CN101805361B - Double-shell hollow spherical organic metal framework material and preparation method thereof - Google Patents
Double-shell hollow spherical organic metal framework material and preparation method thereof Download PDFInfo
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- CN101805361B CN101805361B CN 201010128464 CN201010128464A CN101805361B CN 101805361 B CN101805361 B CN 101805361B CN 201010128464 CN201010128464 CN 201010128464 CN 201010128464 A CN201010128464 A CN 201010128464A CN 101805361 B CN101805361 B CN 101805361B
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Abstract
The invention belongs to an organic metal framework material, and particularly relates to a double-shell hollow spherical organic metal framework material (HS-ZIF-8) and a preparation method thereof. The material is of spherical particles, the granularity is 300 to 500 nm, and the material is provided with a double-layer hollow shell structure. The preparation method comprises the following steps that: sulfonated polystyrene pellets are scattered into methanol aqueous solution to be undertaken the ultrasonic treatment and be mixed for 5 to 15 minutes; zinc salt methanol solution is added and mixed; imidazole ligand is added; the mixed solution is mixed for 1 hour, held, centrifuged, washed by methanol and dried for 12 hours at the temperature of 40 DEG C to obtain white solid; under the protection of N2, the white solid is burned for 2 to 4 hours at the temperature of 300 to 400 DEG C to obtain the double-shell hollow spherical organic metal framework compound material. The double-shell hollow spherical organic metal framework compound material has the advantages that: the material has unique appearance feature, large specific surface area and high chemical and thermal stability, and has promising prospects in the fields such as gas storage, separation, sensor technology, nano parts and the like.
Description
Technical field
The present invention relates to a kind of organic metal framework material, is a kind of double-shell hollow spherical organic metal framework material and preparation method thereof specifically.
Background technology
The metal organic frame material is the method by coordination chemistry, by organic ligand and metal ion self-assembly and a class supramolecule porous material that forms, because of the uniform nano pore structure of its rule, high porosity, large specific surface, have broad application prospects in fields such as absorption, filtration and catalysis.Organic and mineral compound be organic metal framework (the metal-organic frameworks that forms of complexing mutually, MOFs), for example zeolite is different with gac from porous material on architecture model, the structure of its geometric configuration control mesh by part can also utilize organic bridge receipts or other documents in duplicate unit to assemble with metal ion the solid that obtains multiple different geometries simultaneously.Compare with traditional molecular sieve aluminum phosphate system, MOFs has that productive rate is higher, pore size and shape is adjustable, structure and function changes various characteristics.Compare with other unordered porous material with carbon nano-structured, MOFs has the crystal form of high-sequential.
Molecular sieve analog imidazoles framework compound (zeolitic imidazolate frameworks, ZIFs) is a branch of MOF material, and metallic cation and imidazole anion connect into the tetrahedron skeleton construction.This material has the molecular sieve analog structure, has specific surface area large, chemistry and the high characteristics of thermostability.For this material is widely used at aspects such as gaseous storage, separation, inductor block technology, generally assign to obtain corresponding function by appearance structure or the chemical group of regulating the ZIF material.The research of wherein regulating the ZIF properties of materials by the pattern of regulating the ZIF material seldom.Through extensively consulting domestic and international public publication and patent documentation, there are no the technical scheme identical with the organic metal framework material of hollow ball structure of the present invention and preparation method.
Summary of the invention
The purpose of this invention is to provide a kind of double-shell hollow spherical organic metal framework material that has;
Another object of the present invention is to provide the preparation method of double-shell hollow spherical organic metal framework compound-material.
Double-shell hollow spherical organic metal framework material of the present invention is spherical particle, and particle diameter 300～500nm has double-deck hollow shell structure.
