CN107266703A - A kind of method using the materials of micro-diplopore HKUST 1 in neutral template normal temperature synthesis lamella - Google Patents
A kind of method using the materials of micro-diplopore HKUST 1 in neutral template normal temperature synthesis lamella Download PDFInfo
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- CN107266703A CN107266703A CN201710378541.1A CN201710378541A CN107266703A CN 107266703 A CN107266703 A CN 107266703A CN 201710378541 A CN201710378541 A CN 201710378541A CN 107266703 A CN107266703 A CN 107266703A
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Abstract
The invention discloses a kind of method using the materials of micro-diplopore HKUST 1 in neutral template normal temperature synthesis lamella.This method comprises the following steps：First, ZnO is dissolved in water and N, the mixed solution of N dimethylformamides, ultrasound；2nd, it is Gerhardite is soluble in water and be stirred well to clarification；3rd, the solution in step one and step 2 is mixed, stirring；4th, trimesic acid and template hexadecane bromide are dissolved in ethanol and stirred；5th, the solution in step 3 and step 4 is mixed, stirring；6th, by products therefrom suction filtration, drying, the middle materials of micro-diplopore HKUST 1 are obtained.The present invention is used as template by adding hexadecane bromide, not only easy to operate, mild condition, while also shortening generated time.Product shows lamellar structure, with abundant duct, while having micropore, mesoporous two kinds of ducts, not only Stability Analysis of Structures, also has preferable application prospect in terms of the absorption and catalysis of macromolecular.
Description
Technical field
The invention belongs to the quick preparation field of multi-stage porous metal organic framework, and in particular to one kind uses neutral template
The method of micro-diplopore HKUST-1 materials in normal temperature synthesis lamella.
Background technology
Metal organic framework (MOFs) refer to by metal ion or metal cluster and organoligand coordination be self-assembly of it is many
Hole crystalline material.Its high-specific surface area, high porosity and adjustable pore size so that MOFs materials are in gas storage, absorption
There is good application prospect in terms of separation, heterogeneous catalysis, medicine delivery and chemical sensor.But what major part was reported
MOFs only has microcellular structure, its application is confined to the separation and reaction of small molecule, while narrow passage is also limited
The speed of diffusion and mass transfer.Therefore, the multi-stage porous MOFs that synthesis has meso-hole structure and microcellular structure simultaneously has weight
Big meaning.On the one hand, material has larger mesopore orbit, and demand is disclosure satisfy that in terms of the absorption and catalysis of macromolecular.
On the other hand, the microcellular structure in material ensure that high specific surface area and the stability of material.
Williams [Chui S Y, Lo S M, Charmant J P, the et al.A of Hong Kong University of Science and Thchnology in 1999
chemically functionalizable nanoporous material[Cu3(TMA)2(H2O)3]n[J].Science,
1999,283(5405):1148-1150.] reacted first using trimesic acid and copper nitrate, synthesize and removed object in duct
Stable [the Cu of skeleton can also be kept after molecule3(BTC)2·(H2O)3]n(HKUST-1), material has big specific surface area, and aperture exists
1nm or so, is a kind of typical poromerics.On the one hand too small duct is unfavorable for the quick diffusion and transmission of small molecule, makes
It is adsorbed or reaction rate is low, on the other hand causes macromolecular to be difficult to enter generate inside duct or inside duct big
Molecule can not be spread out, and limit MOFs materials has macromolecular (such as catalyst molecule, large-sized drug molecule in many
Deng) participate in reaction in application, this greatly hinders the practical application of MOFs materials.
