CN105237554A - Water-stabilized zinc-copper metal organic frame material and preparation method and application thereof - Google Patents
Water-stabilized zinc-copper metal organic frame material and preparation method and application thereof Download PDFInfo
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- CN105237554A CN105237554A CN201510699019.4A CN201510699019A CN105237554A CN 105237554 A CN105237554 A CN 105237554A CN 201510699019 A CN201510699019 A CN 201510699019A CN 105237554 A CN105237554 A CN 105237554A
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Abstract
The invention relates to a water-stabilized zinc-copper metal organic frame material and a preparation method and application thereof. The water-stabilized zinc-copper metal organic frame material has the chemical formula of ZnxCu1-xBIm, wherein x is smaller than 1. ZnxCu1-xBIm is shown as the structural formula (please see the formula in the specification), wherein zinc or copper occupies metal sites of ZnxCu1-xBIm. The preparation method includes the steps of firstly, mixing organic ligand BIm, Zn(NO3)2.6H2O and Cu(NO3)2 to be dissolved into DMF or the mixed solvent of DMF and ethyl alcohol with the volume ratio between 4 to 1 and 3 to 1, wherein the ratio of the molar weight ratio of BIm to the total molar weight of Zn(NO3)2.6H2O and Cu(NO3)2 is 1 to 1, the molar ratio of Zn(NO3)2.6H2O to Cu(NO3)2 is between 99 to 1 and 85 to 15; secondly, making the materials react for 24-72 h at a temperature of 100-140 DEG C or adding auxiliaries to react to generate solid products, cooling to the room temperature, and conducting filtering, DMF washing and drying. The water-stabilized zinc-copper metal organic frame material can be used as carbon dioxide adsorbent, has high water stability, acid stability and thermal stability, has a high porous property, has a high BET specific surface area and high CO2 adsorption capacity, and has potential application on the aspects of the greenhouse effect and the like.
Description
Technical field
The present invention relates to the coordination chemistry direction of chemical field, main contents are metal-organic framework material, zinc-copper metal-organic framework material of mixing metal that especially a kind of novel water is stable and preparation method thereof and application.
Background technology
Metal organic frame (Metal-OrganicFrameworks, MOFs) or Porous coordination polymer be interconnected by stronger coordinate bond by metal ion and organic part, the class formed has the crystalline state frame material of permanent porosity, the superior part of this material and traditional inorganic porous material is by changing metal ion and part changes frame topological structure, hole size and surface properties, and can have superior physicochemical property.
Within 1999, to synthesize and since reporting metal-organic framework material (MOF-5) from American scientist OmarM.Yaghi, this porous material with extra specific surface area just causes the extensive concern of scientists, and scientists have also discovered it have huge potential application in gas storage, separation, catalysis, magnetic and pharmaceutical carrier etc. subsequently.Due to the cause that coordinate bond is more weak, metal-organic framework material is but faced with the problem of a stability.The water stability of this kind of material is poor, easily framework is caused to cave in the water reaction in air, only have a small amount of metal-organic framework material can have very high water to stablize, as the material of famous ZIF-8 and containing metal zirconium, these materials are by adding hydrophobic group or use the method such as metal ion of difficult hydrolysis to improve water stability in part.Therefore the water stability material that preparation invention is new has very important effect for promotion metal-organic framework material.
Chinese patent CN102241695A discloses a series ofly has the metal-organic framework material STU-1 of three-dimensional spiral duct and BSV topological framework, the synthesis of STU-2, STU-3 and STU-4.But find that this series metal organic framework materials is unstable under hydrothermal conditions, other thing phase can be become by hydrolysis, therefore need to strengthen its water stability further by modification.
Summary of the invention
The zinc that the object of the present invention is to provide a kind of water stable-copper metal-organic framework material and preparation method thereof and application.
