CN108084453A - The aperture expanding method of UiO-66 metal-organic framework materials and application - Google Patents
The aperture expanding method of UiO-66 metal-organic framework materials and application Download PDFInfo
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- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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Abstract
The aperture expanding method of 66 metal-organic framework materials of UiO, comprises the following steps：2.47 parts by weight zirconium chlorides, 1.47 parts by weight terephthalic acid (TPA)s, 95 parts by weight N, N dimethylformamides is taken to be mixed in ultrasonic dissolution in single-necked flask；It is placed in micro-wave oven condensing reflux 15min centrifugations；With ethyl alcohol, N, N dimethylformamides washing solid product takes 1 parts by weight solids product, adds in the N that 20 parts by weight concentration are 0.25 1mol/L dilute sulfuric acids, in N dimethyl formamide solutions, stirring is for 24 hours, it is then centrifuged for separating, with N, then N dimethylformamides and ethyl alcohol washing are dried in the environment of 60 150 DEG C, it is placed in again in apparatus,Soxhlet's, it is washed using acetone as solvent to siphon three times, 6h is dried under 80 DEG C of environment after washing, obtain mesoporous 66 metal-organic framework materials of UiO.It can be used as adsorbent to be applied to Organic Dyestuff Wastewater Treatment.
Description
Technical field
The present invention relates to the aperture expanding methods of porous material technical field, specifically UiO-66 metal-organic framework materials
And application.
Background technology
Metal-organic framework materials have metal ion or ion cluster to be constructed with rigid organic ligand by ligand effect
Hybrid inorganic-organic materials, in recent years, metal-organic framework materials absorption with separating, heterogeneous catalysis, fluorescence sense and
Molecular magnet etc. is widely studied and applied.Metal-organic framework materials are special due to the ligand by metal ion
Seek peace the influences of ligand sizes, the metal-organic framework materials reported are mostly the porous material of pore size, expand metal-
The aperture size of organic framework material will be enlarged by application of the material in fields such as separation science, Journal of Molecular Catalysis, medicament slow releases.
The method for expanding metal-organic framework aperture mainly has template, such as：Qiu L G etc. are in Angewandte
Chemie International Edition, the 49th the 9487-9491 pages of phase in 2008；Zhang W N etc. are in advanced
Materials, the 18th the 962-968 pages paper delivered of phase in 2015.Also had using the synthesising mesoporous MOF materials of template-free method
It reports on a small quantity, such as：Sang X etc. are in Chemphyschem, 2317-2321 pages of o. 11th in 2015；Cao Y etc. are in Crystal
Growth ＆ Design, the 1st phase 504-510 in 2016；McNamara N D etc. are in ACS Applied Materials ＆
Interfaces, the paper that the 9th phase 5338-5346 in 2015 is delivered.In addition, using the method for mixture be also expand metal-
One of the approach in organic backbone aperture, the aperture size for adjusting skeleton by adding in the ligands such as carboxylic acid in presoma.Such as：Cai
G etc. is in Angewandte Chemie International Edition, the 2nd the 578-582 pages of phase in 2017；Shearer G
C et al. is in Chemistry of Materials, the 3749-3761 pages paper delivered of o. 11th in 2016.
Metal-organic framework materials UiO-66 has higher thermal stability and acid resistance, and material is in gas storage, out-phase
Catalysis, selective absorption etc. have a good application prospect, but its aperture is about 0.7nm, so being badly in need of now a kind of
The method that the aperture of UiO-66 metal-organic framework materials can be expanded.
The content of the invention
The technical problems to be solved by the invention be to provide UiO-66 metal-organic framework materials aperture expanding method and
Using this method can obtain the UiO-66 metal-organic framework materials of mesopore size, and preparation process is simple to operation, lead to
The aperture for expanding its UiO-66 metal-organic framework materials is crossed, can be used as the adsorbent of waste water from dyestuff.