In view of diffusion restricted problem of the above-mentioned metal-organic framework materials to guest molecule, increasing scientist will
Sight invests multi-stage porous MOFs materials.Multi-stage porous MOFs refers to the MOFs materials with more than two-stage or two-stage compound duct,
Such as micropore-mesopore, micropore-macropore, mesopore-macropore, micropore-mesopore-macropore etc..Nearly ten years, people deepen continuously pair
The research of MOFs materials, has prepared the MOFs materials of middle micro-diplopore.Extension part method and soft mode edition method are to introduce mesoporous
Conventional two methods., Yaghi groups [Eddaoudi M, Kim J, Rosi N, et al.Systematic in 2002
design of pore size and functionality in isoreticular MOFs and their
application in methane storage.[J].Science,2002,295(5554):469-72.] report one and be
Row based on MOF-5, with various sizes of organic carboxyl acid part synthesize aperture span fromRegular MOFs materials
Material.But synthesising mesoporous purpose is reached by extending the length of organic ligand, easily occurs framework and mutually runs through, and is being moved
Except guest molecule back skeleton easily caves in.And soft template method is more convenient feasible by contrast.By using surfactant and
Block copolymer is as structure directing agent (SDA), the common group of the presoma and structure directing agent of metal ion and organic ligand formation
Dress forms crystal, after SDA is removed from material, is formed being made up of the multilevel hole material of mesoporous wall micropore MOF.Pass through
Skeleton structure and pore size can effectively be adjusted by changing species, the concentration of template agent.In addition, the, [Qiu such as Qiu in 2008
L G,Xu T,Li Z Q,et al.Hierarchically Micro-and Mesoporous Metal-organic
Frameworks with Tunable Porosity[J].Angewandte Chemie International Edition,
2008,47(49):9487-9491.] use Surfactant CTAB (cetyl trimethylammonium bromide) as SDA, synthesize one
Series is based on micropore [Cu3(btc)2(H2O)3] (HKUST-1) aperture from the adjustable mesoporous [Cu of 3.8-31.0nm3(btc)2
(H2O)3] (btc=1,3,5- trimesic acids).The mesoporous wall of middle micro-diplopore MOFs materials is made up of microporous crystalline framework, it
Integrate the advantage of micropore, mesoporous material.Adjustable aperture can strengthen its selective absorption；Micropore hole wall ensures material
With high-specific surface area；Mesopore orbit is conducive to the diffusion of molecule.Its performance of the structures shape of material, so possessing many of prosperity
The middle micro-diplopore MOFs materials of level pore structure are substantially better than the material of only single pore structure in terms of diffusion, mass transfer, absorption
Material.
The MOFs materials of lamella equally possess big advantage., [Li P Z, the Maeda Y, Xu such as Li in 2011
Q.Top-down fabrication of crystalline metal–organic framework nanosheets[J]
.Chemical Communications,2011,47(29):8436-8438.] confirm using top-down chemical stratification
Method can prepare the MOFs nanometer sheets of layer structure, and they are successfully by { Zn2(TPA)4(H2O)2·2DMF}n(MOF-2) } make
Into sheet layer material.In configuration aspects, the MOFs on upper strata can readily extend to other layers, with other layers of interconnection, protect
General MOFs two-dimensional structure is held.Moreover, experiment shows that the material possesses fabulous amine insertion property and reversible friendship
Transsexual matter, this illustrates that the MOFs materials of lamellar structure have big advantage in terms of molecular memory and drug delivery.
Originally the HKUST-1 materials of micro-diplopore in lamella have been researched and proposed, then it is using as " super bright in MOF materials
Star ", is provided simultaneously with lamella, micropore and all advantages of mesoporous material, and it will play huge in terms of diffusion, mass transfer, absorption
Advantage and potential.
The present invention using hexadecane bromide as template, micro-diplopore metal-organic framework material in synthesis lamella under normal temperature
Material.
The content of the invention
Micro-diplopore KUST-1 materials in neutral template normal temperature synthesis lamella are used it is an object of the invention to provide one kind
Method, it is intended to easily synthesis with lamellar structure multi-stage porous HKUST-1 materials.
Raw material of the present invention be ZnO, Gerhardite, trimesic acid, hexadecane bromide, N,N-dimethylformamide,
Ethanol, deionized water, template hexadecane bromide (being purchased from lark prestige), using only hexadecane bromide as structure directing agent, i.e.,
A kind of HKUST-1 materials of micro-diplopore in lamella can be synthesized.
The purpose of the present invention is achieved through the following technical solutions.
A kind of method using micro-diplopore HKUST-1 materials in neutral template normal temperature synthesis lamella, comprises the following steps：
(1) at room temperature, ZnO is dissolved in the mixed solution of deionized water and DMF, ultrasound；
(2) Gerhardite is dissolved in deionized water, is stirred well to clarification；
(3) solution obtained by step (1) and step (2) is mixed, stirring obtains mixed solution；
(4) trimesic acid and template hexadecane bromide are dissolved in ethanol, stirred；
(5) solution in step (3) and step (4) is mixed, stirring；
(6) by the product suction filtration obtained by step (5), it is put into vacuum drying chamber and dries, micro-diplopore in lamella is made
HKUST-1 materials.
Preferably, the ultrasonic time in step (1) is 10-20 minutes.
Preferably, the mixing time in step (2) is 10-30 minutes.
Preferably, the mixing time in step (3) is 1-10 minutes.
Preferably, the mixing time in step (4) is 10-30 minutes.
Preferably, the mixing time in step (5) is 20-40 minutes.
Preferably, the drying temperature in step (6) is 140-150 DEG C, and drying time is 10-12h.
Preferably, the ZnO, Gerhardite, trimesic acid, the mol ratio of hexadecane bromide are (0.5-1.5)：
(1.5-2.5)：(0.6-1.6)：(1.0-3.0).