To achieve these goals, following technical scheme is adopted:
Zinc-copper metal-organic framework material that water is stable, has chemical general formula Zn
xcu
1-xbIm; Described x is less than 1; Described Zn
xcu
1-xbIm structural representation is as follows:
X is the number in the chemical general formula of zine ion, and the number of cupric ion is 1-x, BIm is two-4-imidazoles methyne diamines, and zinc or copper occupy described Zn
xcu
1-xthe metallic site of BIm.Because zinc or copper occupy metallic site jointly, add the hydrophobicity in duct, Cu and Zn is stronger with the coordinate bond of imidazoles, and zinc and the mutual coordinative role of copper make coordinate bond more strengthen, and the frame topological structure of formation has higher stability.Therefore there is higher chemistry and thermostability.
Further, described Zn
xcu
1-xbIm has spiral tetrahexahedron structure, is the 3 D pore canal of mirror image containing left hand helix and right-handed helix.Its skeleton construction has with the identical three-dimensional net structure of STU-1 with BSV molecular sieve.
Further, described x is 0.99-0.85.
A preparation method for zinc-copper metal-organic framework material that water is stable, comprises the steps:
(1) by organic ligand BIm and Zn (NO
3)
26H
2o and Cu (NO
3)
2dissolving in DMF or volume ratio after mixing is in the DMF of 4:1-3:1 and the mixed solvent of ethanol, wherein BIm and Zn (NO
3)
26H
2o and Cu (NO
3)
2the ratio of integral molar quantity be 1:1, Zn (NO
3)
26H
2o and Cu (NO
3)
2mol ratio is 99:1 ~ 85:15;
(2) react 24-72h at 100 ~ 140 DEG C in flask or in horminess glass tube, filter after cool to room temperature, collecting precipitation also washs with DMF, dry.
Wherein DMF is DMF.Present method is solvent-thermal method, and the used time is longer, but can obtain the good large-particle monocrystal of crystal mass.
Water stablizes another preparation method of zinc-copper metal-organic framework material, comprises the steps:
(1) by organic ligand BIm and Zn (NO
3)
26H
2o and Cu (NO
3)
2dissolving in DMF or volume ratio after mixing is in the DMF of 4:1-3:1 and the mixed solvent of ethanol, wherein BIm and Zn (NO
3)
26H
2o and Cu (NO
3)
2the ratio of integral molar quantity be 1:1, Zn (NO
3)
26H
2o and Cu (NO
3)
2mol ratio is 99:1 ~ 85:15;
(2) add after auxiliary agent reaction generates solid product again and filter, collecting precipitation also washs with DMF, dry.
Further, described auxiliary agent is triethylamine/normal hexane mixing solutions, and the reaction conditions of described reaction is for spread at normal temperatures.Normal temperature diffusion process, simple and easy to get, but more difficult control speed of response.Normal hexane is non-good solvent, to reduce compound solvability in the solution, thus separates out crystalline, powder.The effect of triethylamine is to provide alkaline environment, makes the imidazoles in part slough proton (hydrogen atom) thus obtain MOFs with metal-complexing further.
Further, described auxiliary agent is triethylamine, and the mol ratio of described triethylamine and described BIm is 2:1-10:1.
Further, the reaction conditions of described reaction heats for mixture is placed in microwave oven.Microwave method resultant velocity is the fastest, but composite crystals particle is little.
Further, the reaction conditions of described reaction for first to grind 10min, more dropwise drips triethylamine, then grinds 30min.Polishing is a kind of newer synthetic method, and pollute little, energy consumption is low, meet the research direction of Green Chemistry, but productive rate is not high.
The application of described zinc-copper metal-organic framework material, as carbon dioxide absorber.Good adsorption performance under 0 DEG C of normal pressure.Every gram the highest absorption 80.0 milliliters.
Compared with prior art, the present invention has high water stability, ph stability, thermostability and porous character.There is three-dimensional spiral duct there is higher BET specific surface area, there is higher CO
2adsorptive capacity, will have potential application, have a good application prospect at material science in solution Greenhouse effect etc.
