer self-assembly in solvent forms the flexible polymer nano wire of nucleocapsid structure, the then stratum nucleare of crosslinking nano line; Again the solvent of nano wire solution is switched to the needed solvent of MOFs crystallization;
(2) then, in polymer nano rice noodles solution, add metal salt solution and organic ligand solution, form mixing solutions; Under room temperature, leave standstill crystallization, obtain metal organic frame/nucleocapsid structure polymer nano rice noodles mixture;
(3) last, under certain temperature, calcine, remove polymer nano rice noodles, obtain the micropore of existing MOF self, there is again the large mesoporous multilevel hole material forming by after the little mesoporous and stratum nucleare calcining forming after the calcining of polymer nano rice noodles shell; In addition, the multi-stage porous particle after calcining has kept the geometric shape of crystal grain, has ensured the stability of structure.
Wherein, the MOFs of institute is ZIF-8, ZIF-7, ZIF-67, HKUST-1 or CD-MOF-1, here, ZIF-8 represents the MOFs being formed by divalent zinc ion and glyoxal ethyline, ZIF-67 represents the MOFs being formed by divalent cobalt ion and glyoxal ethyline, ZIF-7 represents the MOFs being formed by divalent zinc ion and benzoglyoxaline, and HKUST-1 represents the MOFs that bivalent cupric ion and trimesic acid form, and CD-MOF-1 represents the MOFs being formed by monovalence potassium ion and γ-cyclodextrin;
In the present invention, described polymer nano rice noodles have flexibility, can bending and mutually be wound around; The polymkeric substance of the shell of composition nano wire can interact with metal ion, in the time of metal ion and part crystallization formation MOFs, polymer/nanometer line can well be wrapped up in MOFs particle, forms particle and keeps crystal boundary, and nano wire runs through coated crystal grain.
In the present invention, the stability of described polymer nano rice noodles is lower than metal organic frame compound.
In the present invention, the multi-stage porous MOFs forming after calcining possesses spongy structure, and duct is unordered, is interconnected, and is in communication with the outside.
In step (1), described di-block copolymer is polyethylene glycol-four vinyl pyridine (PEG-
b-P4VP, polyoxyethylene glycol chain segment molecular weight is between 2000-20000, P4VP molecular weight is between 3000-20000; Linking agent is Isosorbide-5-Nitrae-dibromobutane, and the pyridine ring that crosslinking degree is 5%-100% has been crosslinked.
In step (1), can carry out modification to polymer nano rice noodles, introduce functional groups, nanoparticle or other inorganic components, optimize the functional of MOFs.For example, introduce functional functional group by halohydrocarbon with reacting of pyridine ring---pyridine groups, fluorophor; Exchange by counter ion introduce hydrochloro-auric acid induce one Au or by Br-with Ag
+reaction induce one Ag, AgBr; By at the thinner SiO of polymer core surface deposition
2, and SiO
2introduce.
In step (1), switch the method for solvent and comprise that centrifugal going dissolve after supernatant liquor again, dialysis, in dissolving again after freeze-drying any one; Solvent is that methyl alcohol (for ZIF-8, ZIF-67, ZIF-7), ethanol (for HKUST-1), water (for HKUST-1, CD-MOF-1), DMF(are for ZIF-8, ZIF-67, ZIF-7) and their mixing solutions ethanol/water (for HKUST-1) in one.
In step (2), the concentration of described reaction solution polymer nano rice noodles is 0.1mg/ml-10mg/ml.
In step (2), described metal-salt and organic ligand corresponding relation are: Zn (NO
3)
2or ZnCl
2corresponding glyoxal ethyline (ZIF-8), Co (NO
3)
2corresponding glyoxal ethyline (ZIF-67), Zn (NO
3)
2corresponding benzoglyoxaline (ZIF-7), Cu (NO3)
2or Cu (Ac)
2corresponding trimesic acid (HKUST-1), the corresponding γ-cyclodextrin of KOH (CD-MOF-1); In reaction system, the concentration of metal-salt is 10mM-150mM, and the concentration of organic ligand is 10mM-200mM.
In step (2), in the time that the MOFs of preparation is CD-MOF-1, polymer nano rice noodles and KOH, γ-cyclodextrin, all taking water as solvent, adopt the method after mixing, isopyknic methyl alcohol being diffused in the aqueous solution to prepare mixture.
In step (2), time of repose is 24 hours-3 days (for ZIF-8, ZIF-67, ZIF-7), 7-14 days (for HKUST-1, CD-MOF-1).
In step (3), the temperature of described calcining is 150 DEG C-500 DEG C, and calcination time is 0.5 hour-10 hours; Preferably the temperature of calcining is 300 DEG C-400 DEG C, and calcination time is 3 hours-4 hours.
Feature of the present invention is:
1, the method makes by forming after polymer nano rice noodles shell calcining little mesoporously, forms the MOFs material that large micropore mesoporous and MOFs itself forms hierarchical porous structure after stratum nucleare calcining.
2, polymer nano rice noodles add before crystallization forms MOFs, and in single MOFs particle, polymer nanocomposite line forms network-like structure to be run through inside and outside MOFs particle, the unordered hole therefore forming after calcining, and hole is run through mutually, and communicates with the external world.
3, after polymer nano rice noodles are removed in calcining, MOFs structure is not caved in, and has kept original crystal boundary, has ensured the stability of hierarchical porous structure.
Brief description of the drawings
Fig. 1 is field emission scanning electron microscope (a, b), the high-resolution-ration transmission electric-lens (c, d) of multi-stage porous ZIF-8 product in embodiment 1.