In order to solve the above technical problems, the present invention provides the aperture expanding method of UiO-66 metal-organic framework materials,
Comprise the following steps：
(1) take the zirconium chloride powder of 2.47 parts by weight, take 1.47 parts by weight terephthalic acid powders, mixing is placed on Sheng
In the single-necked flask for there are 95 parts by weight n,N-Dimethylformamide, 10min is ultrasonically treated, it is made fully to dissolve；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave treatment 15min, microwave
Power is 500W, obtains the first mixture and is filtered or be centrifugally separating to obtain the first solid product；
(3) by the use of one or more of ethyl alcohol, dichloromethane, water, N,N-dimethylformamide as cleaning solution washing the
Then first solid product drying process is obtained micropore UiO-66 metal-organic framework materials by one solid product；
(4) 1 parts by weight of micropore UiO-66 metal-organic framework materials made from step (3) are taken, it is dense to add in 19-21 parts by weight
It spends in the n,N-Dimethylformamide solution for 0.25-1mol/L dilute sulfuric acids, magnetic agitation for 24 hours, is then centrifuged for separating, and centrifugation turns
Speed is 8000r/min, and centrifugation time 3min obtains the second solid product；
(5) the second solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the second solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, 2-24h is then dried in the environment of 60-150 DEG C and obtains the 3rd solid product；
(6) the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent to siphon three times, after washing
2-24h is dried under 80 DEG C of environment, obtains mesoporous UiO-66 metal-organic framework materials.
For the sake of simple declaration problem, the aperture of UiO-66 metal-organic framework materials of the present invention is expanded below
Method is referred to as this method.
The advantages of this method：This method is by the synthetic microporous UiO-66 metal-organic framework materials of microwave treatment, due to micro-
The process of ripple processing does not have the limitation of temperature and pressure, so can be operated using household microwave oven, it is simple and convenient, then use sulphur
Acid ion occurs part with the terephthalic acid (TPA) ligand of micropore UiO-66 metal organic frameworks and exchanges, and reaches and expands material aperture
Purpose, obtain mesoporous UiO-66 metal-organic framework materials, the reaction time is short, yield is high.
By mesoporous UiO-66 metal-organic framework materials made from this method, give up as adsorbent applied to organic dyestuff
Water process is separated from water dye molecule in waste water from dyestuff.
This method preferred embodiment is as follows：
As preference, the formic acid of 1 parts by weight of addition is also needed in the step (1) in single-necked flask.
As preference, the rotating speed of the centrifugation in the step (2) is 8000r/min, centrifugation time 3min.
As preference, the washing methods in the step (3) is to mix cleaning solution and the first solid product in test tube
Conjunction is subsequently placed in centrifuge and centrifuges, and then removes upper strata washing lotion, and the cleaning solution uses order as N, N- dimethyl methyls
Amide and ethyl alcohol alternately wash at least three times.
As preference, the drying mode in the step (3) is vacuum drying, temperature is 80 DEG C, time 6h.
Description of the drawings
Fig. 1 is the x-ray diffraction pattern of microwave synthesis UiO-66.
Fig. 2 is the transmission electron microscope photo that UiO-66 is etched in various concentration sulfuric acid.
Fig. 3 be UiO-66 and etching after framework material x-ray diffraction pattern.
Fig. 4 is the thermal multigraph of UiO-66 and the dilute sulfuric acid etching back skeleton material for passing through 1mol/L.
Fig. 5 be UiO-66 and etching after framework material N2 absorption/desorption isotherm and graph of pore diameter distribution.
Fig. 6 be UiO-66 and etching after framework material infared spectrum.
Fig. 7 is framework material after UiO-66 and etching to the adsorption curve and dynamic curve diagram of methylene blue.
