CN105521766A - Gold-palladium-modified MIL-101 and preparation method thereof - Google Patents
Gold-palladium-modified MIL-101 and preparation method thereof Download PDFInfo
- Publication number
- CN105521766A CN105521766A CN201510540496.6A CN201510540496A CN105521766A CN 105521766 A CN105521766 A CN 105521766A CN 201510540496 A CN201510540496 A CN 201510540496A CN 105521766 A CN105521766 A CN 105521766A
- Authority
- CN
- China
- Prior art keywords
- mil
- dmf
- modified
- solution
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to gold-palladium-modified MIL-101 and a preparation method thereof. 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, drying, mixing of the DMF-modified MIL-101 product subjected to ethanol activation and a H2PdCl4 solution, mixing of the mixture, HAuCl4 and a proper amount of deionized water, stirring, centrifugation, supernatant removal, washing, drying and reduction treatment. The gold and palladium on MIL-101 can improve catalysis functions without damage to adsorption performances. The gold-palladium-modified MIL-101 has a wide application range.
Description
Technical field
The present invention relates to a kind of preparation method of metal-organic framework materials, MIL-101 of particularly a kind of golden palladium modification and preparation method thereof.
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 absorption be separated, also can as catalyst 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 researchers because of its good physicochemical properties.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 area of MIL-101 has 3000-4000m in addition
2/ g, and the specific area of the MIL-101 of F é rey team report is especially up to 5900m
2/ g.So large specific area is that the application of MIL-101 in gas absorption 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 catalyst such as Pd and polyoxometallate and the Stationary liquid as chromatography of gases capillary column) also play increasing effect.
MIL-101 is as a kind of composite 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 (TPA) (BDC) mutual bridging in space.Connection due to terephthalic acid (TPA) 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 crystal 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, inside dimension 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, inside dimension 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, researcher is made still to pay attention to the research of gas absorption aspect because of its huge specific 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 (mass fraction) of MOF-5: 5.1%, SSA
bET: 2296m
2/ g, SSA
langmuir: 3840m
2/ g; HKUST-1 saturated extent of adsorption (mass fraction): 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 area of the MIL-101 that F é rey research group synthesizes reaches 5900m
2/ g, its hydrogen storage content under 6MPa, 77K can reach 6.1%; And the saturated hydrogen storage content 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 absorption to realize, the research team of Japanese Kobe university then proposes another imagination: utilize the MIL-101 of ethylenediamine, gold and palladium modified to carry out decompose formic acid as catalyst, formic acid itself is made to become the chemical energy source of Chu Qing, and utilizing the product after modifying to make catalyst, under experiment condition in the literature, the resolution ratio of formic acid can reach 100%.
MIL-101 inherits the gap structure of the prosperity of porous material and huge specific 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, Au-Pd is adsorbed in acid condition with the MIL-101 of ethylene diamine-modified mistake as utilized, 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.Carry out finding in adsorption experiment from the MIL-101 this experiment and its a series of modified outcomes to aqueous solution of methylene blue, 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 (TPA) 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 (TPA) 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 golden palladium to modify, the method has the advantages such as experimental implementation 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 golden palladium is modified, 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 acicular crystal of white with DMF, washing terminates, and dry, namely the green powder solid obtained is washed away terephthalic acid (TPA) by DMF and the MIL-101 crude product modified by DMF;
After c, the MIL-101 crude product modified by DMF obtained by step b mix with absolute ethyl alcohol, at closed environment, 100 DEG C of temperature, place 20h, make the MIL-101 product activation obtained, then dry;
The DMF that d, step c obtain modifies MIL-101 product elder generation and the H of rear Ethanol activation
2pdCl
4solution mix, then with HAuCl
4with appropriate amount of deionized water mixing, be made into the solution of pH=3.0 ± 0.2, fully stirred by this solution at 35-37 DEG C of temperature, centrifugal, abandon supernatant liquor, deionized water fully washs rear abundant drying;
E, PdCl
4 2-and AuCl
4 -product is obtained, i.e. the MIL-101 of golden palladium modification after reduction treatment.
As preferably, step a adopts hydrothermal synthesis method synthesis MIL-101 crystal.
As preferably, the concrete steps of step a are: get terephthalic acid (TPA), 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 in reactor, obtain the mixture of terephthalic acid (TPA) 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.
As preferably, the drying course in step c is more than the 12h that dewaters at 150-160 DEG C.
