CN108671892A - A kind of metal organic framework UiO-66 adsorbents and its modified material - Google Patents
A kind of metal organic framework UiO-66 adsorbents and its modified material Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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Abstract
The present invention relates to a kind of 66 adsorbents of metal organic framework UiO and its modified materials, the adsorbent is prepared using the hot method of conventional solvent, it is dissolved in solvent after zirconium source is mixed with organic ligand, it is added in the stainless steel cauldron with polytetrafluoroethyllining lining and reacts after being completely dissolved, the substance formed after reaction is washed with organic solvent, is filtered, obtained solid obtains target affinity agent after drying, and the aperture of adsorbent is 1.4~2.0nm, and specific surface area is 885~1500m2/g.Modified adsorbent uses that P123 is template or CTAB is that surface modifier is prepared with one-step method, and products therefrom has the modification UiO 66 of meso-hole structure or 66 adsorbents of UiO with functional group.Sorbent material performance of the present invention is stablized, and the absorption of 298K~373K Toluenes and the absorption of the toluene in high wet atmosphere are can be applied to.
Description
Technical field
The present invention relates to metal organic framework sorbing material fields, and in particular to a kind of metal organic framework UiO-66 absorption
Agent and its modified material.
Background technology
Substance is carried out using absorption method and detaches existing very long history, and adsorbent is to determine dynamical adsorption treatment process
Key factor.Researcher both domestic and external has made this large amount of research work, while improveing conventional adsorbent product, no
Disconnect the adsorbent for sending out novel.Currently, being concentrated mainly on benzene,toluene,xylene and alkane for the research for adsorbing organic gas
Etc. compounds.Due to the huge specific surface area of MOFs materials and Kong Rong so that they there is the absorption of superelevation to hold many gases
It measures, people just attempt to realize the absorption to gas using various MOFs materials at present.In terms of VOCs absorption, MOFs materials have
Great competitive advantage, first its can have higher adsorption capacity at normal temperatures and pressures, in addition, adjustable pore structure size
And its surface-property-modifying can make its selective absorption VOCs.The MOF-5 materials of O.M.Yaghi research groups synthesis, in 295K
Under the conditions of be respectively to the saturated extent of adsorption of VOCs：1211mg/g(CH2Cl2)、1367mg/g(CHCl3)、802mg/g(C6H6)、
1472mg/g(CCl4) and 703mg/g (C6H12)(Eddaoudi M；Li H L；Yaghi O M.Am.Chem.Soc,2000,
1391-1397.), adsorbance is 4-10 times or more of traditional sorbing material (such as activated carbon, molecular sieve), is shown extremely excellent
Different absorption property.Mohamed et al. uses Zn2+With with hydrophobic group (- C2H4) multi-carboxylic acid's organic ligand (R6-
DBC IRMOF-6) is synthesized by complexing, and it is measured to CH under the conditions of 298K2Cl2、CHCl3、C6H6And CCl4Absorption
Thermoisopleth finds that it is higher than MOF-5 to the equilibrium adsorption capacity outline of these four VOCs.The MIL-101 materials that Ferey team develops
In 303K to C6H6And C6H14Saturated extent of adsorption be respectively 12mmol/g and 17mmol/g or so, be much higher than other conventional inhale
The absorption property of attached dose (activated carbon, molecular sieve).Yaghi etc. has chosen MOF-5, IRMOF-3, MOF-74, MOF-177, MOF-
MOFs materials make adsorbent and are compared with BPL activated carbons in 199 and IRMOF-62 etc. 6, study it to 4 kinds of environment harmful gas
(thiophane, C6H6、CH2Cl2And ethylene oxide) absorption property, find：Tri- kinds of materials of IRMOF-3, MOF-74 and MOF-199
The dynamic adsorption capacity of material is 59 times of BPL activated carbons, it was found that vacancy metallic site (IRMOF-74, MOF-199) and amino
Group (IRMOF-3) plays great role in the absorption of pollutant.But existing adsorbent heat stability and hydrothermal stability are past
Past poor, pore structure is inhomogenous, and specific surface area is smaller, cannot be satisfied industrial application requirement.
Invention content
The purpose of the present invention be exactly to solve the above-mentioned problems and provide a kind of metal organic framework UiO-66 adsorbents and
Its modified material.
The purpose of the present invention is achieved through the following technical solutions：
A kind of metal organic framework UiO-66 adsorbents, the adsorbent aperture be 1.4~2.7nm, specific surface area be 794~
1420m2/ g, is prepared using following methods：
(1) zirconium source and organic ligand are weighed, them is made to be dissolved completely in solvent, obtains mixed solution；
(2) mixed solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and is reacted, obtain reaction production
Object；
(3) by the reaction product of gained washing, filtering, dry to get to metal organic framework UiO-66 adsorbents.