The nitrogen adsorption desorption curve of ZIF-8, ZIF-8/ nanowire composite, multi-stage porous ZIF-8 in Fig. 2 embodiment 1.
The NLDFT graph of pore diameter distribution of ZIF-8, ZIF-8/ nanowire composite, multi-stage porous ZIF-8 in Fig. 3 embodiment 1.
Fig. 4 is the field emission scanning electron microscope figure (a) of multi-stage porous ZIF-7 product in embodiment 3, high-resolution-ration transmission electric-lens figure (b).
Fig. 5 is the field emission scanning electron microscope figure (a) of multi-stage porous HKUST-1 product in embodiment 4, high-resolution-ration transmission electric-lens figure (b).
Embodiment
Below by embodiment, the present invention will be further described, but embodiments of the present invention are not limited to this.
The preparation of embodiment 1, hierarchical porous structure ZIF-8.
(1) in reaction flask, add 10ml(2mg/ml) polymer nano rice noodles solution, 15ml methyl alcohol, then add 25ml Zn (NO
3)
2(250mM) methanol solution, 50ml glyoxal ethyline (250mM) methanol solution.After rocking evenly, under room temperature, leave standstill.After 24h, obtain white precipitate, centrifugal collection, by methanol wash twice, vacuum drying oven is drained and is spent the night, and obtains white solid 0.1238g.
(2) product is put into retort furnace, calcine 4h at 350 DEG C, obtain yellow solid 0.0915g.The field emission scanning electron microscope of product, high-resolution-ration transmission electric-lens, nitrogen adsorption desorption experimental result is as Fig. 1,2,3.
The preparation of embodiment 2, hierarchical porous structure ZIF-8.
(1) in reaction flask, add 2ml polymer nano rice noodles (2mg/ml) solution, 83ml methyl alcohol, then add 5ml Zn (NO
3)
26H
2o(250mM) methanol solution, 10ml glyoxal ethyline (250mM) methanol solution.After rocking evenly, under room temperature, leave standstill.After 24h, obtain white flocks, centrifugal collection, by methanol wash twice, vacuum drying oven is drained and is spent the night, and obtains white solid 0.0727g.
(2) product is put into retort furnace, product is put into retort furnace, calcine 4h at 350 DEG C, obtain yellow solid 0.0504g.
The preparation of embodiment 3, hierarchical porous structure ZIF-7.
(1) in reaction flask, add 10ml(2mg/ml) polymer nano rice noodles solution, 15ml methyl alcohol, then add 25ml Zn (NO
3)
26H
2o(250mM) methanol solution, 50ml benzoglyoxaline (250mM) methanol solution.After rocking evenly, under room temperature, leave standstill.After 3 days, obtain white precipitate, centrifugal collection, by methanol wash twice, vacuum drying oven is drained and is spent the night, and obtains white solid 0.3216g.
(2) product is put into retort furnace, calcine 3h at 400 DEG C, obtain white solid 0.2852g.The field emission scanning electron microscope of product, high-resolution-ration transmission electric-lens experimental result is as Fig. 4.
Embodiment 4, HKUST-1.
(1) in reaction flask, add 10ml(2mg/ml) table polymer nano rice noodles solution, 40ml ethanol/water (1:1), then add 25ml Cu (NO
3)
23H
2o(375mM) aqueous solution, 25ml trimesic acid (250mM) ethanolic soln.After rocking evenly, under room temperature, leave standstill.After 3 days, obtain blue precipitation, centrifugal collection, by washing with alcohol twice, vacuum drying oven is drained and is spent the night, and obtains white solid 0.2321g.
(2) product is put into retort furnace, calcine 3h at 300 DEG C, obtain black solid 0.2018g.The field emission scanning electron microscope of product, high-resolution-ration transmission electric-lens experimental result is as Fig. 5.
Claims (2)
1. a preparation method for multi-stage porous organic frame compound, is characterized in that concrete steps are:
First, di-block copolymer self-assembly in solvent forms the flexible polymer nano wire of nucleocapsid structure, the then stratum nucleare of crosslinking nano line; Again the solvent of nano wire solution is switched to the needed solvent of MOFs crystallization;
Then, in polymer nano rice noodles solution, add metal salt solution and organic ligand solution, form mixing solutions; Crystallization under room temperature, obtains metal organic frame/nucleocapsid structure polymer nano rice noodles mixture;
Finally, calcining, removes polymer nano rice noodles, obtains the micropore of existing MOF self, has again the large mesoporous multilevel hole material forming by after the little mesoporous and stratum nucleare calcining forming after the calcining of polymer nano rice noodles shell;
Wherein, the MOFs of institute is ZIF-8, ZIF-7, ZIF-67, HKUST-1 or CD-MOF-1, here, ZIF-8 represents the MOFs being formed by divalent zinc ion and glyoxal ethyline, ZIF-67 represents the MOFs being formed by divalent cobalt ion and glyoxal ethyline, ZIF-7 represents the MOFs being formed by divalent zinc ion and benzoglyoxaline, and HKUST-1 represents the MOFs that bivalent cupric ion and trimesic acid form, and CD-MOF-1 represents the MOFs being formed by monovalence potassium ion and γ-cyclodextrin;
Described di-block copolymer is polyethylene glycol-four vinyl pyridines, and polyoxyethylene glycol chain segment molecular weight is between 2000-20000, and P4VP molecular weight is between 3000-20000; Linking agent is Isosorbide-5-Nitrae-dibromobutane, and the pyridine ring that crosslinking degree is 5%-100% has been crosslinked.
2. the preparation method of multi-stage porous organic frame compound according to claim 1, is characterized in that described calcining temperature is 150 DEG C-500 DEG C, and calcination time is 0.5 hour-10 hours.
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