As preferably, ED-MIL-101 and H
2pdCl
4, HAuCl
4the mass ratio of three is 2:1:1.
As preferably, the detailed process of step e is: in 150 DEG C of products of drying, add 80% hydrazine hydrate solution, mix, placement is spent the night, every other day that mixed solution is centrifugal, outwells supernatant liquor, after deionized water washing, the solid obtained is dried in 100 DEG C ± 10 DEG C baking ovens.
The MIL-101 that golden palladium is modified, it is made 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 acicular crystal of white with DMF, washing terminates, and dry, namely the green powder solid obtained is washed away terephthalic acid (TPA) by DMF and the MIL-101 crude product modified by DMF;
After c, the MIL-101 crude product modified by DMF obtained by step b mix with absolute ethyl alcohol, at closed environment, 100 DEG C of temperature, place 20h, make the MIL-101 product activation obtained, then dry;
The DMF that d, step c obtain modifies MIL-101 product elder generation and the H of rear Ethanol activation
2pdCl
4solution mix, then with HAuCl
4with appropriate amount of deionized water mixing, be made into the solution of pH=3.0 ± 0.2, fully stirred by this solution at 35-37 DEG C of temperature, centrifugal, abandon supernatant liquor, deionized water fully washs rear abundant drying;
E, PdCl
4 2-and AuCl
4 -product is obtained, i.e. the MIL-101 of golden palladium modification after reduction treatment.
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 (TPA) 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 stereochemical structure, and its XRD angle of diffraction can offset to wide-angle, illustrates that the lattice paprmeter of MIL-101 diminishes, and namely DMF can react with MIL-101 really, changes its lattice character.And in the specific area of nitrogen adsorption assay, find that the specific area of the MIL-101 that DMF modifies is more much smaller than the specific 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.
In order to verify the MIL-101 that DMF modifies and follow-up ethylenediamine (ED), Au-Pd modify after the absorption property of MIL-101, also carried out MIL-101 that MIL-101 and Au-Pd that DMF modifies modify 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 adsorbed water, this MIL-101 illustrating that DMF modifies can be used in the occasion had higher requirements to water quality, and also can adsorb methylene blue completely through the MIL-101 that ED, Au-Pd modify, even may have certain chemical reaction and occur.
The invention has the beneficial effects as follows: the present invention have detected the performance change of ED-MIL-101, 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 adsorption capacity to formic acid.Therefore, ED-MIL-101 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, ED-MIL-101 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.
Although DMF-MIL-101 has the change of part-structure and performance compared to the MIL-101 of unmodified, being through experiment detection can find, and the MIL-101 of unmodified compares, the methylene blue in the complete adsorbent solution of ED-MIL-101 energy.And on the other hand, the follow-up modification of DMF-MIL-101 still can proceed, and modification effect does not weaken.The MIL-101 that ethylenediamine and golden palladium are modified is better than not modified MIL-101, is also have certain effect in the process for formic acid solution.
The MIL-101 that gold palladium is modified is the product obtained on the MIL-101 basis that DMF modifies, and this product is on the basis of the structural change continuing MIL-101, and its absorption property for methylene blue is better than not modified MIL-101's.Therefore, first we can determine that it is unimpaired for modifying the performance of the product after terminating in purifying dyestuff waste water.Secondly, golden palladium is as effective metallic catalyst, and it modifies the catalytic performance that more to give full play to them after to MIL-101.This is because, MIL-101 has very large specific area, it can adsorb the material that more needs are decomposed, catalysis for golden palladium provides basis, therefore, gold palladium can strengthen its catalysis, this product be had and applies widely after modifying on MIL-101 on the basis not damaging absorption property.
