CN105524112A - Preparation method of DMF-modified MIL-101 - Google Patents
Preparation method of DMF-modified MIL-101 Download PDFInfo
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- CN105524112A CN105524112A CN201510540442.XA CN201510540442A CN105524112A CN 105524112 A CN105524112 A CN 105524112A CN 201510540442 A CN201510540442 A CN 201510540442A CN 105524112 A CN105524112 A CN 105524112A
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Abstract
The invention relates to a preparation method of a metal organic skeletal material and especially relates to a preparation method of DMF-modified MIL-101. The preparation method comprises a, MIL-101 crystal synthesis, b, DMF modification and ethanol activation and c, mixing of the DMF-modified MIL-101 crude product obtained through the step b and anhydrous ethanol, standing activation of the MIL-101 product in an enclosed environment at a temperature of 100 DEG C for 20h and then drying. The DMF-modified MIL-101 can be used for treating dye sewage, can completely adsorb dye in an aqueous solution as much as possible and has a great use in water treatment in the dyeing and weaving industry.
Description
Technical field
The present invention relates to a kind of preparation method of metal-organic framework materials, particularly the preparation method of MIL-101 that modifies of a kind of DMF.
Background technology
Metal-OrganicFrameworks (MOFs, metal-organic framework materials) is emerging is in recent years coordination center with metal ion, take organic compound as the porous material of part.MOFs Materials is very fast, has the physics and chemistry character of many uniquenesses, and thus its range of application is extremely extensive, as gas adsorption be separated, also can as catalyzer and sensor.
MIL-101 is as the emerging product of MOFs material family, and it is synthesized in May, 2008 by the F é rey team of France.This novel MOFs material has good hydrothermal stability and chemical stability.As, MIL-101 can stable existence several months in atmosphere and under organic solvent solution condition, and can in boiling water stable existence one week.Although its appearance time is not long, excite the research interest of numerous investigators because of its good physicochemical property.MIL-101 is as typical third generation MOFs material, and it also has the general advantage of third generation MOFs material.In the document consulted, report points out that the specific surface area of MIL-101 has 3000-4000m in addition
2/ g, and the specific surface area of the MIL-101 of F é rey team report is especially up to 5900m
2/ g.So large specific surface area is that the application of MIL-101 in gas adsorption is had laid a good foundation.And along with going deep into of studying MIL-101, (as: Chu Qing studies MIL-101 in other respects, methane is separated with carbon dioxide gas mixture, hydrogen sulfide, propane and sulfur fluoride adsorb, as the carrier of the catalyzer such as Pd and polyoxometallate and the stationary phase as chromatography of gases capillary column) also play increasing effect.
MIL-101 is as a kind of matrix material of metal-organic, and it is by MO
4(OH)
2(M=Fe, Cr) octahedron respectively with the rigidity cage structure of trimesic acid (BTC), terephthalic acid (BDC) mutual bridging in space.Connection due to terephthalic acid makes the pore volume of MIL-101 be generally
cage internal diameter is 30 to arrive
window opening is 12 to arrive
so MIL-101 belongs to typical large cage small structure, this describes its potential application advantage in absorption, catalysis more.
Illustrate component units and the crystalline structure of MIL-101 material in FIG.As can be seen from Figure 1, Cr
3+be in octahedral environment, each octahedron is by 1 Cr
3+, 4 from the O in carboxyl, 1 shared O and 1 from H
2o (or from the F in HF) composition in O, 4 octahedra tripolymers formed are connected by BDC, form large tetrahedron in space, these large tetrahedrons form larger cage structure by sharing O atom in space, and its aperture can reach mesoporous scope.The face of composition cage structure has two kinds, and wherein one is surrounded by pentagon face, and after removing guest molecule, interior dimensions is
left and right, surface micropore is of a size of
left and right; Another kind is surrounded by hexagonal surfaces, and after removing guest molecule, interior dimensions is
left and right, and the mean size of surface micropore is
left and right.Meanwhile, MIL-101 also has the site of much undersaturated chromium on the surface, and these unsaturated sites with electron rich functional group, chelatropic reaction can occur.