Specific embodiment
Embodiment one：
The aperture expanding method of UiO-66 metal-organic framework materials, comprises the following steps：
(1) take the zirconium chloride powder of 2.47 parts by weight, take 1.47 parts by weight terephthalic acid powders, the first of 1 parts by weight
Acid, mixing are placed in the single-necked flask for filling 95 parts by weight n,N-Dimethylformamide, are ultrasonically treated 10min, make it fully
Dissolving；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave treatment 15min, microwave
Power is 500W, obtains the first mixture and carries out being centrifugally separating to obtain the first solid product, the rotating speed of centrifugation is
8000r/min, centrifugation time 3min；
(3) the first solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the first solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, then the first solid product is dried in vacuo, temperature is 80 DEG C, time 6h, obtains the organic bone of micropore UiO-66 metals
Frame material；
(4) 1 parts by weight of micropore UiO-66 metal-organic framework materials made from step (3) are taken, add in 20 parts by weight concentration
For in the n,N-Dimethylformamide solution of 0.25mol/L dilute sulfuric acids, magnetic agitation for 24 hours, is then centrifuged for separating, and centrifugal rotational speed is
8000r/min, centrifugation time 3min obtain the second solid product；
(5) the second solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the second solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, 6h is then dried in the environment of 80 DEG C and obtains the 3rd solid product；
(6) the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent to siphon three times, after washing
6h is dried under 80 DEG C of environment, obtains mesoporous UiO-66 metal-organic framework materials.
Embodiment two：
The aperture expanding method of UiO-66 metal-organic framework materials, comprises the following steps：
(1) take the zirconium chloride powder of 2.47 parts by weight, 1.47 parts by weight terephthalic acid powders, mixing is taken to be placed on Sheng
In the single-necked flask for there are 95 parts by weight n,N-Dimethylformamide, 10min is ultrasonically treated, it is made fully to dissolve；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave reaction 15min, microwave
Power is 500W, obtains the first mixture and carries out being centrifugally separating to obtain the first solid product, the rotating speed of centrifugation is
8000r/min, centrifugation time 3min；
(3) the first solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the first solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, then the first solid product is dried in vacuo, temperature is 80 DEG C, time 6h, obtains the organic bone of micropore UiO-66 metals
Frame material；
(4) 1 parts by weight of micropore UiO-66 metal-organic framework materials made from step (3) are taken, add in 19 parts by weight concentration
For in the n,N-Dimethylformamide solution of 0.50mol/L dilute sulfuric acids, magnetic agitation for 24 hours, is then centrifuged for separating, and centrifugal rotational speed is
8000r/min, centrifugation time 3min obtain the second solid product；
(5) the second solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the second solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, 2h is then dried in the environment of 60 DEG C and obtains the 3rd solid product；
(6) the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent to siphon three times, after washing
6h is dried under 80 DEG C of environment, obtains mesoporous UiO-66 metal-organic framework materials.
Embodiment three：
The aperture expanding method of UiO-66 metal-organic framework materials, comprises the following steps：
(1) take the zirconium chloride powder of 2.47 parts by weight, 1.47 parts by weight terephthalic acid powders, mixing is taken to be placed on Sheng
In the single-necked flask for there are 95 parts by weight n,N-Dimethylformamide, 10min is ultrasonically treated, it is made fully to dissolve；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave reaction 15min, microwave
Power is 500W, obtains the first mixture and carries out filtering isolated first solid product, the rotating speed of centrifugation is
8000r/min, centrifugation time 3min；
(3) the first solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the first solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, then the first solid product is dried in vacuo, temperature is 80 DEG C, time 6h, obtains the organic bone of micropore UiO-66 metals
Frame material；
(4) 1 parts by weight of micropore UiO-66 metal-organic framework materials made from step (3) are taken, add in 21 parts by weight concentration
For in the n,N-Dimethylformamide solution of 1.00mol/L dilute sulfuric acids, magnetic agitation for 24 hours, is then centrifuged for separating, and centrifugal rotational speed is
8000r/min, centrifugation time 3min obtain the second solid product；
(5) the second solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the second solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, then dried in the environment of 150 DEG C and obtain the 3rd solid product for 24 hours；
(6) the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent to siphon three times, after washing
6h is dried under 80 DEG C of environment, obtains mesoporous UiO-66 metal-organic framework materials.