Accompanying drawing explanation
Fig. 1 is construction unit and the crystal structure figure of MIL-101 material;
Fig. 2 is the synthetic method flow chart 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 (TPA) (H of DMF modification
2bDC) infrared spectrogram;
Fig. 7 is the infrared spectrum contrast of ethylene diamine-modified MIL-101 and MIL-101;
Fig. 8 is the XRD spectra contrast of the MIL-101 that modified and unmodified are crossed;
Fig. 9 is the N of ED-MIL-101
2adsorption/desorption curve;
Figure 10 is the N of ED-Au-Pd-MIL-101
2adsorption/desorption curve;
Figure 11 is the pore size distribution curve of Au-Pd-MIL-101;
Figure 12 is the pore size distribution curve of ED-Au-Pd-MIL-101;
Figure 13 is the MIL-101 product absorption methylene blue effect photo of modified, is followed successively by DMF-MIL-101, ED-MIL-101, Au-Pd-MIL-101, ED-Au-Pd-MIL-101 in figure from a left side;
Figure 14 is the MIL-101 product absorption methylene blue effect photo modified without DMF;
Figure 15 is that the MIL-101 that DMF modifies adsorbs UV detect comparison diagram before and after methylene blue solution;
Figure 16 is that Au-Pd-MIL-101 adsorbs UV detect comparison diagram before and after methylene blue solution;
Figure 17 is that ED-Au-Pd-MIL-101 adsorbs UV detect comparison diagram before and after methylene blue solution;
Figure 18 is that the MIL-101 modified without DMF adsorbs UV detect comparison diagram before and after methylene blue solution.
Detailed description of the invention
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, percentage are unit of weight, 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 conventional 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 primary raw material and reagent
The instrument that table 2 mainly uses
Embodiment 1: the synthesis of ethylene diamine-modified MIL-101 (being abbreviated as ED-MIL-101)
MIL-101 product (the embodiment 4 obtains) 0.5g that the DMF taking the 12h that to dewater at 150 DEG C modifies is in 100mL round-bottomed flask, add 30mL dry toluene, add 0.05mL ethylenediamine (0.75mmol) liquid again, in oil bath pan, add hot reflux 12h.When being chilled to room temperature Deng solution, solution is poured in 50mL centrifuge tube, be centrifugal 2min in the centrifuge of 8000r/min at rotating speed, discard supernatant liquor, with absolute ethanol washing remaining solid several, and at room temperature dry, what obtain is ethylene diamine-modified product, is designated as ED-MIL-101.
Embodiment 2: the synthesis of the MIL-101 (being abbreviated as ED-Au-Pd-MIL-101) that ethylenediamine and golden palladium are modified
H
2pdCl
4the preparation of solution: take 0.5gPdCl
2solid is dissolved in the HCl aqueous solution of 20mL10% (v/v), is at room temperature stirred to and dissolves completely, for subsequent use.
Au-Pd double nano fragment in ED-MIL-101 modification is realized by simple dipping method.Detailed process is, takes 0.2gED-MIL-101 product (embodiment 1 obtains) in small beaker, the H prepared before adding 4mL
2pdCl
4solution, then take 0.1gHAuCl
4solid joins in the solution of small beaker, then adds 1mL deionized water, is made into the solution of pH=3.0, and this solution is stirred 24h at 35 DEG C of temperature.Stir after stopping slightly cold, centrifugal, outwell supernatant liquor, fully wash several times by deionized water, by the solid that obtains at 60 DEG C of air dryings.To transfer in crucible dry 8h in 150 DEG C of baking ovens after sample drying, now, being attracted to, ED-MIL-101 is PdCl
4 2-and AuCl
4 -ion.In order to obtain gold, the ED-MIL-101 of palladium bimetal modifying needs PdCl
4 2-and AuCl
4 -carry out reduction treatment: in 150 DEG C of products of drying, add 2mL80% hydrazine hydrate solution, mix, placement is spent the night.Every other day that mixed solution is centrifugal, outwell supernatant liquor, after deionized water washing, the solid obtained is dried in 100 DEG C of baking ovens.
Embodiment 3: the synthesis of the MIL-101 (being abbreviated as Au-Pd-MIL-101) that golden palladium is modified
H
2pdCl
4the preparation of solution: take 0.5gPdCl
2solid is dissolved in the HCl aqueous solution of 20mL10% (v/v), is at room temperature stirred to and dissolves completely, for subsequent use.
The building-up process of Au-Pd-MIL-101 is consistent with the building-up process of ED-Au-Pd-MIL-101.The DMF taking 0.2g150 DEG C of dehydration 12h in experiment modifies the MIL-101 product of rear Ethanol activation (embodiment 4 obtains) and in small beaker, adds 4mLH
2pdCl
4solution, 0.1gHAuCl
4, then add 1mL deionized water, be made into the solution of pH=3.0, and this solution is stirred 24h at 35 DEG C of temperature.Slightly cold, centrifugal after stopping stirring, outwell supernatant liquor, by the solid that obtains at 60 DEG C of air dryings, after drying by this solid transfer to crucible in 150 DEG C of baking ovens dry 8h.Equally also need to carry out reduction treatment to this dry products: in 150 DEG C of products of drying, add 2mL80% hydrazine hydrate solution, mix, placement is spent the night.Every other day that mixed solution is centrifugal, outwell supernatant liquor, after deionized water washing, the solid obtained is dried in 100 DEG C of baking ovens.