Preferably, the zirconium source is one kind in zirconium chloride, zirconium sulfate or zirconium acetate.
Preferably, the organic ligand be selected from trimesic acid, terephthalic acid (TPA), 2,5-Dihydroxyterephthalic acid,
One or more of phthalic acid, succinic acid, trimellitic acid, 1,2,3,4- butane tetracarboxylic acid, oxalic acid or succinic acid.
Preferably, the solvent is one in ethyl alcohol, n,N-Dimethylformamide, n,N-dimethylacetamide or ethylene glycol
Kind is several.
Preferably, step (2) stainless steel cauldron reacts 20~24 hours at 120 DEG C.
A kind of modified material of metal organic framework UiO-66 adsorbents, by surface modifier CTAB to the organic bone of metal
Frame UiO-66 adsorbents are modified, and are specifically prepared using following methods：
(1) zirconium source, organic ligand and CTAB are weighed, them is made to be dissolved completely in solvent, obtains mixed solution；
(2) mixed solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and is reacted, obtain reaction production
Object；
(3) by the washing of the reaction product of gained, filtering, drying, the solid of gained is flowed back with ethyl alcohol using soxhlet extraction
Washing is dried to get the metal organic framework UiO-66 adsorbents being modified to CTAB.
Preferably, the molar ratio of the CTAB and Zr is 1：0.1~10.
A kind of modified material of metal organic framework UiO-66 adsorbents, by P123 be template to metal organic framework
UiO-66 adsorbents are modified, and are specifically prepared using following methods：
(1) P123 is taken to be dissolved in the hydrochloric acid solution of 2mol/L, 35 DEG C of water-baths are completely dissolved；
(2) zirconium source and organic ligand are taken, is dissolved in solvent and mixed solution is made, mixed solution is added drop-wise to P123 dropwise
Hydrochloric acid solution in, 35 DEG C of stirring in water bath 20h, and ethyl alcohol is added during churning；
(3) solution of step (2) is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and is reacted；
(4) by the washing of step (3) products therefrom, filtering, drying, solid product ethyl alcohol is washed using soxhlet extraction reflux
It washs, dry to get the metal organic framework UiO-66 adsorbents being modified to P123.
Preferably, the molar ratio of the P123 and Zr is 1：0.1~0.5.
Compared with prior art, the method have the characteristics that：
(1) use UiO-66 adsorbents prepared by hydro-thermal method that there is preferable thermal stability and hydrothermal stability, it is uniform
Pore structure and high-specific surface area.
(2) with the UiO-66 adsorbents of CTAB modified synthesis, skeleton surface function group has effectively been regulated and controled, has been conducive to wave
Active force between hair property organic molecule and adsorbent, while there is preferable thermal stability and hydrothermal stability, it is uniform
Pore structure and high-specific surface area.
(3) using P123 as the UiO-66 adsorbents of templated synthesis, the pore passage structure of skeleton has effectively been regulated and controled, has been conducive to wave
Diffusion of the hair property organic molecule in duct, while there is preferable thermal stability and hydrothermal stability, uniform pore structure
And high-specific surface area.
(4) UiO-66 adsorbents of the present invention and its modified material, not only have preferable adsorption energy for toluene at room temperature
Power also has certain toluene adsorption capacity, in addition, the adsorbent is also used as CO in 373K2Capture contains sulfur dioxide gas
In the reactions such as the NO_x elimination of atmosphere.
(5) preparation process and equipment of the present invention are simple, reproducible, there is good prospects for commercial application.
Description of the drawings
Fig. 1 is the x-ray diffraction pattern of UiO-66 adsorbents；
Fig. 2 is the N of UiO-66 adsorbents2Adsorption-desorption figure；
Fig. 3 is the graph of pore diameter distribution of UiO-66 adsorbents；
Fig. 4 is the TEM figures of UiO-66 adsorbents；
Fig. 5 is the breakthrough curve of UiO-66 adsorbent room temperature Toluene Dynamic Adsorptions.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
0.053g zirconium chlorides and 0.034g terephthalic acid (TPA)s are weighed, is made it completely dissolved in 5mL n,N-Dimethylformamide
In solvent；Solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and is reacted 24 hours at 120 DEG C；By institute
Product washing, filtering, drying are obtained, solid Zr Base Metal organic framework sorbents UiO-66 is obtained.Its XRD, N2Adsorption-desorption,
Pore-size distribution and TEM results such as Fig. 1, shown in 2,3,4.