Example IV：
The aperture expanding method of UiO-66 metal-organic framework materials, comprises the following steps：
(1) take the zirconium chloride powder of 2.47 parts by weight, 1.47 parts by weight terephthalic acid powders, mixing is taken to be placed on Sheng
In the single-necked flask for there are 95 parts by weight n,N-Dimethylformamide, 10min is ultrasonically treated, it is made fully to dissolve；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave reaction 15min, microwave
Power is 500W, obtains the first mixture and carries out being centrifugally separating to obtain the first solid product, the rotating speed of centrifugation is
8000r/min, centrifugation time 3min；
(3) the first solid product is washed as cleaning solution by the use of dichloromethane and water, washing methods is, by cleaning solution and first
Solid product is mixed to be subsequently placed in centrifuge in test tube and centrifuged, and then removes upper strata washing lotion, alternately washing four times, then will
First solid product is dried in vacuo, and temperature is 80 DEG C, time 6h, obtains micropore UiO-66 metal-organic framework materials；
(4) 1 parts by weight of micropore UiO-66 metal-organic framework materials made from step (3) are taken, add in 20 parts by weight concentration
For in the n,N-Dimethylformamide solution of 0.50mol/L dilute sulfuric acids, magnetic agitation for 24 hours, is then centrifuged for separating, and centrifugal rotational speed is
8000r/min, centrifugation time 3min obtain the second solid product；
(5) the second solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the second solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, 6h is then dried in the environment of 80 DEG C and obtains the 3rd solid product；
(6) the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent to siphon three times, after washing
6h is dried under 80 DEG C of environment, obtains mesoporous UiO-66 metal-organic framework materials.
Embodiment five：
The aperture expanding method of UiO-66 metal-organic framework materials, comprises the following steps：
(1) take the zirconium chloride powder of 2.47 parts by weight, take 1.47 parts by weight terephthalic acid powders, the first of 1 parts by weight
Acid, mixing are placed in the single-necked flask for filling 95 parts by weight n,N-Dimethylformamide, are ultrasonically treated 10min, make it fully
Dissolving；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave treatment 15min, microwave
Power is 500W, obtains the first mixture and carries out filtering isolated first solid product；
(3) the first solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the first solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Four times, then the first solid product is dried in vacuo, temperature is 80 DEG C, time 6h, obtains the organic bone of micropore UiO-66 metals
Frame material；
(4) 1 parts by weight of micropore UiO-66 metal-organic framework materials made from step (3) are taken, add in 20 parts by weight concentration
For in the n,N-Dimethylformamide solution of 0.50mol/L dilute sulfuric acids, magnetic agitation for 24 hours, is then centrifuged for separating, and centrifugal rotational speed is
8000r/min, centrifugation time 3min obtain the second solid product；
(5) the second solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the second solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, 6h is then dried in the environment of 80 DEG C and obtains the 3rd solid product；
(6) the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent to siphon three times, after washing
6h is dried under 80 DEG C of environment, obtains mesoporous UiO-66 metal-organic framework materials.
Embodiment six：
The aperture expanding method of UiO-66 metal-organic framework materials, comprises the following steps：
(1) take the zirconium chloride powder of 2.47 parts by weight, take 1.47 parts by weight terephthalic acid powders, the first of 1 parts by weight
Acid, mixing are placed in the single-necked flask for filling 95 parts by weight n,N-Dimethylformamide, are ultrasonically treated 10min, make it fully
Dissolving；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave treatment 15min, microwave
Power is 500W, obtains the first mixture and carries out filtering isolated first solid product；
(3) the first solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and water, washing methods is that will wash
Liquid is mixed to be subsequently placed in centrifuge in test tube and centrifuged with the first solid product, then removes upper strata washing lotion, alternately washing three
It is secondary, then the first solid product is dried in vacuo, temperature is 80 DEG C, time 6h, obtains micropore UiO-66 metal organic frameworks
Material；
(4) 1 parts by weight of micropore UiO-66 metal-organic framework materials made from step (3) are taken, add in 20 parts by weight concentration
For in the n,N-Dimethylformamide solution of 0.25mol/L dilute sulfuric acids, magnetic agitation for 24 hours, is then centrifuged for separating, and centrifugal rotational speed is
8000r/min, centrifugation time 3min obtain the second solid product；
(5) the second solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the second solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, 6h is then dried in the environment of 80 DEG C and obtains the 3rd solid product；
(6) the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent to siphon three times, after washing
6h is dried under 80 DEG C of environment, obtains mesoporous UiO-66 metal-organic framework materials.