The synthesis of the MIL-101 (being abbreviated as DMF-MIL-101) that embodiment 4:DMF modifies
The present embodiment adopts hydro-thermal method as the synthetic method of preparation MIL-101.As shown in Figure 2, concrete steps are the flow chart of hydrothermal synthesis method synthesis MIL-101 crystal: electronic balance takes 2.0gCr (NO
3)
39H
2o and 0.83g terephthalic acid (TPA) (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 liquor in reactor carefully, now can see the bottom having a large amount of unreacted terephthalic acid (TPA)s and product MIL-101 to stay reactor.
Purge process (rear Ethanol activation is modified in DMF process): 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 centrifuge of 8000r/min at rotating speed.At the end of once centrifugal, pour out supernatant liquor carefully.Still have many terephthalic acid (TPA)s in centrifuge tube, now add DMF, and heated solution is to low-grade fever, after centrifuge, pour out supernatant liquor, centrifugal repeatedly till the acicular crystal (terephthalic acid (TPA)) no longer including white with DMF, washing terminates.Now, the pulverulent solids of the green bottom centrifuge tube is exactly washed away terephthalic acid (TPA) 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 polytetrafluoroethylene (PTFE), pour 50mL absolute ethyl 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 (TPA) 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 (being abbreviated as MIL-101) that DMF modifies
Electronic balance takes 2.0gCr (NO
3)
39H
2o and 0.83g terephthalic acid (TPA) (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 liquor in reactor carefully, now can see the bottom having a large amount of unreacted terephthalic acid (TPA)s 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 (TPA) is water insoluble and density is relatively little, in filtration, terephthalic acid (TPA) can be deposited on above MIL-101, after suction filtration terminates, carefully most for upper strata terephthalic acid (TPA) is removed with spoon.Remaining green powder solid and the terephthalic acid (TPA) 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 polytetrafluoroethylene (PTFE), pours 50mL absolute ethyl 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 (TPA) 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, by the solid that obtains 100 DEG C of oven dry.
For effect is described, inventor utilizes X-ray diffraction (XRD), N
2the characterization methods such as Static Adsorption, infrared absorption spectroscopy (IR) determine MIL-101 with ED, Au-Pd that the DMF that synthesizes modifies modify after the stereochemical structure of MIL-101, specific area and the aspect such as pore structure, thing are formed mutually character.
1, the X-ray diffraction analysis of MIL-101
Utilize X-ray diffractometer analysis, obtain the diffraction maximum of MIL-101, and compared with the XRD diffraction maximum 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 4 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 relevant position in document near have the appearance of characteristic peak, but obviously see that the characteristic peak of the MIL-101 modified through DMF offsets to wide-angle direction, this illustrates that the MIL-101 lattice paprmeter that DMF modifies diminishes (diffraction surfaces pitch smaller), confirms that DMF can change the stereochemical structure of MIL-101.
2, the infrared spectrum of MIL-101
MIL-101 is with Cr
3+centered by, terephthalic acid (TPA) is the crystalline product that part self assembly is formed.Terephthalic acid (TPA) has obvious carbonyl absorption peak (1600cm in infrared absorption spectroscopy
-1left and right) and the fingerprint region absworption peak of phenyl ring, so MIL-101 is carried out IR Characterization, its spectrogram should have very large similitude with the infrared spectrum of terephthalic acid (TPA).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 see 3000 by contrast, 1700cm
-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 absorption.
The MIL-101 product modify DMF and terephthalic acid (TPA) carry out infrared test and obtain corresponding infrared contrast spectrogram as shown in Figure 6.As seen in Fig., the infrared spectrum of the MIL-101 of DMF process and the infrared spectrum of terephthalic acid (TPA) 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 process 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 oxygen atom in carboxyl and chromic nitrate can be utilized to carry out coordination for terephthalic acid (TPA), 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 (TPA) and tripolymer carry out coordination, the environment of terephthalic acid (TPA) inside changes, so its Vibration Condition also changes thereupon.Go out within the scope of peak at fingerprint region phenyl ring, the MIL-101 of DMF process is on all four compared with terephthalic acid (TPA), illustrates in complexation process, is almost non-existent on the impact of phenyl ring.