The dynamic adsorption capacity evaluation of adsorbent carries out in fixed bed continuously flows differential reactor, and reactor is internal diameter
The glass U-tube of 4mm, adsorbent inventory 200mg, unstripped gas a concentration of 1000ppm, gas flow rate 50ml/min, instead
Toluene after answering in gas passes through the GC-2060 gas chromatograph on-line analyses equipped with hydrogen flame detector, and adsorbance is by penetrating
Curve calculates, and breakthrough curve result is shown in Fig. 5.Test shows the UiO-66 adsorbents agent prepared using this method in room temperature (25
DEG C) there is higher toluene adsorbance.
Embodiment 2
0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, a certain amount of CTAB is weighed for 0.1 by CTAB/Zr molar ratios,
It makes it completely dissolved in 5mL N,N-dimethylformamide solvents；Solution is transferred to the stainless of polytetrafluoroethyllining lining
It is reacted 24 hours at 120 DEG C in steel reaction kettle；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction, which is dried, to be changed
Property adsorbent.The evaluation method of adsorbent is the same as embodiment 1.Test shows that the UiO-66 adsorbent agent prepared using this method is existed
(25 DEG C) of room temperature has higher toluene adsorbance.
Embodiment 3
0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, a certain amount of CTAB is weighed for 0.3 by CTAB/Zr molar ratios,
It makes it completely dissolved in 5mL N,N-dimethylformamide solvents；Solution is transferred to the stainless of polytetrafluoroethyllining lining
It is reacted 24 hours at 120 DEG C in steel reaction kettle；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction, which is dried, to be changed
Property adsorbent.The evaluation method of adsorbent is the same as embodiment 1.Test shows that the UiO-66 adsorbent agent prepared using this method is existed
(25 DEG C) of room temperature has higher toluene adsorbance.
Embodiment 4
0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, a certain amount of CTAB is weighed for 0.5 by CTAB/Zr molar ratios,
It makes it completely dissolved in 5mL N,N-dimethylformamide solvents；Solution is transferred to the stainless of polytetrafluoroethyllining lining
It is reacted 24 hours at 120 DEG C in steel reaction kettle；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction, which is dried, to be changed
Property adsorbent.The evaluation method of adsorbent is the same as embodiment 1.Test shows that the UiO-66 adsorbent agent prepared using this method is existed
(25 DEG C) of room temperature has higher toluene adsorbance.
Embodiment 5
0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, a certain amount of CTAB is weighed for 1 by CTAB/Zr molar ratios, makes
It is dissolved completely in 5mL N,N-dimethylformamide solvents；Solution is transferred to the stainless steel with polytetrafluoroethyllining lining
It is reacted 24 hours at 120 DEG C in reaction kettle；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction, which is dried, to be modified
Adsorbent.The evaluation method of adsorbent is the same as embodiment 1.Test shows the UiO-66 adsorbent agent prepared using this method in room
(25 DEG C) of temperature has higher toluene adsorbance.
Embodiment 6
0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, a certain amount of CTAB is weighed for 3 by CTAB/Zr molar ratios, makes
It is dissolved completely in 5mL N,N-dimethylformamide solvents；Solution is transferred to the stainless steel with polytetrafluoroethyllining lining
It is reacted 24 hours at 120 DEG C in reaction kettle；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction, which is dried, to be modified
Adsorbent.The evaluation method of adsorbent is the same as embodiment 1.Test shows the UiO-66 adsorbent agent prepared using this method in room
(25 DEG C) of temperature has higher toluene adsorbance.
Embodiment 7
0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, a certain amount of CTAB is weighed for 5 by CTAB/Zr molar ratios, makes
It is dissolved completely in 5mL N,N-dimethylformamide solvents；Solution is transferred to the stainless steel with polytetrafluoroethyllining lining
It is reacted 24 hours at 120 DEG C in reaction kettle；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction, which is dried, to be modified
Adsorbent.The evaluation method of adsorbent is the same as embodiment 1.Test shows the UiO-66 adsorbent agent prepared using this method in room
(25 DEG C) of temperature has higher toluene adsorbance.
