CN103193804A - Preparation method of metal-organic coordination polymer material - Google Patents
Preparation method of metal-organic coordination polymer material Download PDFInfo
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- CN103193804A CN103193804A CN2013100844246A CN201310084424A CN103193804A CN 103193804 A CN103193804 A CN 103193804A CN 2013100844246 A CN2013100844246 A CN 2013100844246A CN 201310084424 A CN201310084424 A CN 201310084424A CN 103193804 A CN103193804 A CN 103193804A
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- coordination polymer
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 29
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003751 zinc Chemical class 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract 2
- 239000011701 zinc Substances 0.000 claims description 26
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- 239000003755 preservative agent Substances 0.000 claims description 9
- 230000002335 preservative effect Effects 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 238000007605 air drying Methods 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical class O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000002178 crystalline material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000000935 solvent evaporation Methods 0.000 abstract 1
- 230000003407 synthetizing effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 8
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003639 trimesic acids Chemical class 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000013254 iso-reticular metal–organic framework Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
The invention discloses a preparation method of a metal-organic coordination polymer material. The preparation method is characterized by comprising the following steps of: (1) adding metal zinc salt and carboxyl-contained polydentate ligand into deionized water; (2) adding ammonia water into a solution obtained in the step (1) and stirring the solution to be clear; (3) carrying out a heating reaction on the solution obtained in the step (2) under constant pressure, cooling the solution to the constant pressure so as to obtain a metal-organic coordination polymer material; and (4) carrying out suction filtration on the metal-organic coordination polymer material obtained in the step (3), successively washing by utilizing deionized water and absolute ethyl alcohol, and carrying out natural withering to obtain the pure crystalline phase metal-organic coordination polymer material. The method provided by the invention has the advantages that the reaction temperature is increased under constant pressure, the synthetic crystal time is effectively shortened by utilizing a conventional solvent evaporation method, the porous crystalline material obtained by synthetizing has potential application on aspects such as adsorption separation and catalysis of gas and dissolvent micromolecule as well as nanoreactors.
Description
Technical field
The invention belongs to the preparation field of a kind of metal-organic coordination polymer material, refer more particularly to the preparation of a kind of porous metal-organic coordination polymer material.
Background technology
Metal-organic coordination polymer (Metal-Organic Coordination Polymer, MOCPs) material refers to contain the multiple tooth organic ligand of nitrogen, oxygen etc. and the class material with periodic network topological framework that the self-assembly of transition metal particle forms, claim again metallic organic framework (Metal-Organic Framework, MOF).Characteristics such as regular pore canal structure, high porosity, specific surface area are big because it has, controllable structure and unusual light, electricity, magnetic effect.This class is unique, the diversified material of structure in gas storage, fractionation by adsorption, catalysis, nonlinear optics, magnetics, serve as aspects such as nano-reactor potential application prospect arranged, be to study a kind of new function material widely in recent years.
Williams had reported 3-dimensional metal-organic coordination polymer [Cu that is constructed by cupric ion and trimesic acid at Science in 1999
3(TMA)
2(H
2O)
3] n(HKUST-1).This structure comprises wheel slurry formula (Paddle-wheel) secondary structure unit [Cu
2(O
2CR)
4], the interlaced three-dimensional net structure that is connected to form of these secondary structure units has the aperture and is about 9 * 9
2Square duct.Guest molecule in the duct can be removed, and can be replaced by other guest molecule such as pyridine etc.
Yaghi research group in 2002 is prototype with MOF-5, by modification and the expansion to organo-functional group (terephthalic acid), successfully constructed the IRMOF(Isoreticular Metal-Organic Framework of aperture span from 3.8 to 28.8) serial molecular sieve analog material.Meanwhile, French Ferey research group has also synthesized the MIL-n series material of a series of relative macropores.
Present synthesizing porous metal organic coordination polymer method is varied: solution evaporation method, diffusion process, the hot method of hydrothermal/solvent and ultrasonic, microwave and ultraviolet Technology etc., but generally have deficiencies such as length consuming time or complicated operation.
Summary of the invention
The present invention relates to the preparation of a kind of metal-organic coordination polymer material, this material is to have reached the purpose of improving the reaction times by the conditioned reaction temperature under normal pressure.