3, the sign of the MIL-101 of modified
Preceding sections has carried out the detailed modification of MIL-101, and meanwhile, for above to the characterizing method of MIL-101, the present invention has also carried out corresponding sign to the MIL-101 of modified and compared with the characterization result of the MIL-101 without modified.
1. the infrared spectrum contrast of ED-MIL-101 and MIL-101
Amino in ethylenediamine is at 3400cm
-1to 3500cm
-1between have strong infrared absorption peak, amino characteristic peak will be equipped with to go out accordingly peak position when ethylenediamine is received on MIL-101.Fig. 7 shows the infrared spectrum contrast of ED-MIL-101 and DMF-MIL-101, as can clearly see from the figure at 3428cm
-1place ED-MIL-101 has obvious amino infrared absorption peak than DMF-MIL-101, illustrates that DMF-MIL-101 is by ethylene diamine-modified success.Can see, ED-MIL-101 is at 1700cm simultaneously
-1the carbonyl peak at place disappears, and these all describe ethylenediamine and create impact to DMF-MIL-101, also illustrates that ethylenediamine has successfully modified DMF-MIL-101.
The XRD spectra contrast of MIL-101 and MIL-101 after 2. modifying
Contrasted by the XRD spectra that MIL-101:ED-MIL-101, ED-Au-Pd-MIL-101 and Au-Pd-MIL-101 after modification is XRD spectra and MIL-101 respectively, Fig. 8 is the contrast situation of four XRD spectras.
Have correspondence in the XRD spectra of the MIL-101 of characteristic peak after modification in the XRD spectra of as can be seen from Figure 8 MIL-101, although this illustrates that MIL-101 is through modifying, its basic structure and morphology does not change.Just Comparatively speaking, the characteristic peak of ED-MIL-101 is more more than the characteristic peak of MIL-101, and this should be the change of the stereochemical structure causing MIL-101 due to ethylenediamine, and this also again illustrates ethylenediamine and has successfully modified MIL-101.And at the MIL-101 absworption peak that about 2 θ=40 ° Shi You have more of the MIL-101 modified containing Au and Pd than simple DMF process, this should be the characteristic peak of Au and Pd, this also illustrates that Au, Pd have by modification on MIL-101, and modification is also successful.
3. the N of MIL-101 and MIL-101 after modifying
2absorption contrast
MIL-101 for DMF modified carries out modifying ED-MIL-101, Au-Pd-MIL-101 and ED-Au-Pd-MIL-101 of obtaining and has also carried out N
2adsorption/desorption tests the result that obtains as shown in Fig. 9, Figure 10, Figure 11 and Figure 12, various MIL-101 product N
2absorption result is in table 3.
Table 3 various MIL-101 product N
2absorption result gathers
Can be seen by data in table 3 and to reduce much than the specific area of simple MIL-101 with ethylene diamine-modified MIL-101, and aperture also becomes greatly.And the aperture of the MIL-101 product of Au-Pd modified does not change a lot, but specific area is significantly large than MIL-101 a lot, this should be when carrying out Au-Pd modification, MIL-101 product is after 20% (v/v) salt acid soak, the DMF HCl in solution being adsorbed on MIL-101 is combined and forms salt, can remove a part when washing and remain in DMF in MIL-101, the specific area of the MIL-101 after Au-Pd is modified increases a lot.
3, not modified and after modifying MIL-101 adsorbs methylene blue test
MIL-101 receives the research of researcher because of its huge specific area and larger pore volume character, especially gas absorption 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 each absorption terminates, the color before and after methylene blue is carried out contrast of taking pictures, as shown in figure 13, 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.Figure 14 is the color 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 modified adsorbs the effective of methylene blue.
Methylene blue has obvious ultraviolet absorption peak at 660nm, 290nm and 245nm, carried out UV absorbance detection in order to the adsorption effect of methylene blue is better described, Figure 15,16,17 and Figure 18 be each sample to the UV absorption contrast before and after methylene blue adsorption number.And MIL-101 and ED-MIL-101 also doing simple DMF process in the result of Figure 15 stir in distilled water after the ultraviolet result that measures, to determine that MIL-101 and ED-MIL-101 of DMF process is to pure water mitigation.