Embodiment 8
A certain amount of P123 is weighed for 0.1 by P123/Zr molar ratios, is dissolved in 80mL 2mol/L hydrochloric acid solutions, 35 DEG C of water-baths are complete
Fully dissolved.0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, is made it completely dissolved molten in 5mL n,N-Dimethylformamide
In agent, formamide mixed solution is added drop-wise to dropwise in the hydrochloric acid solution containing P123,35 DEG C of stirring in water bath 20h, and stirred
A certain amount of ethyl alcohol is added in period；Solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining at 120 DEG C instead
It answers 24 hours；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction dries to obtain modified adsorbent.The evaluation of adsorbent
Method is the same as embodiment 1.Test shows that the UiO-66 adsorbents agent prepared using this method has higher toluene for (25 DEG C) in room temperature
Adsorbance.
Embodiment 9
A certain amount of P123 is weighed for 0.2 by P123/Zr molar ratios, is dissolved in 80mL 2mol/L hydrochloric acid solutions, 35 DEG C of water-baths are complete
Fully dissolved.0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, is made it completely dissolved molten in 5mL n,N-Dimethylformamide
In agent, formamide mixed solution is added drop-wise to dropwise in the hydrochloric acid solution containing P123,35 DEG C of stirring in water bath 20h, and stirred
A certain amount of ethyl alcohol is added in period；Solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining at 120 DEG C instead
It answers 24 hours；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction dries to obtain modified adsorbent.The evaluation of adsorbent
Method is the same as embodiment 1.Test shows that the UiO-66 adsorbents agent prepared using this method has higher toluene for (25 DEG C) in room temperature
Adsorbance.
Embodiment 10
A certain amount of P123 is weighed for 0.3 by P123/Zr molar ratios, is dissolved in 80mL 2mol/L hydrochloric acid solutions, 35 DEG C of water-baths are complete
Fully dissolved.0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, is made it completely dissolved molten in 5mL n,N-Dimethylformamide
In agent, formamide mixed solution is added drop-wise to dropwise in the hydrochloric acid solution containing P123,35 DEG C of stirring in water bath 20h, and stirred
A certain amount of ethyl alcohol is added in period；Solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining at 120 DEG C instead
It answers 24 hours；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction dries to obtain modified adsorbent.The evaluation of adsorbent
Method is the same as embodiment 1.Test shows that the UiO-66 adsorbents agent prepared using this method has higher toluene for (25 DEG C) in room temperature
Adsorbance.
Embodiment 11
A certain amount of P123 is weighed for 0.4 by P123/Zr molar ratios, is dissolved in 80mL 2mol/L hydrochloric acid solutions, 35 DEG C of water-baths are complete
Fully dissolved.0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, is made it completely dissolved molten in 5mL n,N-Dimethylformamide
In agent, formamide mixed solution is added drop-wise to dropwise in the hydrochloric acid solution containing P123,35 DEG C of stirring in water bath 20h, and stirred
A certain amount of ethyl alcohol is added in period；Solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining at 120 DEG C instead
It answers 24 hours；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction dries to obtain modified adsorbent.The evaluation of adsorbent
Method is the same as embodiment 1.Test shows that the UiO-66 adsorbents agent prepared using this method has higher toluene for (25 DEG C) in room temperature
Adsorbance.
Embodiment 12
A certain amount of P123 is weighed for 0.5 by P123/Zr molar ratios, is dissolved in 80mL 2mol/L hydrochloric acid solutions, 35 DEG C of water-baths are complete
Fully dissolved.0.053g zirconium chlorides, 0.034g terephthalic acid (TPA)s are weighed, is made it completely dissolved molten in 5mL n,N-Dimethylformamide
In agent, formamide mixed solution is added drop-wise to dropwise in the hydrochloric acid solution containing P123,35 DEG C of stirring in water bath 20h, and stirred
A certain amount of ethyl alcohol is added in period；Solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining at 120 DEG C instead
It answers 24 hours；By products therefrom washing, filtering, drying, ethyl alcohol Soxhlet extraction dries to obtain modified adsorbent.The evaluation of adsorbent
Method is the same as embodiment 1.Test shows that the UiO-66 adsorbents agent prepared using this method has higher toluene for (25 DEG C) in room temperature
Adsorbance.
1 UiO-66 of table and its modified adsorbent performance indicator
The absorption property of 2 UiO-66 of table and its modified adsorbent
Claims (9)
1. a kind of metal organic framework UiO-66 adsorbents, which is characterized in that the adsorbent aperture is 1.4~2.7nm, specific surface
Product is 794~1420m2/ g, is prepared using following methods：
(1) zirconium source and organic ligand are weighed, them is made to be dissolved completely in solvent, obtains mixed solution；
(2) mixed solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and is reacted, obtain reaction product；
(3) by the reaction product of gained washing, filtering, dry to get to metal organic framework UiO-66 adsorbents.