Accompanying drawing explanation
Fig. 1 is the structural representation of the stable zinc-copper metal-organic framework material of water of the present invention;
Fig. 2 is three kinds of metal-organic framework material Zn in the present invention
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10the powder diagram of BIm;
Fig. 3 is three kinds of metal-organic framework material Zn in the present invention
0.99cu
0.01bim, Zn
0.95cu
0.05bim and Zn
0.90cu
0.10the ICP data histograms of BIm;
Fig. 4 is three kinds of metal-organic framework material Zn in the present invention
0.99cu
0.01bim, Zn
0.95cu
0.05bim and Zn
0.90cu
0.10the EDS data histograms of BIm;
Fig. 5 is metal-organic framework material Zn in the present invention
0.99cu
0.01the thermogravimetic analysis (TGA) figure of BIm;
Fig. 6 is metal-organic framework material Zn in the present invention
0.95cu
0.05the thermogravimetic analysis (TGA) figure of BIm;
Fig. 7 is metal-organic framework material Zn in the present invention
0.90cu
0.10the thermogravimetic analysis (TGA) figure of BIm;
Fig. 8 is three kinds of metal-organic framework material Zn in the present invention
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10bIm, soaks certain hour powder diagram in normal temperature;
Fig. 9 is Zn
0.99cu
0.01bIm is immersed in the powder diagram in boiling water after 7d;
Figure 10 is Zn
0.95cu
0.05bIm is immersed in the powder diagram in boiling water after 7d;
Figure 11 is Zn
0.90cu
0.10bIm is immersed in the powder diagram in boiling water after 7d;
Figure 12 is Zn
0.99cu
0.01at BIm is immersed in 100 DEG C, pH is the powder diagram in the aqueous solution of 3 after 24h;
Figure 13 is Zn
0.95cu
0.05at BIm is immersed in 100 DEG C, pH is the powder diagram in the aqueous solution of 3 after 24h;
Figure 14 is Zn
0.90cu
0.10at BIm is immersed in 100 DEG C, pH is the powder diagram in the aqueous solution of 3 after 24h;
Figure 15 is Zn
0.99cu
0.01at BIm is immersed in 100 DEG C, pH is the powder diagram in the aqueous solution of 13 after 24h;
Figure 16 is Zn
0.95cu
0.05at BIm is immersed in 100 DEG C, pH is the powder diagram in 13 aqueous solution after 24h;
Figure 17 is Zn
0.90cu
0.10at BIm is immersed in 100 DEG C, pH is the powder diagram in the aqueous solution of 13 after 24h;
Figure 18 is Zn
0.90cu
0.10bIm is immersed in the powder diagram in the organic solvent of multiple boiling or 100 DEG C after 24h;
Figure 19 is metal-organic framework material Zn in the present invention
0.90cu
0.10the CO of BIm
2adsorption curve;
Figure 20 is metal-organic framework material Zn in the present invention
0.90cu
0.10the N of BIm
2adsorption curve;
Figure 21 is all metal-organic framework material Zn in the present invention
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm, Zn
0.90cu
0.10the water vapor adsorption curve of BIm and STU-1.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1
(1) Zn
0.99cu
0.01the preparation of BIm.
By 883.49mg and 2.97mmolZn (NO
3)
26H
2cu (the NO of O, 7.248mg and 0.03mmol
3)
2be dissolved in 160mLDMF and 40mL ethanol with the organic ligand BIm of 564.6mg and 3mmol, at 100 DEG C, react 72h, be then cooled to room temperature.Filter and obtain product, productive rate with 60mLDMF washing, drying: 91.16%.Structure as shown in Figure 1, has chemical general formula Zn
xcu
1-xbIm(x < 1), zinc or copper occupy Zn
0.99cu
0.01the metallic site of BIm, has spiral tetrahexahedron structure, is the 3 D pore canal of mirror image containing left hand helix and right-handed helix.
(2) Zn
0.95cu
0.05the preparation of BIm.