To embody the invention effect of the present invention, below by confirmatory experiment, the present invention is further described：
Preparation process：
(1) zirconium chloride 0.3914g, terephthalic acid (TPA) 0.2324g, formic acid 0.13ml, N, N- dimethyl methyls accurately are weighed
Amide 16ml mixing is placed in single-necked flask, is ultrasonically treated 10min, it is made fully to dissolve；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave treatment 15min, microwave
Power is 500W, obtains the first mixture and carries out being centrifugally separating to obtain the first solid product, the rotating speed of centrifugation is
8000r/min, centrifugation time 3min；
(3) the first solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is that will wash
It washs liquid and mixes to be subsequently placed in centrifuge in test tube with the first solid product and centrifuge, then remove upper strata washing lotion, alternately wash
Three times, then the first solid product is dried in vacuo, temperature is 80 DEG C, time 6h, obtains the organic bone of micropore UiO-66 metals
Frame material, yield 71.3%；
(4) tri- parts of micropore UiO-66 metal-organic framework materials 0.2000g made from step (3) is taken, corresponding addition 2mL is dense
Degree is respectively magnetic agitation in the n,N-Dimethylformamide solution of 0.25mol/L, 0.50mol/L, 1.00mol/L dilute sulfuric acid
For 24 hours, it is then centrifuged for separating, centrifugal rotational speed 8000r/min, centrifugation time 3min, obtains three kind of second solid product；
(5) three kind of second solid product being washed by the use of n,N-Dimethylformamide and ethyl alcohol as cleaning solution, washing methods is,
Cleaning solution is mixed to be subsequently placed in centrifuge in test tube with the second solid product and is centrifuged, then removes upper strata washing lotion, alternately
Washing dries 6h in the environment of 80 DEG C three times, then and obtains three kind of the 3rd solid product；
(6) three kind of the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent respectively to siphon three
It is secondary, 6h is dried under 80 DEG C of environment after washing, three kinds of mesoporous UiO-66 metal-organic framework materials is obtained, is denoted as respectively：E-
UiO-66 (0.25), E-UiO-66 (0.5) and E-UiO-66 (1).
Above-mentioned ultrasonic instrument uses Kunshan Shu Mei table type numerical control type ultrasonic cleaners, model KQ-100DB.
Above-mentioned micro-wave oven uses Glanz micro-wave oven, model P70D20P.
Above-mentioned centrifuge is using Town in Shanghai booth TGL-15B high speed tabletop centrifuges.
Above-mentioned vacuum drying chamber is using the permanent electric heating constant-temperature blowing drying box in Shanghai one, model DHG-9023A.
Evaluation experimental：
1st, referring to Fig. 1, Fig. 1 is the x-ray diffraction pattern of the micropore UiO-66 metal-organic framework materials of step (3) synthesis
Spectrum, using the X-ray diffractometer of Rigaku Co., Ltd., model Rigaku Ultima III, abscissa is in figure
2 θ (θ is the angle of diffraction), ordinate are diffracted intensity, and upside curve prepares the XRD diagram of the micropore UiO-66 of gained for step (3)
Spectrum, lower curve are the XRD standard diagrams of UiO-66, it can be found that the XRD spectrum of synthetic sample and standard diagram base from figure
This is consistent, and it is UiO-66 metal-organic framework materials to show synthetic product.
2nd, referring to Fig. 2, Fig. 2 is the transmission electron microscope photo that different UiO-66 are etched in various concentration sulfuric acid, using
Jeol Ltd. projects Electronic Speculum, in model JEOL 2100, Fig. 2 (a) be step (3) synthesis micropore UiO-66,
(b) be E-UiO-66 (0.25), (c) is E-UiO-66 (0.5), (d) is E-UiO-66 (1), it can be found that micropore from figure
UiO-66 samples are etched through persulfuric acid, and the aperture size of material is significantly improved, and even aperture distribution is orderly, show to adopt
UiO-66 skeletons aperture can be expanded with sulfuric acid etching method.