By adsorbing the ultraviolet Comparative result before and after methylene blue above, find that MIL-101 and ED-MIL-101 can adsorb methylene blue completely, and Au-Pd-MIL-101 and ED-Au-Pd-MIL-101 is adsorbing on the basis of methylene blue completely, also find ultraviolet absorption curve its curve of shortwave strong point can to some extent on move, judge thus, may there occurs some chemical reactions in the process stirred, thus the absorption of these two kinds of products should be not only physical absorption.
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 slightly lighter, does not adsorb 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 characteristic absorption peak near this because remained a lot of terephthalic acid (TPA)s in the MIL-101 of DMF process.Relatively can be found out by these data of two groups, the MIL-101 without DMF process will be much better than through the MIL-101 of DMF process in absorption methylene blue effect.
To sum up, the present invention carries out modification to the MIL-101 product that DMF modifies and obtains corresponding modified outcome ED-MIL-101, Au-Pd-MIL-101, ED-Au-Pd-MIL-101, display is characterized to the XRD of these products, these modify the stereochemical structure substantially remaining MIL-101, but the stereochemical structure of the ethylene diamine-modified product ED-MIL-101 obtained can change more.Find in the measurement of specific area, it is maximum that the specific area of ethylene diamine-modified MIL-101 reduces, this should be that ethylenediamine grafting makes the aperture of MIL-101 diminish on MIL-101, and can become large in the specific area of the MIL-101 having Au-Pd to modify, because MIL-101 can through the immersion of hydrochloric acid solution when Au-Pd modifies, make DMF salify and washed away, increasing the specific area of the MIL-101 that Au-Pd modifies on the contrary.
The dyestuffs such as the methylene blue in the complete adsorption aqueous solution of MIL-101 energy that gold palladium is modified, and be easy to subsequent metal modification, as the carrier of metallic catalyst.
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 (8)
1. a preparation method of the MIL-101 of golden palladium 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 acicular crystal of white with DMF, washing terminates, and dry, namely the green powder solid obtained is washed away terephthalic acid (TPA) by DMF and the MIL-101 crude product modified by DMF;
After c, the MIL-101 crude product modified by DMF obtained by step b mix with absolute ethyl alcohol, at closed environment, 100 DEG C of temperature, place 20h, make the MIL-101 product activation obtained, then dry;
The DMF that d, step c obtain modifies MIL-101 product elder generation and the H of rear Ethanol activation
2pdCl
4solution mix, then with HAuCl
4with appropriate amount of deionized water mixing, be made into the solution of pH=3.0 ± 0.2, fully stirred by this solution at 35-37 DEG C of temperature, centrifugal, abandon supernatant liquor, deionized water fully washs rear abundant drying;
E, PdCl
4 2-and AuCl
4 -product is obtained, i.e. the MIL-101 of golden palladium modification after reduction treatment.
2. the preparation method of the MIL-101 of golden palladium 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 golden palladium modification according to claim 2, is characterized in that the concrete steps of step a are: get terephthalic acid (TPA), 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 in reactor, obtain the mixture of terephthalic acid (TPA) and MIL-101.
4. the preparation method of the MIL-101 of golden palladium 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. the preparation method of the MIL-101 of golden palladium modification according to claim 1, is characterized in that: the drying course in step c is more than the 12h that dewaters at 150-160 DEG C.
6. the preparation method of the MIL-101 of golden palladium modification according to claim 1, is characterized in that in steps d, ED-MIL-101 and H
2pdCl
4, HAuCl
4the mass ratio of three is 2:1:1.
7. the preparation method of the MIL-101 of golden palladium modification according to claim 1, it is characterized in that the detailed process of step e is: in 150 DEG C of products of drying, add 80% hydrazine hydrate solution, mix, placement is spent the night, every other day that mixed solution is centrifugal, outwell supernatant liquor, after deionized water washing, the solid obtained is dried in 100 DEG C ± 10 DEG C baking ovens.