By the Zn (NO of 847.79mg and 2.85mmol
3)
26H
2cu (the NO of O, 36.24mg and 0.15mmol
3)
2be dissolved in 150mLDMF and 50mL ethanol with the organic ligand BIm of 564.6mg and 3mmol, at 100 DEG C, react 72h, be then cooled to room temperature.Filter and obtain target product, productive rate with 60mLDMF washing, drying: 90.28%.Structure as shown in Figure 1, has chemical general formula Zn
xcu
1-xbIm(x < 1), zinc or copper occupy Zn
0.95cu
0.05the metallic site of BIm, has spiral tetrahexahedron structure, is the 3 D pore canal of mirror image containing left hand helix and right-handed helix.
(3) Zn
0.90cu
0.10the preparation of BIm.
By the Zn (NO of 803.17mg and 2.70mmol
3)
26H
2cu (the NO of O, 72.48mg and 0.30mmol
3)
2, the organic ligand BIm of 564.6mg and 3mmol is dissolved in 150mLDMF and 50mL ethanol, reacts 72h, be then cooled to room temperature at 100 DEG C.Filter and obtain product, productive rate with 60mLDMF washing, drying: 92.61%.Structure as shown in Figure 1, has chemical general formula Zn
xcu
1-xbIm(x < 1), zinc or copper occupy Zn
0.90cu
0.10the metallic site of BIm, has spiral tetrahexahedron structure, is the 3 D pore canal of mirror image containing left hand helix and right-handed helix.
(4) Zn
0.85cu
0.15the preparation of BIm.
By the Zn (NO of 8.50mmol
3)
26H
2cu (the NO of O, 1.5mmol
3)
2, the organic ligand BIm of 10mmol is dissolved in 600mLDMF solution, reacts 72h, be then cooled to room temperature at 100 DEG C.Filter and obtain product, productive rate with 180mLDMF washing, drying: 94.61%.Structure as shown in Figure 1, has chemical general formula Zn
xcu
1-xbIm(x < 1), zinc or copper occupy Zn
0.85cu
0.15the metallic site of BIm, has spiral tetrahexahedron structure, is the 3 D pore canal of mirror image containing left hand helix and right-handed helix.
(5) Zn
0.99cu
0.01the preparation of BIm.
By the Zn (NO of 9.90mmol
3)
26H
2cu (the NO of O, 0.10mmol
3)
2, the organic ligand BIm of 10mmol is dissolved in 600mLDMF solution, reacts 72h, be then cooled to room temperature at 100 DEG C.Filter and obtain product, productive rate with 180mLDMF washing, drying: 87.33%.Structure as shown in Figure 1, has chemical general formula Zn
xcu
1-xbIm(x < 1), zinc or copper occupy Zn
0.99cu
0.01the metallic site of BIm, has spiral tetrahexahedron structure, is the 3 D pore canal of mirror image containing left hand helix and right-handed helix.
Embodiment 2
Different methods prepares Zn
0.99cu
0.01bIm.
Method 1:
By 11.78mg and 0.0396mmolZn (NO
3)
26H
2o, 0.09664mg and 0.0004mmolCu (NO
3)
2be dissolved in 2mLDMF and 0.5mL ethanol with 7.45mg and 0.04mmol organic ligand BIm, solution be transferred in flask, after sealing, put into baking oven, at 140 DEG C, react 24h, be then cooled to room temperature with the speed of 5 DEG C/h.Filter and obtain light green bulk crystals, productive rate with DMF washing: 50.25%.
Method 2:
By 11.78mg and 0.0396mmolZn (NO
3)
26H
2o, 0.09664mg and 0.0004mmolCu (NO
3)
2be dissolved in 2mLDMF and 0.5mL ethanol with 7.45mg and 0.04mmol organic ligand BIm, solution be transferred in horminess glass tube that internal diameter is 8mm, put into baking oven after sealing, at 100 DEG C, react 72h, be then cooled to room temperature with the speed of 5 DEG C/h.Filter and obtain light green bulk crystals, productive rate with DMF washing: 51.68%.