The double-shell hollow spherical organic metal framework material preparation process is as follows:
(1) preparation sulfonated polystyrene bead:
A, with ghost polystyrene sphere ultra-sonic dispersion in the vitriol oil, stirred 10～100 minutes under 30～50 ℃;
B, mentioned solution is inserted in the mixing solutions of the water of 20 times of volumes and ethanol, sedimentation, centrifugal;
C, the solid water after centrifugal is washed till pH is 7.0;
D, the material lyophilize that above-mentioned steps C is made get the sulfonated polystyrene bead;
(2) with the sulfonated polystyrene bead for preparing, be dispersed in methanol solution 90W supersound process 3～7 minutes, stirring 5～15 minutes;
(3) inorganic salt with zinc add in methanol solution, the methanol solution of preparation zinc salt;
(4) the zinc salt methanol solution that step (3) is made joins in the solution that step (2) makes, and continues to stir 5～15 minutes;
(5) add glyoxaline ligand to step (4) solution, in solution, the mol ratio of zinc, imidazoles and methyl alcohol is 1: 6～10: 600～800; Stirred 0.5～2 hour, standing, centrifugal, methanol wash, 40 ℃ of dryings 12 hours obtain white solid;
(6) with above-mentioned white solid at N
2Under protection, the sulfonated polystyrene bead is removed in 300～400 ℃ of roastings 2～4 hours, obtains the double-shell hollow spherical organic metal framework compound-material.
The inorganic salt of the described zinc of step (3) are a kind of in zinc nitrate, zinc chloride, zinc sulfate or zinc acetate.
The described glyoxaline ligand of step (4) is a kind of in imidazoles, glyoxal ethyline or aminooimidazole.
The product of the present invention's preparation carries out structural characterization by following means: the wide-angle x-ray diffraction carries out the structural analysis of sample on Rigaku Rigaku D/Max-RB type X-ray diffractometer; Transmission electron microscope photo obtains under 200kV at Japanese JEOL JEM2011 type high-resolution-ration transmission electric-lens; Stereoscan photograph obtains under 3.0kV at the S 4800 type awkward silence at a meeting emission scan electron microscopes that Japanese HITACHI company produces; The heat stability testing of sample adopts Japanese Shimadzu DT-60 thermal analyzer, and temperature range is room temperature to 1000 ℃, 10 ℃ of temperature rise rate per minutes, and carrier gas is air; Measure N by the NOVA 4000 type surface area test instrument that U.S. Kang Ta company produces
2Sorption isotherm, the specific surface area of sample obtains by the BET Equation for Calculating.
The present invention is take the sulfonated polystyrene bead as template, synthesized the spherical organic metal framework compound H of novel nano S-ZIF-8 by hard template method, this organic metal framework compound has the hollow shell structure of bivalve layer, as a kind of novel material, has very large wide application prospect in fields such as gaseous storage, separation, inductor block technology, nano-devices.
Preparation method's of the present invention main points are:
The preparation of sulfonation PS bead template: the ghost PS bead ultra-sonic dispersion that will process through lyophilize is at dense H
2SO
4In, stirred in the oil bath of 30～50 ℃ 10～100 minutes, be scattered in the mixing solutions of the water of 20 times of amounts and ethanol, sedimentation, centrifugal, washing is to becoming neutral, and lyophilize is standby;
Get the PS bead of the above-mentioned sulfonation of 100～300mg, ultra-sonic dispersion is inserted in methanol solution, stirs 5～15 minutes; Add the zinc nitrate methanol solution, continue to stir after 5～15 minutes and add glyoxal ethyline, stirred one as a child, standing, centrifugal, methanol wash, 40 ℃ of dryings 12 hours obtain white solid;
White solid obtained above is carried out aftertreatment: at N
2Under protection, polystyrene moulding is removed in 300～400 ℃ of roastings 2～4 hours, obtains the spherical organic metal frame compound ZIF-8 with bivalve layer of ghost.
Advantage of the present invention is:
1, the double-shell hollow spherical organic metal framework compound-material specific surface area that makes of the present invention is large.
2, double-shell hollow spherical organic metal framework compound-material chemistry of the present invention and thermostability are high.
3, material of the present invention is widely used in fields such as gaseous storage, separation, inductor block technology, nano-components.
Description of drawings
Fig. 1 is the XRD figure of removing the spherical ZIF-8 of the front ghost of polystyrene moulding;
Fig. 2 is the XRD figure of removing the spherical ZIF-8 of the ghost after polystyrene moulding;
Fig. 3 is the SEM photo of removing ZIF-8 spherical before polystyrene moulding;
Fig. 4 is the SEM photo of removing the spherical HS-ZIF-8 of ghost after polystyrene moulding;
Fig. 5 is the TEM photo of removing ZIF-8 spherical before polystyrene moulding;
Fig. 6 is the TEM photo of removing the spherical HS-ZIF-8 of ghost with bivalve layer after polystyrene moulding.