8. a MIL-101 for golden palladium modification, is characterized in that the MIL-101 that this golden palladium is modified makes 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 acicular crystal of white with DMF, washing terminates, and dry, namely the green powder solid obtained is washed away terephthalic acid (TPA) by DMF and the MIL-101 crude product modified by DMF;
After c, the MIL-101 crude product modified by DMF obtained by step b mix with absolute ethyl alcohol, at closed environment, 100 DEG C of temperature, place 20h, make the MIL-101 product activation obtained, then dry;
The DMF that d, step c obtain modifies MIL-101 product elder generation and the H of rear Ethanol activation
2pdCl
4solution mix, then with HAuCl
4with appropriate amount of deionized water mixing, be made into the solution of pH=3.0 ± 0.2, fully stirred by this solution at 35-37 DEG C of temperature, centrifugal, abandon supernatant liquor, deionized water fully washs rear abundant drying;
E, PdCl
4 2-and AuCl
4 -product is obtained, i.e. the MIL-101 of golden palladium modification after reduction treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510540496.6A CN105521766A (en) | 2015-08-28 | 2015-08-28 | Gold-palladium-modified MIL-101 and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510540496.6A CN105521766A (en) | 2015-08-28 | 2015-08-28 | Gold-palladium-modified MIL-101 and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105521766A true CN105521766A (en) | 2016-04-27 |
Family
ID=55764489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510540496.6A Pending CN105521766A (en) | 2015-08-28 | 2015-08-28 | Gold-palladium-modified MIL-101 and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105521766A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397797A (en) * | 2016-08-29 | 2017-02-15 | 山东师范大学 | Gold-MOFs-polymer composite membrane, and production method and application thereof |
| CN107774331A (en) * | 2017-10-25 | 2018-03-09 | 宿迁市振兴化工有限公司 | A kind of Metal Supported MOFs catalyst and preparation method thereof and the application in PMDPTA synthesis |
| CN111359670A (en) * | 2020-03-10 | 2020-07-03 | 浙江工业大学 | Au-Pd/NH2-MIL-101(Cr) catalyst and preparation and application thereof |
| CN114452945A (en) * | 2022-02-15 | 2022-05-10 | 中国船舶重工集团公司第七一九研究所 | Preparation method of MOF composite material adsorbent for removing toluene gas |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733162A (en) * | 2009-12-24 | 2010-06-16 | 上海交通大学 | Organic metal framework supported palladium, preparation method and application thereof |
| WO2011099967A1 (en) * | 2010-02-10 | 2011-08-18 | The Board Of Regents Of The University Of Texas System | Acetylene storage using metal-organic frameworks with open metal sites |
| CN103008012A (en) * | 2012-12-12 | 2013-04-03 | 华东师范大学 | Metal organic skeleton structure material load platinum catalyst, as well as preparation method and application thereof |
| CN104525122A (en) * | 2014-12-05 | 2015-04-22 | 昆明理工大学 | Preparation method and application of metal-organic framework material |
| CN104667980A (en) * | 2015-02-17 | 2015-06-03 | 浙江工业大学 | Metal organic framework compound loaded metal-carbon oxide nano particle catalyst as well as preparation method and application thereof |
| CN104722338A (en) * | 2015-04-02 | 2015-06-24 | 哈尔滨工业大学 | Preparation method of titanium modified MIL-101(Cr) catalyst |
| WO2015119887A1 (en) * | 2014-02-04 | 2015-08-13 | Nivo Systems, Inc. | Open framework composites, methods for producing and using such composites |
-
2015
- 2015-08-28 CN CN201510540496.6A patent/CN105521766A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733162A (en) * | 2009-12-24 | 2010-06-16 | 上海交通大学 | Organic metal framework supported palladium, preparation method and application thereof |
| WO2011099967A1 (en) * | 2010-02-10 | 2011-08-18 | The Board Of Regents Of The University Of Texas System | Acetylene storage using metal-organic frameworks with open metal sites |
| CN103008012A (en) * | 2012-12-12 | 2013-04-03 | 华东师范大学 | Metal organic skeleton structure material load platinum catalyst, as well as preparation method and application thereof |
| WO2015119887A1 (en) * | 2014-02-04 | 2015-08-13 | Nivo Systems, Inc. | Open framework composites, methods for producing and using such composites |
| CN104525122A (en) * | 2014-12-05 | 2015-04-22 | 昆明理工大学 | Preparation method and application of metal-organic framework material |
| CN104667980A (en) * | 2015-02-17 | 2015-06-03 | 浙江工业大学 | Metal organic framework compound loaded metal-carbon oxide nano particle catalyst as well as preparation method and application thereof |