Method 3:
By 156.08mg and 0.5247mmolZn (NO
3)
26H
2o, 1.28mg and 0.0053mmolCu (NO
3)
2be dissolved in 25.0mLDMF with 100.00mg and 0.53mmol organic ligand BIm, and solution is on average poured in 5 phials, separately get 1.0mL triethylamine and 25.0mL normal hexane in a carboy, above-mentioned 5 phials are placed in large bottle spread at normal temperatures, light green crystallite will be obtained after 3d, solid filtering is used respectively 15mLDMF and 15mL methanol wash three times, after drying, obtain product Zn
0.99cu
0.01bIm, productive rate: 77.40%.
Method 4:
By 156.08mg and 0.5247mmolZn (NO
3)
26H
2o, 1.28mg and 0.0053mmolCu (NO
3)
2100.00mg and 0.53mmol organic ligand BIm is dissolved in 50.0mL methyl alcohol, dropwise adds 0.265mmol triethylamine, and will obtain shallow green powder by after mixture stirring at normal temperature 24h, solid filtering is used respectively 15.0mLDMF and 15.0mL methanol wash three times, obtain product Zn
0.99cu
0.01bIm, productive rate: 75.23%.
Method 5:
By 78.04mg and 0.26mmolZn (NO
3)
26H
2o, 0.64mg and 0.0026mmolCu (NO
3)
2be dissolved in 15.0mL methyl alcohol with 50.00mg and 0.26mmol organic ligand BIm, dropwise add 0.265mmol triethylamine, and mixture is placed in microwave oven to obtain shallow green powder after 200W power heating 10min, solid filtering is also used 10mLDMF and 10mL methanol wash three times, obtains product Zn
0.99cu
0.01bIm, productive rate: 84.75%.
Method 6:
By 156.08mg and 0.5247mmolZn (NO
3)
26H
2o, 1.28mg and 0.0053mmolCu (NO
3)
2, 100.00mg and 0.53mmol organic ligand BIm grinds 10min in mortar, dropwise drips 0.053mmol triethylamine grind 30min, obtains shallow green powder, by solid 15mLDMF and 15mL methanol wash three times, obtains product Zn
0.99cu
0.01bIm, productive rate: 27.30%.
The Zn that different methods prepares
0.99cu
0.01as shown in Figure 1, zinc or copper occupy Zn to BIm structure
0.99cu
0.01the metallic site of BIm, has spiral tetrahexahedron structure, is the 3 D pore canal of mirror image containing left hand helix and right-handed helix.
Embodiment 3
Embodiment 1 and embodiment 2 are prepared the carrying out that zinc-copper mixes each performance of the metal-organic framework material of metal to characterize.
1, powdery diffractometry characterizes purity:
By Zn
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10bIm sample powder Diffraction Data Collection completes on BrukerD8advance diffractometer, the operating voltage of instrument is 40KV, and electric current is 40mA, uses graphite monochromatised copper target X-ray (CuK, λ=1.5418), within the scope of 5 ° to 40 °, continuous sweep completes.Single crystal structure powdery diffractometry spectrum analog transforms and uses Mercury software.From the known the present invention of the powder diffraction data of Fig. 2, three kinds of materials are isomorphisms.
2, the mensuration of metal ion content in zinc-copper metal organic frame.
(1) inductively coupled plasma atomic emission spectrometry (ICP)
1.0mg title complex sample 3 ~ 4 concentrated nitric acids are dissolved, be made into 25.0mL solution, use full spectrum ICP emission spectrometer (ICPE-9000) to test the metal ion in this solution, can be calculated the metal ion content ratio in zinc-copper metal organic frame.
ICP data as Fig. 3, Zn in the present invention as we know from the figure
0.99cu
0.01in BIm, the content of zine ion is 99.12%, and the content of cupric ion is 0.88%; Zn
0.95cu
0.05in BIm, the content of zine ion is 94.62%, and the content of cupric ion is 5.38%; Zn
0.90cu
0.10in BIm, the content of zine ion is 88.42%, and the content of cupric ion is 11.58%.