3rd, referring to Fig. 3, Fig. 3 be UiO-66 and etching after framework material x-ray diffraction pattern, using Japan
The X-ray diffractometer of Co., Ltd. of science, model Rigaku Ultima III, in figure abscissa be 2 θ (θ is the angle of diffraction),
Ordinate is diffracted intensity, and curve is respectively from top to bottom in figure：The XRD spectrum of E-UiO-66 (1), E-UiO-66 (0.5)
The XRD spectrum for the micropore UiO-66 that XRD spectrum, the XRD spectrum of E-UiO-66 (0.25), step (3) synthesize, the XRD of UiO-66
Standard diagram, as can be seen from the figure UiO-66 skeletons after the sulfuric acid solution etching of various concentration, do not send out by the structure of sample
Raw significant change.
4th, referring to Fig. 4, Fig. 4 is the thermal multigraph of UiO-66 and the dilute sulfuric acid etching back skeleton material for passing through 1mol/L, is adopted
It is the thermal analysis system of German Nai Chi companies, model STA449C, ordinate is mass fraction (%) in figure, abscissa
For temperature (DEG C), by, it can be found that UiO-66 samples are after etching, the thermal stability of material does not reduce significantly in figure,
Show that the framework material after etching can still be able to keep stablizing at 495 DEG C.
5th, referring to Fig. 5, Fig. 5 (a) is absorption/desorption isotherm collection of illustrative plates of material, using the more of Merck ＆ Co., Inc of the U.S.
The full-automatic specific surface area of passage and lacunarity analysis instrument, ordinate is suction/desorption in model TriStarII 3020, Fig. 5 (a)
Measure (cm3/ g), abscissa is relative pressure, it can be found that with the increase of sulfate ion concentration in figure, material is to nitrogen
Adsorption capacity step up, show increase of the UiO-66 skeletons with etching degree, in system the amount of sulfate ion by
Step increases, and due to the polarization of sulfate ion, material is caused to step up the adsorption capacity of nitrogen.Fig. 5 (b) is hole
Footpath distribution map, in Fig. 5 (b), ordinate is dV/dD (cm3/ g), abscissa is pore-size distribution (nm), it is found that material is being carved
Aperture after erosion is expanded, and the aperture of sample E-UiO-66 (0.5) and E-UiO-66 (1) are 3.7nm or so, and pore volume has
A degree of increase.
6th, referring to Fig. 6, Fig. 6 be UiO-66 and etching after framework material infared spectrum, ordinate is transmitance
(%), abscissa are wave number (cm-1), four curves in figure are from top to bottom followed successively by E-UiO-66 (1) infrared absorption line, E-
UiO-66 (0.5) infrared absorption line, E-UiO-66 (0.25) infrared absorption line, the micropore UiO-66 of step (3) synthesis are red
Outer absorption line, by, it can be found that with the increase of etching degree, sample is in 1650cm in figure-1There is stretching for carboxyl in left and right
Contracting vibration peak gradually weakens, this is because compared to green bone frame UiO-66, since the terephthalic acid (TPA) of sulfate ion and skeleton is matched somebody with somebody
Body exchanges, and the zirconium ion in skeleton is caused to be gradually reduced with carboxyl coordination amount, so that its infrared absorption peak slowly subtracts
It is weak.
7th, UiO-66, E-UiO-66 (0.25), E-UiO-66 (0.5) and E-UiO-66 (1) 20mg is weighed respectively to add in
20mL concentration is the methylene blue solution of 10ppm, and the magnetic agitation at 20 DEG C makes ultraviolet-visible spectrophotometer measure not
With the absorbance of methyl blue solution next time time, using the ultraviolet-visible spectrophotometer of Japanese Shimadzu Corporation, model
For Shimadzu UV-3900, UiO-66 and the material obtained after being etched in different sulfuric acid concentration solution are evaluated to secondary first
The absorption property of base indigo plant.