| CN104722338A (en) * | 2015-04-02 | 2015-06-24 | 哈尔滨工业大学 | Preparation method of titanium modified MIL-101(Cr) catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 刘宏利: "MIL-101负载金属纳米催化剂的制备及其绿色催化研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397797A (en) * | 2016-08-29 | 2017-02-15 | 山东师范大学 | Gold-MOFs-polymer composite membrane, and production method and application thereof |
| CN106397797B (en) * | 2016-08-29 | 2018-11-13 | 山东师范大学 | A kind of gold-MOFs- composite membrane of polymer and the preparation method and application thereof |
| CN107774331A (en) * | 2017-10-25 | 2018-03-09 | 宿迁市振兴化工有限公司 | A kind of Metal Supported MOFs catalyst and preparation method thereof and the application in PMDPTA synthesis |
| CN107774331B (en) * | 2017-10-25 | 2020-05-15 | 宿迁市振兴化工有限公司 | Metal-loaded MOFs catalyst, preparation method thereof and application thereof in PMDPTA synthesis |
| CN111359670A (en) * | 2020-03-10 | 2020-07-03 | 浙江工业大学 | Au-Pd/NH2-MIL-101(Cr) catalyst and preparation and application thereof |
| CN114452945A (en) * | 2022-02-15 | 2022-05-10 | 中国船舶重工集团公司第七一九研究所 | Preparation method of MOF composite material adsorbent for removing toluene gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105503958A (en) | Ethylenediamine-modified MIL-101 and preparation method thereof | |
| Ma et al. | Assembling ultrafine TiO2 nanoparticles on UiO-66 octahedrons to promote selective photocatalytic conversion of CO2 to CH4 at a low concentration | |
| Bai et al. | A novel functional porous organic polymer for the removal of uranium from wastewater | |
| CN108671892A (en) | A kind of metal organic framework UiO-66 adsorbents and its modified material | |
| Yue et al. | Metal ion-assisted carboxyl-containing covalent organic frameworks for the efficient removal of Congo red | |
| CN109569521B (en) | Rhodanine functionalized MOFs adsorbent and preparation method and application thereof | |
| CN105521766A (en) | Gold-palladium-modified MIL-101 and preparation method thereof | |
| CN108339522B (en) | Amino acid @ Cu-BTC composite adsorbent and preparation method thereof | |
| WO2021143112A1 (en) | Super-microporous zirconium-based metal-organic framework material, preparation method therefor, and use thereof | |
| CN108993419B (en) | Method for preparing Ni-MOF adsorption material by ultrasonic-assisted solvothermal method and application | |
| Zhang et al. | Effects of different defective linkers on the photocatalytic properties of Cu-BTC for overall water decomposition | |
| CN108329484A (en) | Double ligand metal organic framework materials of a kind of iron-based of Preferential adsorption ethane and the preparation method and application thereof | |
| Khosroshahi et al. | Fabrication of a novel heteroepitaxial structure from an MOF-on-MOF architecture as a photocatalyst for highly efficient Cr (vi) reduction | |
| Shi et al. | A metal-OH group modification strategy to prepare highly-hydrophobic MIL-53-Al for efficient acetone capture under humid conditions | |
| CN113441114A (en) | Mixed metal MOF and preparation method and application thereof | |
| CN113004275A (en) | Copper complex and preparation method and application thereof | |
| CN102614833A (en) | Modified titanium nanotube absorbent for absorbing carbon dioxide and preparation method and application thereof | |
| Huang et al. | A steric hindrance alleviation strategy to enhance the photo-switching efficiency of azobenzene functionalized metal–organic frameworks toward tailorable carbon dioxide capture | |
| Lu et al. | Bimetallic CoCu-ZIF material for efficient visible light photocatalytic fuel denitrification | |
| Yuan et al. | High-alumina fly ash as sustainable aluminum sources for the in situ preparation of Al-based eco-MOFs | |
| CN113842889B (en) | Microwave synthesis metal organic framework material DUT-5 (Al), synthesis method and application thereof | |
| CN108160041A (en) | A kind of sulfide in gas deep absorption desulfurization agent and preparation method | |
| Timofeeva et al. | Tuning the Catalytic Performance of Novel Composites Based on ZIF‐8 and Nafen through Dimensional and Concentration Effects in the Synthesis of Propylene Glycol Methyl Ether | |
| Bai et al. | Membrane adsorber with hierarchically porous HKUST-1 immobilized in membrane pores by flowing synthesis | |
| Thoresen et al. | Strongly visible light-absorbing metal–organic frameworks functionalized by cyclometalated ruthenium (II) complexes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160427 |