(2) X-ray energy spectrometer measures (EDS)
Use analysis mode scanning electron microscope (JSM-6360LA) to measure single crystal in title complex, obtain metal ion ratio and make histogram.Known by test result, containing zine ion, cupric ion two metal ion species in same crystal.
EDS data as Fig. 4, Zn in the present invention as we know from the figure
0.99cu
0.01in BIm, the content of zine ion is 96.95%, and the content of cupric ion is 3.05%; Zn
0.95cu
0.05in BIm, the content of zine ion is 93.91%, and the content of cupric ion is 6.09%; Zn
0.90cu
0.10in BIm, the content of zine ion is 89.19%, and the content of cupric ion is 10.81%.
The stability test of 3, zinc-copper metal-organic framework material.
(1) thermal stability determination
Utilize the hot synthesis analyzer of TAQ-50 of TA instrument company of the U.S. to carry out thermal property analysis, under nitrogen protection, measuring tempeature scope is 25-800 DEG C, and per minute heats 10 DEG C.
Thermogravimetic analysis (TGA) data as Fig. 5, Fig. 6 and Fig. 7, by Zn known in figure
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10bIm respectively when 375 DEG C, 405 DEG C and 380 DEG C skeleton start to cave in, three kinds of materials in visible the present invention have higher thermostability.
(2) normal-temperature water stability test
Get the Zn of 20.0mg
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10bIm sample, in flask, adds 10.0mL water, by powder diffractometer stability to solid sample tests after soaking certain hour in normal temperature.Test result as shown in Figure 8, has the water stability of superelevation, and is better than most of same type of material from the metal-organic framework material the known the present invention of data.
(3) stability test in boiling water
Get 100.0mgZn
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10bIm sample is in flask, add 50.0mL water, 7d is reacted after ebuillition of heated, and after 7d, take out sample powder diffractometer test, test result is as Fig. 9, Figure 10, Figure 11, there is from the metal-organic framework material the known the present invention of data the water stability of superelevation, and be better than most of same type of material.
(4) acidic solution stability test
Get 100.0mgZn
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10bIm sample, in flask, adds the aqueous solution that 50.0mLpH is 3, reacts 24h after ebuillition of heated, and reacted solid sample powder diffractometer is tested its acidic solution stability.Test result, as Figure 12, Figure 13, Figure 14, has higher acid acceptance from the metal-organic framework material the known the present invention of data.
(5) basic solution stability test
Get 100.0mgZn
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10bIm sample, in flask, adds the aqueous solution that 50.0mLpH is 13, reacts 24 hours, reacted solid sample powder diffractometer is tested its basic solution stability after ebuillition of heated.Test result, as Figure 15, Figure 16, Figure 17, has higher alkaline stability from the metal-organic framework material the known the present invention of data.
(6) stability test seethed with excitement in organic solvent
Get 100.0mgZn
0.90cu
0.10bIm sample is in flask, add 50.0mL organic solvent solution (being respectively dimethyl sulfoxide (DMSO), methyl alcohol, tetrahydrofuran (THF), benzene, normal hexane), ebuillition of heated (or 100 DEG C) reacts 24 hours afterwards, reacted solid sample powder diffractometer is tested its stability in boiling solvent.Test result as Figure 18, the Zn from the known the present invention of experimental data
0.90cu
0.10bIm can keep stable in multiple common boiling organic solvent, and this also for providing feasibility study in the future in industrial application.
4, gas adsorption test.
The metal-organic framework material Zn that 100.0mg has just been synthesized
0.90cu
0.10after BIm exchanges 3d in 30.0mL methyl alcohol, vacuum activating 10h at 120 DEG C, then use the full-automatic specific surface of Micromeritics company and the CO of Porosimetry sample
2and N
2adsorptive capacity measures; And use the intelligent weight adsorption system (IGA100B) of Hiden company to carry out water vapor adsorption mensuration to sample.