MIL-101 has good skeleton stability, guest molecule is withdrawn does not affect matrix morphology, find that the equilibrium temperature of MIL-101 crystal can reach more than 300 DEG C in thermogravimetric analysis (TGA) experiment, when exposing in atmosphere, can stable existence some months, and can stable existence under room temperature in multiple organic solvent and heat steam.
Although MOFs is obtained for some researchs in all many-sided application, investigator is made still to pay attention to the research of gas adsorption aspect because of its huge specific surface area.Especially now energy problem is one of focus of global concern, and hydrogen is as a kind of fuel gas of novel environment friendly, and its application prospect widely.Although hydrogen has many advantages, its huge shortcoming is exactly storage problem.And the appearance of MOFs material, the especially appearance of MIL-101, then provide new approaches for addressing this problem.Therefore, up to the present, the hydrogen storage ability of several MOFs under liquid nitrogen is had to obtain confirmation: the saturated extent of adsorption (massfraction) of MOF-5: 5.1%, SSA
bET: 2296m
2/ g, SSA
langmuir: 3840m
2/ g; HKUST-1 saturated extent of adsorption (massfraction): 3.6%, SSA
bET: 1154m
2/ g, SSA
langmuir: 1958m
2/ g; The saturated extent of adsorption of MIL-53 (Al): 4.5%, SSA
bET: 1100m
2/ g, SSA
langmuir: 1540m
2/ g.And the specific surface area of the MIL-101 that F é rey research group synthesizes reaches 5900m
2/ g, its hydrogen-storage amount under 6MPa, 77K can reach 6.1%; And the saturated hydrogen-storage amount of MOF-177 under 77K can reach 7.5%.The hydrogen storage capability of the MOFs material mentioned in document above just leans on physical adsorption to realize, the research team of Japanese Kobe university then proposes another imagination: the MIL-101 utilizing quadrol, gold and palladium to modify carrys out decompose formic acid as catalyzer, formic acid itself is made to become the chemical energy source of Chu Qing, and utilizing the product after modifying to make catalyzer, under experiment condition in the literature, the rate of decomposition of formic acid can reach 100%.
MIL-101 inherits the pore texture of the prosperity of porous material and huge specific surface area as the newcomer of MOFs family, make it in absorption, have abnormal advantage, and according to the selective absorbing of these materials to some specific molecular, the problems such as the separation between gas can be solved.And owing to can utilize MIL-101 can the characteristic of adsorbing metal nanometer fragment, there is the metal-modified of catalytic performance on MIL-101, just can give full play to the catalytic performance of MIL-101, as utilized with the MIL-101 of ethylene diamine-modified mistake and then adsorbing Au/Pd in acid condition, obtain the MIL-101 that Au/Pd duplex metal nano granule fragment is modified, so just can as catalyst decomposes formic acid, the product obtained is hydrogen, and this solves hydrogen preparation and storage problem simultaneously.
Confirm that the absorption property of MIL-101 is not merely for gas aspect through experiment, the adsorption effect of MIL-101 to dyestuff (the being mainly methylene blue solution) aqueous solution is also good.MIL-101 in this experiment and its a series of modified outcomes find the part that aqueous solution of methylene blue adsorbs, the methylene blue composition in the complete adsorbent solution of these MIL-101 products energy.This is used for the high water treatment of requirement degree to MIL-101 and provides a thinking solved.In addition, because have terephthalic acid in the raw material of synthesis MIL-101, it is the impurity of more difficult removing in the product, and the purifying therefore for MIL-101 is also be difficult to one of the process of carrying out.
Summary of the invention
The present invention is directed to the technical problem that terephthalic acid in the raw material of MIL-101 in prior art is difficult to remove, the preparation method of the MIL-101 providing a kind of DMF to modify, the method has the advantages such as operating process is simple and convenient, with low cost.