The preparation of metal of the present invention-organic coordination polymer material is characterized in that, comprises the steps:
1) gets metal zinc salt and contain the carboxylic acid polydentate ligand and put into deionized water and obtain A solution;
2) ammoniacal liquor is added in the A solution that step 1) obtains, stir to clarify, obtain B solution, the envelope film is used the pinprick hole;
3) with step 2) described B solution, react 12-72h down at normal pressure 60-90 ℃, be cooled to room temperature, obtain metal-organic coordination polymer material;
4) with the described metal of step 3)-organic coordination polymer filtration of material, use deionized water and absolute ethanol washing successively, natural air drying namely gets target product.
Further, in the described step 1), the metal zinc salt is a kind of or its mixture of zinc nitrate hexahydrate, two hydration zinc acetates or six zinc sulphate hydrates;
In the described step 1), containing the carboxylic acid polydentate ligand is terephthalic acid or trimesic acid;
The concentration of zine ion is 0.15-0.25mol/L in the described step 1).
Described step 2) in, it is 1:1.25-2 with the mol ratio that contains the carboxylic acid polydentate ligand that the B GOLD FROM PLATING SOLUTION belongs to Zn salt; The control of the starting point concentration of ammoniacal liquor is at 2.0-7.5mol/L in the B solution.
If when organic ligand was trimesic acid in the described step 1), the target product of step 4) was porous material Zn
6BTC
412NH
310H
2O, structural formula is as follows:
Compare with background technology, of the present invention have a following effect:
With routine with organic deprotonation reagent such as triethylamine synthetic comparing in the High Temperature High Pressure high temperature and high pressure kettle, the present invention selects for use ammoniacal liquor as deprotonation reagent, can be relatively gentle at reaction conditions, namely shorten under the condition in reaction times by the conditioned reaction temperature under the normal pressure and synthesized pure crystalline phase metal-organic coordination polymer material.
Description of drawings
Fig. 1 is Zn synthetic in the invention example 1
6BTC
412NH
310H
2The cell configuration of O, wherein hydrogen atom is omitted;
Fig. 2 is Zn synthetic in the invention example 1
6BTC
412NH
310H
2The accumulation graph of O, wherein hydrogen atom is omitted;
Fig. 3 is Zn synthetic in the invention example 1
6BTC
412NH
310H
2The X-ray powder diffraction pattern of O;
Fig. 4 is Zn synthetic in the invention example 1
6BTC
412NH
310H
2The infrared spectrogram of O;
Fig. 5 is Zn synthetic in the invention example 1
6BTC
412NH
310H
2O's
13C CP MAS nuclear magnetic spectrogram;
Fig. 6 is Zn synthetic in the invention example 1
6BTC
412NH
310H
2The TG curve of O;
Fig. 7 is ZnBDC2NH synthetic in the invention example 3
3Cell configuration.
Embodiment
1) takes by weighing Zn (CH
3COO)
22H
2O(1.19 g, 5 mmol), (2.10 g 10mmol) put into the 24ml deionized water to trimesic acid, and note is done solvent orange 2 A;
2) with 6 ml NH
3H
2O adds in the above-mentioned solvent orange 2 A, is stirred to the solution clarification, seals with preservative film, and the area of pricking 15 apertures (the diameter D=0.6mm in hole)/preservative film at preservative film with pin is 78.5cm
2, as follows; Pricking the hole is for ammoniacal liquor can volatilize, but does not need strict control rate of volatilization, and note is solvent B, and this moment, the concentration of ammoniacal liquor was 5.1mol/L;
3) solvent B is reacted 48h down at 80 ℃, take out and be cooled to room temperature, obtain the metal organic coordination polymer crystalline material.
4) will wash through deionization successively after the crystal filtration, dehydrated alcohol is washed, and natural air drying namely makes metal-organic cooperation polymer materials Zn
6BTC
412NH
310H
2O.