Figure 19 is temperature CO when being 273K
2adsorption curve figure, the Zn as we know from the figure in the present invention
0.90cu
0.10bIm has higher CO a standard atmosphere pressure
2adsorptive capacity.Zn
0.99cu
0.01bIm, Zn
0.95cu
0.05bIm and Zn
0.90cu
0.10bIm all has higher CO at normal temperatures and pressures
2adsorptive capacity.Material as can be seen here in the present invention can as carbon dioxide absorber, will have potential application in solution Greenhouse effect etc.
The adsorption curve figure of water vapour when Figure 21 is temperature 298K, in the present invention, the water vapor adsorption amount of material is extremely low as we know from the figure, compared with STU-1, there is hydrophobicity in larger duct, water molecules is difficult to enter in duct and forms water bunch and the title complex that hydrolized metal ion and imidazole ligands are formed, thus improves the water stability of this material.
5, the mensuration of specific surface area.
The metal-organic framework material Zn that 100.0mg has just been synthesized
0.90cu
0.10after BIm exchanges 3d in 30.0mL ethanol, vacuum activating 10h at 100 DEG C, more respectively the sample before and after reaction is measured with the full-automatic specific surface of Micromeritics company and Porosimetry.
The N that Figure 20 is temperature when being 77K
2adsorption curve figure, by learning Zn in the present invention to the calculating of data
0.90cu
0.10the BET specific surface area of BIm is 948.08m
3/ g.Test result shows that the material in the present invention has higher BET specific surface area.
Above disclosedly be only preferred embodiment of the present invention, certainly can not limit the interest field of the present invention with this, therefore according to the equivalent variations that the claims in the present invention are done, still belong to the scope that the present invention is contained.
Claims (10)
1. zinc-copper metal-organic framework material that water is stable, is characterized in that, described zinc-copper metal-organic framework material has chemical general formula Zn
xcu
1-xbIm; Described x is less than 1; Described Zn
xcu
1-xbIm structural representation is as follows:
Zinc or copper occupy described Zn
xcu
1-xthe metallic site of BIm.
2. zinc-copper metal-organic framework material according to claim 1, is characterized in that, described Zn
xcu
1-xbIm has spiral tetrahexahedron structure, is the 3 D pore canal of mirror image containing left hand helix and right-handed helix.
3. zinc-copper metal-organic framework material according to claim 1, it is characterized in that, described x is 0.99-0.85.
4. the preparation method of zinc-copper metal-organic framework material according to any one of claim 1-3, is characterized in that, comprise the steps:
(1) by organic ligand BIm and Zn (NO
3)
26H
2o and Cu (NO
3)
2adding DMF or volume ratio after mixing is in the DMF of 4:1-3:1 and the mixed solvent of ethanol, wherein BIm and Zn (NO
3)
26H
2o and Cu (NO
3)
2the ratio of integral molar quantity be 1:1, Zn (NO
3)
26H
2o and Cu (NO
3)
2mol ratio is 99:1 ~ 85:15;
(2) react 24-72h at 100 ~ 140 DEG C in flask or in horminess glass tube, filter after cool to room temperature, collecting precipitation also washs with DMF, dry.
5. the preparation method of zinc-copper metal-organic framework material according to any one of claim 1-3, is characterized in that, comprise the steps:
(1) by organic ligand BIm and Zn (NO
3)
26H
2o and Cu (NO
3)
2dissolving in DMF or volume ratio after mixing is in the DMF of 4:1-3:1 and the mixed solvent of ethanol, wherein BIm and Zn (NO
3)
26H
2o and Cu (NO
3)
2the ratio of integral molar quantity be 1:1, Zn (NO
3)
26H
2o and Cu (NO
3)
2mol ratio is 99:1 ~ 85:15;
(2) add after auxiliary agent reaction generates solid product again and filter, collecting precipitation also washs with DMF, dry.