The technical solution adopted for the present invention to solve the technical problems is:
The preparation method of the MIL-101 that DMF modifies, the method comprises the steps:
The synthesis of a, MIL-101 crystal,
B, DMF modifies, Ethanol activation: pour appropriate amount of deionized water in reactor, then the water in reactor and solid are all transferred in centrifuge tube, centrifugal 3min under rotating speed is 8000-12000r/min, abandon supernatant, appropriate DMF is added again to centrifuge tube, and this mixture is heated 10-12min at 70-75 DEG C, centrifugal, abandon supernatant, MIL-101 many times is washed to no longer including the needle-like crystal (terephthalic acid) of white with DMF, washing terminates, dry, namely the green powder solid obtained is washed away terephthalic acid by DMF and the MIL-101 crude product modified by DMF,
After c, the MIL-101 crude product modified by DMF b step obtained mix with dehydrated alcohol, at closed environment, 100 DEG C of temperature, place 20h, make the MIL-101 product activation obtained, then dry, obtain product.
As preferably, step a adopts hydrothermal synthesis method synthesis MIL-101 crystal.
As preferably, the concrete steps of step a are: get terephthalic acid, Cr (NO
3)
39H
2o and hydrofluoric acid successively add in reactor for 1:1:1 in molar ratio, and then add appropriate amount of deionized water, react 7-8h under sealing is placed on 220 DEG C of temperature, take out reactor afterwards and cool at room temperature, discard the supernatant liquor in reactor, obtain the mixture of terephthalic acid and MIL-101.MIL-101 can with HF and H added
2f and O in O carries out coordination connection.
As preferably, the centrifuge tube described in step b is 50mL, and the amount of deionized water added is 30-40mL, and the amount of the DMF added during washing is 30-40mL.
In the present invention, the purifying of the MIL-101 product of synthesis, modification are that some DMF can modify grafting on MIL-101 simultaneously by the unreacted terephthalic acid of DMF washing removing.
First the present invention utilizes hydrothermal synthesis method to synthesize MIL-101, and after being modified by Ethanol activation after direct suction filtration and DMF, Ethanol activation two kinds of methods are purified to the MIL-101 product obtained.And the sign such as XRD, nitrogen adsorption has been carried out to two kinds of products, obtain the comparable situation between two kinds of MIL-101 products.Result shows, and the MIL-101 that DMF modifies has some to change in three-dimensional arrangement, and its XRD angle of diffraction can offset to wide-angle, illustrates that the lattice parameter of MIL-101 diminishes, and namely DMF can react with MIL-101 really, changes its lattice character.And in the specific surface area of nitrogen mensuration, find that the specific surface area of the MIL-101 that DMF modifies is more much smaller than the specific surface area of MIL-101, this should be that part DMF remains in MIL-101 space, and is not easy removing, so the aperture of MIL-101 can be caused to reduce.
The inventive method is not limited to water heat transfer, and being equally applicable to other has the remaining MIL-101 synthetic method of a large amount of terephthalic acid.
In order to verify the absorption property of the MIL-101 that DMF modifies, also carry out the MIL-101 of DMF modification in the present invention to the adsorption experiment of methylene blue.In the result of ultraviolet test, find that MIL-101 that a small amount of DMF modifies just can methylene blue completely in planar water, illustrate that MIL-101 that DMF modifies can be used in the occasion had higher requirements to water quality.
The invention has the beneficial effects as follows: the present invention have detected the performance change of the MIL-101 after DMF modification, and the qualitative detection of the absorption property of MIL-101 in methylene blue, aqueous formic acid of DMF modification, found that MIL-101 that DMF modifies can methylene blue completely in adsorbent solution, at room temperature also can have certain adsorptive power to formic acid.Therefore, the MIL-101 that DMF modifies can for the treatment of dye wastewater, can as far as possible fully dye substance in adsorption aqueous solution, has great use in the water treatment of the industries such as dyeing and weaving.In some other other application aspect water quality being had to requirements at the higher level, the MIL-101 that DMF modifies also can have certain effect.In addition, because DMF modifies the absorption property drastically increasing MIL-101, great application prospect be also present to the catalytic performance strengthening MIL-101.
Accompanying drawing explanation
Fig. 1 is construction unit and the crystalline structure figure of MIL-101 material;
Fig. 2 is the synthetic method schema of MIL-101;
Fig. 3 is the standard x RD spectrogram of MIL-101 in document;
The XRD that Fig. 4 is through the MIL-101 product that two kinds of purification process obtain contrasts spectrogram;
Fig. 5 is the infrared spectrogram of DMF in document;
Fig. 6 is MIL-101 and the terephthalic acid (H of DMF modification
2bDC) infrared spectrogram;
Fig. 7 is that the MIL-101 that DMF modifies adsorbs methylene blue effect photo;
Fig. 8 is the MIL-101 product absorption methylene blue effect photo modified without DMF;
Fig. 9 is that the MIL-101 that DMF modifies adsorbs ultraviolet detection comparison diagram before and after methylene blue solution;
Figure 10 is that the MIL-101 modified without DMF adsorbs ultraviolet detection comparison diagram before and after methylene blue solution.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.