Zn
6BTC
412NH
310H
2O belongs to oblique system, crystal group is C2/c, unit cell parameters is a=18.7297 (11), alpha=90 deg., b=8.0929 (5), beta=99.6650 (10) deg., c=20.0274 (13), contain a tetrahedral structure in gamma=90 deg. crystal, tetrahedral center is Zn
2+, Zn
2+Respectively with from two NH
3Two N Atomic coordinates, Zn
2+Two oxygen atom ligands with two trimesic acids.In view of this crystal Zn
6BTC
412NH
310H
2O is porous material, and has planar water in the hole, has wide application prospect with regard to having established this crystal in the adsorbing domain of gas or small solvent molecule like this, and potential application is being arranged aspect the nano molecular reactor.The X-ray powder diffraction pattern of Fig. 3 has proved that synthetic target product is pure crystalline phase.
Embodiment 2
1) takes by weighing Zn (NO
3)
26H
2O(1.49g, 5 mmol), (1.57 g 7.5mmol) put into the 20ml deionized water to trimesic acid, and note is done solvent orange 2 A;
2) with 5 ml NH
3H
2O adds in the above-mentioned solvent orange 2 A, is stirred to the solution clarification, seals with preservative film, pricks 10 apertures (D=0.6mm)/78.5cm with pin at preservative film
2, note is solvent B, and this moment, the concentration of ammoniacal liquor was 5.14mol/L;
3) solvent B is reacted 12h down at 90 ℃, take out and be cooled to room temperature, obtain metal-organic coordination polymer crystalline material.
4) with deionized water washing successively after the crystal filtration, dehydrated alcohol is washed, and natural air drying namely makes metal-organic coordination polymer material Zn
6BTC
412NH
310H
2O.
Zn
6BTC
412NH
310H
2O belongs to oblique system, crystal group is C2/c, unit cell parameters is a=18.7297 (11), alpha=90 deg., b=8.0929 (5), beta=99.6650 (10) deg., c=20.0274 (13), contain a tetrahedral structure in gamma=90 deg. crystal, tetrahedral center is Zn
2+, Zn
2+Respectively with two NH
3Two N Atomic coordinates, Zn
2+Respectively with two oxygen atom ligands of two trimesic acids.
Embodiment 3
5) take by weighing Zn (NO
3)
26H
2O(1.49g, 5 mmol), (1.66 g 10mmol) put into the 24ml deionized water to terephthalic acid, and note is done solvent orange 2 A;
6) with 6 ml NH
3H
2O adds in the above-mentioned solvent orange 2 A, is stirred to the solution clarification, seals with preservative film, pricks 15 apertures (D=0.6mm)/78.5cm with pin at preservative film
2, note is solvent B, and this moment, the concentration of ammoniacal liquor was 5.14mol/L;
7) solvent B is reacted 72h down at 70 ℃, take out and be cooled to room temperature, obtain the metal organic coordination polymer crystalline material.
8) will wash through deionization successively after the crystal filtration, dehydrated alcohol is washed, and natural air drying namely makes metal-organic cooperation polymer materials ZnBDC2NH
3
ZnBDC2NH
3Belong to oblique system, crystal group is P2 (1)/m, unit cell parameters is a=5.235 (2), alpha=90 deg., b=16.240 (6), beta=111.168 (5) deg., c=6.002 (5), contain a tetrahedral structure in gamma=90 deg. crystal, tetrahedral center is Zn
2+, Zn
2+Respectively with two NH
3Two N Atomic coordinates, Zn
2+Respectively with two oxygen atom ligands of two terephthalic acids.
Trimesic acid makes the crystal results of elemental analyses:
C36H68Zn6N12O34 ultimate analysis Theoretical Calculation content (%): C, 36.46; H, 3.83; N, 10.63. measured value content: C, 36.52; H, 4.17; N, 10.34.