6. preparation method according to claim 5, it is characterized in that, described auxiliary agent is triethylamine/normal hexane mixing solutions, and the reaction conditions of described reaction is for spread at normal temperatures.
7. preparation method according to claim 5, it is characterized in that, described auxiliary agent is triethylamine, and the mol ratio of described triethylamine and described BIm is 2:1-10:1.
8. preparation method according to claim 7, it is characterized in that, the reaction conditions of described reaction heats for mixture is placed in microwave oven.
9. preparation method according to claim 7, it is characterized in that, the reaction conditions of described reaction for first to grind 10min, more dropwise drips triethylamine, then grinds 30min.
10. the application of zinc-copper metal-organic framework material according to any one of claim 1-3, is characterized in that, as carbon dioxide absorber.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106706742A (en) * | 2017-01-09 | 2017-05-24 | 广西民族大学 | Method for preparing high-sensitivity piribedil molecular imprinting electrochemical transducer |
| CN109438717A (en) * | 2018-09-21 | 2019-03-08 | 暨南大学 | A kind of metal-organic framework material and its preparation method and application |
| CN110433867A (en) * | 2019-08-30 | 2019-11-12 | 济南大学 | A kind of preparation method and application of chirality Cu/Zn-MOF/NiF nano-composite catalyst |
| CN112795023A (en) * | 2019-10-28 | 2021-05-14 | 暨南大学 | Ultra-stable metal organic framework material and preparation method and application thereof |
| CN117362660A (en) * | 2023-08-31 | 2024-01-09 | 中山大学 | Metal organic framework material Zr-MOF, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
| CN103691398A (en) * | 2013-12-13 | 2014-04-02 | 北京化工大学常州先进材料研究院 | Carbon dioxide adsorbent and preparation method thereof |
| CN104415737A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院大连化学物理研究所 | Magnesium-based metal organic framework material for methane-nitrogen adsorption separation and preparation |
-
2015
- 2015-10-26 CN CN201510699019.4A patent/CN105237554A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962037A (en) * | 2012-11-01 | 2013-03-13 | 中国科学院大连化学物理研究所 | Metal-organic framework material for methane adsorption separation and preparation method thereof |
| CN104415737A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院大连化学物理研究所 | Magnesium-based metal organic framework material for methane-nitrogen adsorption separation and preparation |
| CN103691398A (en) * | 2013-12-13 | 2014-04-02 | 北京化工大学常州先进材料研究院 | Carbon dioxide adsorbent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAO-PING ZHOU等: "Gyroidal Metal-Organic Frameworks", 《J. AM. CHEM. SOC.》 * |
| 朱晓威等: "具有超高水稳定性的 Gyroidal金属有机框架", 《中国化学会第九届全国无机化学学术会议论文集－B配位化学》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106706742A (en) * | 2017-01-09 | 2017-05-24 | 广西民族大学 | Method for preparing high-sensitivity piribedil molecular imprinting electrochemical transducer |
| CN109438717A (en) * | 2018-09-21 | 2019-03-08 | 暨南大学 | A kind of metal-organic framework material and its preparation method and application |
| CN109438717B (en) * | 2018-09-21 | 2021-07-23 | 暨南大学 | Metal organic framework material and preparation method and application thereof |
| CN110433867A (en) * | 2019-08-30 | 2019-11-12 | 济南大学 | A kind of preparation method and application of chirality Cu/Zn-MOF/NiF nano-composite catalyst |
| CN110433867B (en) * | 2019-08-30 | 2022-01-04 | 济南大学 | Preparation method and application of chiral Cu/Zn-MOF/NiF nano composite catalyst |
| CN112795023A (en) * | 2019-10-28 | 2021-05-14 | 暨南大学 | Ultra-stable metal organic framework material and preparation method and application thereof |
| CN117362660A (en) * | 2023-08-31 | 2024-01-09 | 中山大学 | Metal organic framework material Zr-MOF, and preparation method and application thereof |
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