In the present invention, if not refer in particular to, all parts, per-cent are weight unit, and the equipment adopted and raw material etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the ordinary method of this area.List raw material and the reagent of main use in embodiment in table 1, table 2 lists instrument and the model of main use.
Table 1 main raw material and reagent
The instrument that table 2 mainly uses
The synthesis of the MIL-101 (DMF-MIL-101) that embodiment 1:DMF modifies
The present embodiment adopts hydrothermal method as the synthetic method of preparation MIL-101.As shown in Figure 2, concrete steps are the schema of hydrothermal synthesis method synthesis MIL-101 crystal: electronic balance takes 2.0gCr (NO
3)
39H
2o and 0.83g terephthalic acid (H
2bDC) in 100mL polytetrafluoroethyllining lining autoclave, add 24mL deionized water, then add 1mL hydrofluoric acid.8h in 220 DEG C of high temperature ovens is placed on by airtight for reactor.Take out reactor afterwards, and cool at room temperature.After question response still is chilled to room temperature, pour out the supernatant liquid in reactor carefully, now can see the bottom having a large amount of unreacted terephthalic acids and product MIL-101 to stay reactor.
Purge process (DMF modifies rear Ethanol activation): pouring 40mL deionized water in reactor, then all transfer in 50mL centrifuge tube by the water in reactor and solid, is centrifugal 3min in the whizzer of 8000r/min at rotating speed.At the end of once centrifugal, pour out supernatant liquid carefully.Still have many terephthalic acids in centrifuge tube, now add DMF, and heated solution is to low-grade fever, after centrifuge, pour out supernatant liquid, centrifugal repeatedly to no longer including the needle-like crystal (terephthalic acid) of white with DMF, washing terminates.Now, the pulverulent solids of the green bottom centrifuge tube is exactly washed away terephthalic acid by DMF and by the MIL-101 product that DMF modifies, dried by the solid obtained in 100 DEG C of baking ovens.
The product of oven dry is placed in the autoclave of tetrafluoroethylene, pour 50mL dehydrated alcohol into, after good seal, in 100 DEG C of baking ovens, place 20h, the MIL-101 product obtained is activated, remove the terephthalic acid still remained in MIL-101 hole, finally solid is dried in 100 DEG C of baking ovens.
Comparative example: without the synthesis of the MIL-101 that DMF modifies
Electronic balance takes 2.0gCr (NO
3)
39H
2o and 0.83g terephthalic acid (H
2bDC) in 100mL polytetrafluoroethyllining lining autoclave, add 24mL deionized water, then add 1mL hydrofluoric acid.8h in 220 DEG C of high temperature ovens is placed on by airtight for reactor.Take out reactor afterwards, and cool at room temperature.After question response still is chilled to room temperature, pour out the supernatant liquid in reactor carefully, now can see the bottom having a large amount of unreacted terephthalic acids and product MIL-101 to stay reactor.
Purge process (after direct suction filtration Ethanol activation): add appropriate distilled water in reactor, use core filtration devices, because terephthalic acid is water insoluble and density is relatively little, in suction filtration, terephthalic acid can be deposited on above MIL-101, after suction filtration terminates, carefully most for upper strata terephthalic acid is removed with spoon.Remaining green powder solid and the terephthalic acid that is not removed are dried in 100 DEG C of baking ovens.
The solid of oven dry is still placed in the autoclave of tetrafluoroethylene, pours 50mL dehydrated alcohol into, after good seal, in 100 DEG C of baking ovens, place 20h, the MIL-101 product obtained is activated, so that removing terephthalic acid as much as possible.After activation terminates, after reactor is slightly cold, supernatant liquid is carefully poured out, in reactor, add appropriate distilled water, carry out suction filtration, the solid obtained is dried in 100 DEG C of baking ovens.