Table 1 results of elemental analyses
| C | H | N | |
| Theoretical Calculation content (%) | 36.46 | 3.83 | 10.63 |
| Measured value content (%) | 36.52 | 4.17 | 10.34 |
Claims (5)
1. metal-organic coordination polymer preparation methods comprises the steps:
1) gets metal zinc salt and contain the carboxyl polydentate ligand and put into deionized water and obtain A solution; The described carboxylic acid polydentate ligand that contains is terephthalic acid or trimesic acid; It is 1:1.25-2 with the mol ratio that contains the carboxyl polydentate ligand that described GOLD FROM PLATING SOLUTION belongs to zinc salt;
2) ammoniacal liquor is added in the A solution that step 1) obtains, stir to clarify, obtain B solution, seal with preservative film, prick the hole with pin at preservative film;
3) with step 2) described B solution, react 12-72h down at normal pressure 60-90 ℃, be cooled to room temperature, obtain metal-organic coordination polymer material;
4) with the described metal of step 3)-organic coordination polymer material suction filtration, use deionized water and absolute ethanol washing successively, natural air drying namely gets target product.
2. a kind of metal according to claim 1-organic coordination polymer preparation methods is characterized in that, the metal zinc salt in the step 1) is a kind of or its mixture of zinc nitrate hexahydrate, two hydration zinc acetates, six zinc sulphate hydrates.
3. according to the described a kind of metal of claim 1-organic coordination polymer preparation methods, it is characterized in that the concentration of zine ion is 0.15-0.25mol/L in the step 1) A solution.
4. according to the described a kind of metal of claim 1-organic coordination polymer preparation methods, it is characterized in that step 2) described in the B solution ammonia concn be 2.0-7.5mol/L.
5. according to the described a kind of metal of claim 1-organic coordination polymer preparation methods, it is characterized in that when being trimesic acid as if organic ligand in the described step 1), the target product of step 4) is porous material Zn
6BTC
412NH
310H
2O, structural formula is as follows:
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106501230A (en) * | 2016-12-22 | 2017-03-15 | 郑州大学 | A kind of application of sulfydryl silver cluster coordination polymer in organic solvent detection |
| CN107158964A (en) * | 2017-07-04 | 2017-09-15 | 中国石油大学(华东) | A kind of composite film material based on metal organic framework nanometer sheet and graphene oxide, preparation method and the application in gas separation |
| CN108101736A (en) * | 2017-12-13 | 2018-06-01 | 湖北大学 | A kind of ligand compound and preparation method thereof and a kind of two-dimensional nano reactor and its application |
| CN110028759A (en) * | 2018-11-15 | 2019-07-19 | 许文强 | A kind of preparation method of the epoxy resin electronic package material modified based on porous gel |
| CN111118533A (en) * | 2020-01-07 | 2020-05-08 | 中国科学院化学研究所 | Preparation method of two-dimensional tetracarboxyphenyl porphyrin metal organic framework film |
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2013
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106501230A (en) * | 2016-12-22 | 2017-03-15 | 郑州大学 | A kind of application of sulfydryl silver cluster coordination polymer in organic solvent detection |
| CN106501230B (en) * | 2016-12-22 | 2019-01-08 | 郑州大学 | A kind of application of sulfydryl silver cluster coordination polymer in organic solvent detection |
| CN107158964A (en) * | 2017-07-04 | 2017-09-15 | 中国石油大学(华东) | A kind of composite film material based on metal organic framework nanometer sheet and graphene oxide, preparation method and the application in gas separation |
| CN107158964B (en) * | 2017-07-04 | 2020-03-03 | 中国石油大学(华东) | Composite membrane material based on metal organic framework nanosheets and graphene oxide, preparation method and application in gas separation |
| CN108101736A (en) * | 2017-12-13 | 2018-06-01 | 湖北大学 | A kind of ligand compound and preparation method thereof and a kind of two-dimensional nano reactor and its application |
| CN108101736B (en) * | 2017-12-13 | 2020-12-22 | 湖北大学 | Ligand compound and preparation method thereof, and two-dimensional nano reactor and application thereof |
| CN110028759A (en) * | 2018-11-15 | 2019-07-19 | 许文强 | A kind of preparation method of the epoxy resin electronic package material modified based on porous gel |
| CN111118533A (en) * | 2020-01-07 | 2020-05-08 | 中国科学院化学研究所 | Preparation method of two-dimensional tetracarboxyphenyl porphyrin metal organic framework film |
| CN111118533B (en) * | 2020-01-07 | 2021-08-17 | 中国科学院化学研究所 | Preparation method of two-dimensional tetracarboxyphenyl porphyrin metal organic framework film |
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| CN103193804B (en) | 2016-03-30 |
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