By the XRD of sample, the contrast mimic diagram we as can be known synthetic sample all have identical single crystal structure (as Fig. 1, Fig. 2) before and after removing polystyrene moulding; According to the contrast of the SEM photo of Fig. 3 and Fig. 4, after template is removed, there is the fragmentation of part ghost ball can confirm that template removes, but the successful spherical HS-ZIF-8 of synthetic hollow shell structure; Also prove more intuitively according to the TEM photo, after the removal template, the hollow shell structure of bivalve layer has appearred in sample, the thermally-stabilised test that contrast is removed before and after template also can be learnt removal substantially of template, the spherical HS-ZIF-8 of the ghost with bivalve layer that finally obtains has higher specific surface area, larger pore volume, well thermostability.
Embodiment
Come by the following examples the present invention is further described, only as illustrating, content of the present invention is not limited to this to embodiment.In embodiment, agents useful for same is chemical pure.
Embodiment 1:
The preparation of the PS bead template of sulfonation: at ambient temperature, 10g is passed through the ghost PS bead ultra-sonic dispersion of lyophilize processing at the dense H of 300ml
2SO
4In, stirred in the oil bath of 40 ℃ 15 minutes, be scattered in the mixing solutions of 1000 ml waters and ethanol, sedimentation, centrifugal, washing is to becoming neutral, and it is standby that the PS bead of sulfonation is made in lyophilize.
Embodiment 2:
Get the PS bead of the above-mentioned sulfonation of 200mg, the 90W ultra-sonic dispersion stirred 10 minutes in 45ml methyl alcohol.The methanol solution of zinc nitrate hexahydrate is dissolved in the 0.667g zinc nitrate hexahydrate in 45ml methyl alcohol, adds to continue to stir, and adds the glyoxal ethyline of 1.47g after 10 minutes, stir one as a child after, standing, centrifugal, methanol wash, 40 ℃ of dried overnight obtain white solid.
Embodiment 3:
White solid obtained above is carried out aftertreatment, at N
2Under protection, template is removed in 350 ℃ of roastings 3 hours, obtains the spherical organic metal frame compound ZIF-8 with bivalve layer of ghost.
Embodiment 4
Above-mentioned spherical organic metal frame compound ZIF-8 with bivalve layer is carried out a series of signs.The wide-angle x-ray diffraction carries out the structural analysis of sample on Rigaku Rigaku D/Max-RB type X-ray diffractometer; Transmission electron microscope photo obtains under 200kV at Japanese JEOLJEM2011 type high-resolution-ration transmission electric-lens; Stereoscan photograph obtains under 3.0kV at the S 4800 type awkward silence at a meeting emission scan electron microscopes that Japanese HITACHI company produces; The heat stability testing of sample adopts Japanese Shimadzu DT-60 thermal analyzer, and temperature range is room temperature to 1000 ℃, 10 ℃ of temperature rise rate per minutes, and carrier gas is air; Measure N by the NOVA 4000 type surface area test instrument that U.S. Kang Ta company produces
2Sorption isotherm gets the specific surface area of sample by the BET Equation for Calculating.
The above is only the preferred embodiments of the present invention, is not limited to the present invention, and is within the spirit and principles in the present invention all for a person skilled in the art, and any modification of doing, improvement etc. are within all should being included in protection scope of the present invention.
Claims (3)
1. double-shell hollow spherical organic metal framework material, it is characterized in that: the organic metal framework compound is spherical particle, and particle diameter 300～500nm has double-deck hollow shell structure, and its preparation method is as follows:
(1) preparation sulfonated polystyrene bead:
A, with ghost polystyrene sphere ultra-sonic dispersion in the vitriol oil, stirred under 30～50 ℃ 10～100 minutes;
B, mentioned solution is inserted in the mixing solutions of the water of 20 times of volumes and ethanol, sedimentation, centrifugal;
C, the solid water after centrifugal is washed till pH is 7.0;
D, the material lyophilize that above-mentioned steps C is made get the sulfonated polystyrene bead;
(2) with the sulfonated polystyrene bead for preparing, be dispersed in methanol solution 90W supersound process 3～7 minutes, stirring 5～15 minutes;
(3) inorganic salt with zinc add in methanol solution, the methanol solution of preparation zinc salt;
(4) the zinc salt methanol solution that step (3) is made joins in the solution that step (2) makes, and continues to stir 5～15 minutes;
(5) add glyoxaline ligand to step (4) solution, in solution, the mol ratio of zinc, glyoxaline ligand and methyl alcohol is 1:6～10:600～800; Stirred 0.5～2 hour, standing, centrifugal, methanol wash, 40 ℃ of dryings 12 hours obtain white solid;
(6) with above-mentioned white solid at N
2Under protection, the sulfonated polystyrene bead is removed in 300～400 ℃ of roastings 2～4 hours, obtains the double-shell hollow spherical organic metal framework compound-material.