For description effect, contriver utilize X-ray diffraction (XRD), infrared absorption spectrum (IR), etc. characterization method determine MIL-101 with Au/Pd that DMF modifies modify after the three-dimensional arrangement of MIL-101, thing form mutually, etc. the character of aspect.
1, the X-ray diffraction analysis of MIL-101
Utilize X-ray diffractometer analysis, obtain the diffraction peak of MIL-101, and compared with the XRD diffraction peak reported in document, Fig. 3 is the X-ray diffraction spectrogram of MIL-101 in document, and the XRD of the MIL-101 that Fig. 4 obtains through embodiment 1 and comparative example two kinds of purification process contrasts spectrogram.Being compared by two parts of spectrograms, be carry out diffraction analysis from 1 °, and characteristic peak is also mainly present in less than 10 ° in document.Through two kinds of purification process process MIL-101 with corresponding position in document near have the appearance of characteristic peak, but obviously see that larger skew has appearred in the characteristic peak of the MIL-101 modified through DMF, this illustrates that the three-dimensional arrangement of DMF on MIL-101 creates larger impact.And can judge from XRD diffraction peak deflection wide-angle direction, the lattice parameter of the MIL-101 that DMF modifies diminishes, and confirms that DMF can change the three-dimensional arrangement of MIL-101.
2, the infrared spectrum of MIL-101
MIL-101 is with Cr
3+centered by, terephthalic acid is the crystalline product that part self-assembly is formed.Terephthalic acid has obvious carbonyl absorption peak (1600cm in infrared absorption spectrum
-1left and right) and the fingerprint region absorption peak of phenyl ring, so MIL-101 is carried out Infrared Characterization, its spectrogram should have very large similarity with the infrared spectrum of terephthalic acid.And after DMF modifies on MIL-101, the spectrogram obtained and the infrared spectrum of simple DMF also have corresponding change, and Fig. 5 is the infrared spectrum of DMF, can be seen 3000 and 1700cm by contrast
-1all there is skew at the peak at place, and after DMF modification MIL-101 is described, its structure also can change, thus illustrates that DMF modifies on MIL-101, but not simple physical adsorption.
The MIL-101 product modify DMF and terephthalic acid carry out infrared test and obtain corresponding infrared contrast spectrogram as shown in Figure 6.As seen in Fig., the infrared spectrum of MIL-101 and the infrared spectrum of terephthalic acid that DMF modifies to go out peak position place basically identical, but compare phthalic acid, and the peak position that goes out of the MIL-101 of DMF modification slightly offsets, at 1700cm
-1place MIL-101 peak position slightly toward left avertence some, this should be have impact on the vibration of carbonyl because the tripolymer of the Sauerstoffatom in carboxyl and chromium nitrate can be utilized to carry out coordination for terephthalic acid, uses peak position and there occurs change.And the change going out peak position or go out peak intensity at other wavelength places should be all after terephthalic acid and tripolymer carry out coordination, the environment of terephthalic acid inside changes, so its Vibration Condition also changes thereupon.Go out within the scope of peak at fingerprint region phenyl ring, the MIL-101 that DMF modifies is on all four compared with terephthalic acid, and illustrating in complexation process, is almost non-existent on the impact of phenyl ring.
3, MIL-101 adsorbs methylene blue test
MIL-101 receives the research of investigator because of its huge specific surface area and larger pore volume character, especially gas adsorption aspect.In the present invention, also the application of some absorption aspects of the MIL-101 that DMF modifies is studied.
Because methylene blue has obvious blueness, the adsorption effect of MIL-101 product can be found out under the observation of naked eyes, so, after absorption terminates, the color before and after methylene blue is carried out contrast of taking pictures, as shown in Figure 7, in every picture group, being the methylene blue solution before absorption in the cuvette on the left side, is the methylene blue solution after absorption in the cuvette of the right.Fig. 8 is the colour contrast photo that the MIL-101 modified without DMF adsorbs before and after methylene blue solution, and as can be seen from the figure, the MIL-101 modified without DMF adsorbs the effect of methylene blue also not as the MIL-101 of DMF process adsorbs the effective of methylene blue.