2. a kind of metal organic framework UiO-66 adsorbents according to claim 1, which is characterized in that the zirconium source is chlorine
Change one kind in zirconium, zirconium sulfate or zirconium acetate.
3. a kind of metal organic framework UiO-66 adsorbents according to claim 1, which is characterized in that the organic ligand
Selected from trimesic acid, terephthalic acid (TPA), 2,5- dihydric para-phthalic acids, M-phthalic acid, succinic acid, trimellitic acid,
One or more of 1,2,3,4- butane tetracarboxylic acid, oxalic acid or succinic acid.
4. a kind of metal organic framework UiO-66 adsorbents according to claim 1, which is characterized in that the solvent is second
One or more of alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or ethylene glycol.
5. a kind of metal organic framework UiO-66 adsorbents according to claim 1, which is characterized in that step (2) is stainless
Steel reaction kettle reacts 20~24 hours at 120 DEG C.
6. a kind of a kind of modified material of metal organic framework UiO-66 adsorbents as described in claim 1, which is characterized in that
Metal organic framework UiO-66 adsorbents are modified by surface modifier CTAB, are specifically prepared into using following methods
It arrives：
(1) zirconium source, organic ligand and CTAB are weighed, them is made to be dissolved completely in solvent, obtains mixed solution；
(2) mixed solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and is reacted, obtain reaction product；
(3) by the reaction product of gained washing, filtering, dry, the solid of gained with ethyl alcohol using soxhlet extraction reflux washing,
Drying is to get the metal organic framework UiO-66 adsorbents being modified to CTAB.
7. a kind of modified material of metal organic framework UiO-66 adsorbents according to claim 6, which is characterized in that institute
The molar ratio for stating CTAB and Zr is 1：0.1~10.
8. a kind of a kind of modified material of metal organic framework UiO-66 adsorbents as described in claim 1, which is characterized in that
It is that template is modified metal organic framework UiO-66 adsorbents by P123, is specifically prepared using following methods：
(1) P123 is taken to be dissolved in the hydrochloric acid solution of 2mol/L, 35 DEG C of water-baths are completely dissolved；
(2) zirconium source and organic ligand are taken, is dissolved in solvent and mixed solution is made, mixed solution is added drop-wise to the salt of P123 dropwise
In acid solution, 35 DEG C of stirring in water bath 20h, and ethyl alcohol is added during churning；
(3) solution of step (2) is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining and is reacted；
(4) by step (3) products therefrom washing, filtering, dry, solid product with ethyl alcohol using soxhlet extraction reflux washing,
Drying is to get the metal organic framework UiO-66 adsorbents being modified to P123.
9. a kind of modified material of metal organic framework UiO-66 adsorbents according to claim 8, which is characterized in that institute
The molar ratio for stating P123 and Zr is 1：0.1~0.5.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
| WO2010096464A1 (en) * | 2009-02-18 | 2010-08-26 | Boyes Stephen G | Gold/lanthanide nanoparticle conjugates and uses thereof |
| CN105214612A (en) * | 2015-09-18 | 2016-01-06 | 北京化工大学 | A kind of application of metal-organic framework functionalization material |
| CN105693750A (en) * | 2016-03-01 | 2016-06-22 | 青岛大学 | Rapid preparation method of environment-friendly metal-organic framework material |
| CN107694611A (en) * | 2017-09-29 | 2018-02-16 | 中国石油大学(华东) | A kind of preparation and application of grade mesoporous metal organic backbone carried heteropoly acid catalyst |
-
2018
- 2018-04-19 CN CN201810356030.4A patent/CN108671892A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
| WO2010096464A1 (en) * | 2009-02-18 | 2010-08-26 | Boyes Stephen G | Gold/lanthanide nanoparticle conjugates and uses thereof |
| CN105214612A (en) * | 2015-09-18 | 2016-01-06 | 北京化工大学 | A kind of application of metal-organic framework functionalization material |
| CN105693750A (en) * | 2016-03-01 | 2016-06-22 | 青岛大学 | Rapid preparation method of environment-friendly metal-organic framework material |
| CN107694611A (en) * | 2017-09-29 | 2018-02-16 | 中国石油大学(华东) | A kind of preparation and application of grade mesoporous metal organic backbone carried heteropoly acid catalyst |
Non-Patent Citations (2)
| Title |
|---|
| CAVKA, JASMINA HAFIZOVIC ET AL.,: ""A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 秦卫平，: ""甲苯在UIO-66及UIO-66-(CH3)2上的吸附"", 《广东化工》 * |
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