2. according to double-shell hollow spherical organic metal framework material claimed in claim 1, it is characterized in that: the inorganic salt of the described zinc of step (3) are a kind of in zinc nitrate, zinc chloride and zinc sulfate.
3. according to described double-shell hollow spherical organic metal framework material claimed in claim 1, it is characterized in that: the described glyoxaline ligand of step (5) is a kind of in imidazoles, glyoxal ethyline or aminooimidazole.
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| CN102218298B (en) * | 2011-04-28 | 2013-01-23 | 华南理工大学 | Preparation method of modified ZIF-8 zeolitic imidazolate framework material |
| CN102896001B (en) * | 2012-10-16 | 2015-03-18 | 中国石油大学(北京) | Preparation method for cascade porous ZIFs and hydrogen desulfurization catalyst |
| CN104387702B (en) * | 2014-11-25 | 2016-03-30 | 邵阳学院 | A kind of PVC metal-organic framework material based composite heat stabilizer and application |
| CN105110315A (en) * | 2015-07-28 | 2015-12-02 | 大连理工大学 | Method for synthesis of double-casing layer carbon nanometer hollow polyhedron by metal-organic framework as template |
| CN105837509B (en) * | 2016-04-01 | 2018-08-31 | 南开大学 | A kind of preparation method of the 2-methylimidazole Zn complex with hierarchical porous structure |
| CN107434815B (en) * | 2016-05-27 | 2020-01-10 | 北京化工大学 | Method for preparing multi-shell hollow structure metal organic framework material |
| CN106098941A (en) * | 2016-06-17 | 2016-11-09 | 同济大学 | There is micro-nano pore structure organic field effect tube sensor and making thereof and application |
| CN108031455B (en) * | 2017-12-21 | 2019-11-12 | 常州大学 | A kind of preparation method of hollow porous micro sphere adsorbent |
| CN111318304A (en) * | 2018-12-13 | 2020-06-23 | 国家纳米科学中心 | Hollow sandwich structure metal organic framework catalyst and preparation method and application thereof |
| CN109847723A (en) * | 2019-01-25 | 2019-06-07 | 北京理工大学 | A kind of preparation method that polyvinyl alcohol/ZIF-8 is composite porous |
| CN109867532B (en) * | 2019-04-15 | 2022-01-28 | 大庆悦众塑料制品有限公司 | Building insulation board and preparation method thereof |
| CN112397690A (en) * | 2019-08-12 | 2021-02-23 | 中国科学院化学研究所 | Method for in-situ construction of surface coating layer based on metal-organic framework material |
| CN110600656B (en) * | 2019-09-12 | 2022-03-25 | 肇庆市华师大光电产业研究院 | Preparation method of lithium-sulfur battery diaphragm material |
| CN112038648B (en) * | 2020-09-04 | 2022-07-26 | 北京化工大学 | Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof |
| CN112509823B (en) * | 2020-12-22 | 2022-02-15 | 上海第二工业大学 | Hollow carbon microsphere supercapacitor electrode material and solvent-free preparation method thereof |
| CN114772561B (en) * | 2022-05-07 | 2023-09-26 | 合肥工业大学 | Hollow multi-shell Sn-containing metal selenide @ carbon heterojunction and application thereof |
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| CN101432070A (en) * | 2006-02-28 | 2009-05-13 | 密歇根大学董事会 | Preparation of functionalized zeolitic frameworks |
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| CN101432070A (en) * | 2006-02-28 | 2009-05-13 | 密歇根大学董事会 | Preparation of functionalized zeolitic frameworks |
Non-Patent Citations (3)
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| Janosch Cravillon etc.Rapid room-temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework.《Chemistry of Materials》.2009,第21卷第1410-1411页. * |
| MuYang et al..General synthetic route toward functional hollow spheres with double-shelled structures.《Angewandte Chemie International Edition》.2005,第44卷(第41期),第6728页. * |
| MuYang et al..Synthesis of Spheres with Complex Structures Using Hollow Latex Cages as Templates.《Advanced Functional Materials》.2005,第15卷(第9期),第1524-1525页. * |
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