Preferably, the ZnO, Gerhardite, trimesic acid, hexadecane bromide, DMF, second
Alcohol, the mol ratio of water are (0.5-1.5)：(1.5-2.5)：(0.6-1.6)：(1.0-3.0)：(57.2-58.2)：(75.6-
76.6)：(400.7-401.7).
Relative to prior art, the invention has the advantages that and effect：
(1) method of the invention is using neutral template hexadecane bromide, what it was formed between part be hydrogen bond and compared with
Weak coordinate bond, can just be removed, this just protects the structure of material not to be destroyed completely without carrying out high-temperature process, and neutral
The low evil of template low toxicity, will not cause big damage to human body.
(2) the HKUST-1 materials of method of the invention synthesis show lamellar structure, and possess abundant duct knot
Also there is preferable application prospect in terms of structure, not only Stability Analysis of Structures, and absorption, the transmission of material and catalysis in macromolecular.
(3) present invention is only by adding template, you can synthesize multi-stage porous HKUST-1 materials at normal temperatures, simple to operate,
Mild condition, it is to avoid the step such as heating, saves the energy.
Brief description of the drawings
Fig. 1 is micro-diplopore in the lamella prepared using the HKUST-1 materials and embodiment 1,3 of conventional hydrothermal method synthesis
The X-ray diffractogram of HKUST-1 materials.
Fig. 2 is the stereoscan photograph of micro-diplopore HKUST-1 materials in lamella prepared by embodiment 1.
Fig. 3 is the N of micro-diplopore HKUST-1 materials in lamella prepared by embodiment 12Adsorption-desorption isothermal figure.
Fig. 4 is the graph of pore diameter distribution of micro-diplopore HKUST-1 materials in lamella prepared by embodiment 1.
Fig. 5 is the stereoscan photograph of micro-diplopore HKUST-1 materials in lamella prepared by embodiment 3.
Fig. 6 is the N of micro-diplopore HKUST-1 materials in lamella prepared by embodiment 32Adsorption-desorption isothermal figure.
Fig. 7 is the graph of pore diameter distribution of micro-diplopore HKUST-1 materials in lamella prepared by embodiment 3.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the scope of embodiment statement.
Embodiment 1
In the mixed solution that 0.293g ZnO are dissolved in 8mL deionized waters and 16mL DMFs, ultrasound 15
Minute, obtain ZnO solution；1.74g Gerhardites are dissolved in 18mL deionized waters and stirred 20 minutes, copper nitrate are obtained molten
Liquid；ZnO solution and copper nitrate solution are mixed 5 minutes, the mixed solution of ZnO and copper nitrate is obtained；By the equal benzene front threes of 0.84g
Acid and 2.2g hexadecane bromides, which are dissolved in 16mL ethanol, to be stirred 20 minutes, obtains template solution；By template solution and ZnO and nitre
The mixed solution mixing of sour copper, is stirred 30 minutes；It is put into after suction filtration in 150 DEG C of vacuum drying chambers and dries 12h, is made micro- in lamella
Diplopore HKUST-1 materials, labeled as sample A.
Embodiment 2
In the mixed solution that 0.293g ZnO are dissolved in 8mL deionized waters and 16mL DMFs, ultrasound 15
Minute, obtain ZnO solution；1.74g Gerhardites are dissolved in 18mL deionized waters and stirred 20 minutes, copper nitrate are obtained molten
Liquid；ZnO solution and copper nitrate solution are mixed 5 minutes, the mixed solution of ZnO and copper nitrate is obtained；By the equal benzene front threes of 0.84g
Acid and 4.4g hexadecane bromides, which are dissolved in 16mL ethanol, to be stirred 20 minutes, obtains template solution；By template solution and ZnO and nitre
The mixed solution mixing of sour copper, is stirred 30 minutes；It is put into after suction filtration in 150 DEG C of vacuum drying chambers and dries 12h, is made micro- in lamella
Diplopore HKUST-1 materials, labeled as sample B.
Embodiment 3
In the mixed solution that 0.293g ZnO are dissolved in 8mL deionized waters and 16mL DMFs, ultrasound 15
Minute, obtain ZnO solution；1.74g Gerhardites are dissolved in 18mL deionized waters and stirred 20 minutes, copper nitrate are obtained molten
Liquid；ZnO solution and copper nitrate solution are mixed 5 minutes, the mixed solution of ZnO and copper nitrate is obtained；By the equal benzene front threes of 0.84g
Acid and 6.6g hexadecane bromides, which are dissolved in 16mL ethanol, to be stirred 20 minutes, obtains template solution；By template solution and ZnO and nitre
The mixed solution mixing of sour copper, is stirred 30 minutes；It is put into after suction filtration in 150 DEG C of vacuum drying chambers and dries 12h, is made micro- in lamella
Diplopore HKUST-1 materials, labeled as sample C.