Referring to Fig. 7, Fig. 7 is that the framework material after UiO-66 and etching is bent to the adsorption curve and dynamics of methylene blue
Line chart.Ordinate is equilibrium adsorption capacity (mg/g) in Fig. 7 (a), and abscissa is for the time (min) by Fig. 7 (a) it can be found that sample
By etching, since its aperture size increases, material, which has reached the adsorption capacity of methylene blue, significantly to be improved, and shows material
There is preferable absorption property to organic macromolecule.Ordinate is time/equilibrium adsorption capacity (ming/mg) in Fig. 7 (b), horizontal
Coordinate is the time (min), by Fig. 7 (b) it can be found that material meets the absorption of methylene blue quasi- secondary absorption dynamics side
Journey.
Claims (6)
1.UiO-66 the aperture expanding method of metal-organic framework materials, which is characterized in that comprise the following steps：
(1) take the zirconium chloride powder of 2.47 parts by weight, take 1.47 parts by weight terephthalic acid powders, mixing, which is placed on, fills 95
In the single-necked flask of parts by weight n,N-Dimethylformamide, 10min is ultrasonically treated, it is made fully to dissolve；
(2) condensation reflux unit in single-necked flask is installed, and is placed it in micro-wave oven, microwave treatment 15min, microwave power
For 500W, obtain the first mixture and filtered or be centrifugally separating to obtain the first solid product；
(3) it is solid by the use of one or more of ethyl alcohol, dichloromethane, water, N,N-dimethylformamide as cleaning solution washing first
Then first solid product drying process is obtained micropore UiO-66 metal-organic framework materials by body product；
(4) 1 parts by weight of micropore UiO-66 metal-organic framework materials made from step (3) are taken, adding in 19-21 parts by weight concentration is
In the n,N-Dimethylformamide solution of 0.25-1mol/L dilute sulfuric acids, magnetic agitation for 24 hours, is then centrifuged for separating, and centrifugal rotational speed is
8000r/min, centrifugation time 3min obtain the second solid product；
(5) the second solid product is washed as cleaning solution by the use of n,N-Dimethylformamide and ethyl alcohol, washing methods is, by cleaning solution
It mixes to be subsequently placed in centrifuge in test tube with the second solid product and centrifuge, then remove upper strata washing lotion, alternately wash three times,
Then 2-24h is dried in the environment of 60-150 DEG C and obtains the 3rd solid product；
(6) the 3rd solid product is placed in apparatus,Soxhlet's, is washed using acetone as solvent to siphon three times, 80 after washing
2-24h is dried under DEG C environment, obtains mesoporous UiO-66 metal-organic framework materials.
2. the aperture expanding method of UiO-66 metal-organic framework materials according to claim 1, it is characterised in that：It is described
The formic acid of 1 parts by weight of addition is also needed in step (1) in single-necked flask.
3. the aperture expanding method of UiO-66 metal-organic framework materials according to claim 1, it is characterised in that：It is described
The rotating speed of centrifugation in step (2) is 8000r/min, centrifugation time 3min.
4. the aperture expanding method of UiO-66 metal-organic framework materials according to claim 1, it is characterised in that：It is described
Washing methods in step (3) is to mix to be subsequently placed in centrifuge in test tube with the first solid product by cleaning solution to centrifuge,
Then upper strata washing lotion is removed, the cleaning solution is n,N-Dimethylformamide and ethyl alcohol using order, and alternating washing is at least
Three times.
5. the aperture expanding method of UiO-66 metal-organic framework materials according to claim 1, it is characterised in that：It is described
Drying mode in step (3) is vacuum drying, and temperature is 80 DEG C, time 6h.
6. obtained by the aperture expanding method of the UiO-66 metal-organic framework materials according to any one of claim 1-5
Mesoporous UiO-66 metal-organic framework materials, as adsorbent be applied to Organic Dyestuff Wastewater Treatment, make to contaminate in waste water from dyestuff
Material molecule is separated from water.
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