Methylene blue has obvious ultraviolet absorption peak at 660nm, 290nm and 245nm, has carried out UV absorbance detection in order to the adsorption effect of methylene blue is better described, Fig. 9, Figure 10 are that each sample is to the uv-absorbing contrast before and after methylene blue adsorption number.
By adsorbing the ultraviolet Comparative result before and after methylene blue above, find that the MIL-101 that DMF modifies can adsorb methylene blue completely.The result that MIL-101 simultaneously by modifying without DMF adsorbs methylene blue is seen, MIL-101 performance in absorption methylene blue of modifying without DMF is poor, first found in the observable aspect of naked eyes by the contrast of photo, the color of methylene blue solution is also just slightly lighter, is not adsorbed completely.Also can see in ultraviolet curve, solution after absorption, the concentration of methylene blue be also decline very little, and near the characteristic peak of 250nm phenyl ring, peak height after absorption rises very large on the contrary, that phenyl ring is wherein have larger charateristic avsorption band near this because remained a lot of terephthalic acids in the MIL-101 of DMF modification.Relatively can be found out by these data of two groups, the MIL-101 modified through DMF is adsorbing the MIL-101 that will be much better than in methylene blue effect to modify without DMF.
To sum up, the MIL-101 that DMF that the present invention obtains modifies has the dyestuffs such as absorption methylene blue, the purposes of the aspect such as to purify water.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (5)
1. a preparation method of the MIL-101 of DMF modification, is characterized in that the method comprises the steps:
The synthesis of a, MIL-101 crystal,
B, DMF modify, Ethanol activation: in reactor, pour appropriate amount of deionized water into, then the water in reactor and solid are all transferred in centrifuge tube, centrifugal 3min under rotating speed is 8000-12000r/min, abandon supernatant, appropriate DMF is added again to centrifuge tube, and this mixture is heated 10-12min at 70-75 DEG C, centrifugal, abandon supernatant, MIL-101 many times is washed to no longer including the needle-like crystal of white with DMF, washing terminates, and dry, namely the green powder solid obtained is washed away terephthalic acid by DMF and the MIL-101 crude product modified by DMF;
After c, the MIL-101 crude product modified by DMF b step obtained mix with dehydrated alcohol, at closed environment, 100 DEG C of temperature, place 20h, make the MIL-101 product activation obtained, then dry, obtain product.
2. the preparation method of the MIL-101 of DMF modification according to claim 1, is characterized in that: step a adopts hydrothermal synthesis method synthesis MIL-101 crystal.
3. the preparation method of the MIL-101 of DMF modification according to claim 2, is characterized in that the concrete steps of step a are: get terephthalic acid, Cr (NO
3)
39H
2o and hydrofluoric acid successively add in reactor for 1:1:1 in molar ratio, and then add appropriate amount of deionized water, react 7-8h under sealing is placed on 220 DEG C of temperature, take out reactor afterwards and cool at room temperature, discard the supernatant liquor in reactor, obtain the mixture of terephthalic acid and MIL-101.
4. the preparation method of the MIL-101 of DMF modification according to claim 1, it is characterized in that: the centrifuge tube described in step b is 50mL, the amount of deionized water added is 30-40mL, and the amount of the DMF added during washing is 30-40mL.
5. a MIL-101 for DMF modification, is characterized in that the MIL-101 that this DMF modifies obtains by the following method:
The synthesis of a, MIL-101 crystal,
B, DMF modify, Ethanol activation: in reactor, pour appropriate amount of deionized water into, then the water in reactor and solid are all transferred in centrifuge tube, centrifugal 3min under rotating speed is 8000-12000r/min, abandon supernatant, appropriate DMF is added again to centrifuge tube, and this mixture is heated 10-12min at 70-75 DEG C, centrifugal, abandon supernatant, MIL-101 many times is washed to no longer including the needle-like crystal of white with DMF, washing terminates, and dry, namely the green powder solid obtained is washed away terephthalic acid by DMF and the MIL-101 crude product modified by DMF;
After c, the MIL-101 crude product modified by DMF b step obtained mix with dehydrated alcohol, at closed environment, 100 DEG C of temperature, place 20h, make the MIL-101 product activation obtained, then dry, obtain product.
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Application publication date: 20160427 |