Micro-diplopore HKUST-1 materials are analyzed as representative in the lamella prepared using embodiment 1,3, prepared by other embodiments
HKUST-1 materials the basic be the same as Example 1,3 of analysis result, do not provide one by one.
(1) using the crystal structure properties of micro-diplopore HKUST-1 in neutral template normal temperature synthesis lamella
The D8-ADVANCE models X-ray diffractometer produced using German Bruker companies is to the embodiment of the present invention 1,3
Crystal structure is characterized.
Fig. 1 is the middle micro-diplopore prepared using the HKUST-1 materials and the embodiment of the present invention 1,3 of conventional hydrothermal method synthesis
The Wide angle X-ray diffraction figure of HKUST-1 materials.From figure 1 it appears that compared with the HKUST-1 materials of simulation, embodiment 1,
3 sample A, C prepared occur in that the characteristic diffraction peak of stronger HKUST-1 metal organic frameworks, illustrate there is height in product
The HKUST-1 components of crystallinity.
(2) using the SEM figures of micro-diplopore HKUST-1 materials in neutral template normal temperature synthesis lamella
The product of embodiment 1, embodiment 3 is carried out using JSM-6330F types ESEM (electronics corporation JEOL, Japan)
Characterize, as a result as shown in Fig. 2, Fig. 5.Can be seen that by Fig. 2, Fig. 5 has in sample A, C presentation lamellar structure of preparation, material
Even micropore, mesopore orbit, mesoporous cell walls are made up of microporous crystal.
(3) pore properties
The ASAP2460 produced using Micro companies of the U.S. is than surface apertures distribution instrument to sample A, C prepared by the present invention
Pore structure characterized, as a result as shown in table 1.As can be seen from Table 1, the present invention prepared by HKUST-1 materials have compared with
High mesoporous pore volume.
Table 1
Fig. 3, Fig. 6 are the embodiment of the present invention 1, the N of the middle micro-diplopore HKUST-1 materials of the preparation of embodiment 32Adsorption-desorption
Isollaothermic chart, in P/P0<I type adsorption isotherms are shown as under 0.01 pressure, adsorbance steeply rises, and shows that sample has micropore
Structure.There are IV type adsorption hysteresis rings in relative pressure 0.5 or so, this is mesoporous material in N2Typical case in adsorption desorption curve is special
Levy, show containing mesoporous material.
Fig. 4, Fig. 7 are embodiment 1, the graph of pore diameter distribution of the middle micro-diplopore HKUST-1 materials of the preparation of embodiment 3.Show in figure
Show embodiment 1, embodiment 3 prepare middle micro-diplopore HKUST-1 materials in addition to possessing a large amount of 0.8nm or so micropore canals,
Also possess a large amount of 40nm or so mesoporous and bigger macropore duct simultaneously.
Above-described embodiment is comparatively ideal embodiment of the invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, it is simple
Change, should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (7)
1. a kind of method using micro-diplopore HKUST-1 materials in neutral template normal temperature synthesis lamella, it is characterised in that including
Following steps：
（1）In the mixed solution that ZnO is dissolved in deionized water and DMF, ultrasound obtains ZnO solution；
（2）Gerhardite is dissolved in deionized water, clarification is stirred well to, obtains copper nitrate solution；
（3）By step（1）ZnO solution and step（2）Copper nitrate solution mixing, stirring, obtain mixed solution；
（4）Trimesic acid and template hexadecane bromide are dissolved in ethanol, stirs, obtains template solution；
（5）By step（3）Mixed solution and step（4）Template solution mixing, stirring；
（6）By step（5）Products therefrom suction filtration, products therefrom is put into vacuum drying chamber and dried, and micro-diplopore in lamella is made
HKUST-1 materials.
2. according to the method described in claim 1, it is characterised in that：Step（1）The ultrasonic time is 10-20 minutes.
3. according to the method described in claim 1, it is characterised in that：Step（2）, step（4）The time of the stirring is 10-30
Minute.
4. according to the method described in claim 1, it is characterised in that：Step（3）The time of the stirring is 1-10 minutes.
5. according to the method described in claim 1, it is characterised in that：Step（5）The time of the stirring is 20-40 minutes.
6. according to the method described in claim 1, it is characterised in that：Step（6）The temperature of the drying is 140-150 DEG C, is done
The dry time is 10-12h.
7. according to the method described in claim 1, it is characterised in that：The ZnO, Gerhardite, trimesic acid, 16
Alkyl bromide, N,N-dimethylformamide, ethanol, the mol ratio of deionized water are (0.5-1.5)：(1.5-2.5)：(0.6-1.6)：
(1.0-3.0)：(57.2-58.2)：(75.6-76.6)：(400.7-401.7).
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