CN102775430B - Coordination polymer porous material MAF-X8 and preparing method and application thereof - Google Patents
Coordination polymer porous material MAF-X8 and preparing method and application thereof Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title abstract description 8
- 239000013256 coordination polymer Substances 0.000 title abstract description 5
- 229920001795 coordination polymer Polymers 0.000 title abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000013110 organic ligand Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000002470 solid-phase micro-extraction Methods 0.000 abstract description 12
- -1 Zn2+ ions Chemical class 0.000 abstract description 7
- 238000003795 desorption Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract description 2
- JNHKHFADRGJMJS-UHFFFAOYSA-N 2-(3,5-dimethyl-1h-pyrazol-4-yl)benzoic acid Chemical compound CC1=NNC(C)=C1C1=CC=CC=C1C(O)=O JNHKHFADRGJMJS-UHFFFAOYSA-N 0.000 abstract 1
- 150000001555 benzenes Chemical class 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000013259 porous coordination polymer Substances 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 7
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a coordination polymer porous material MAF-X8 and a preparing method and an application thereof. The chemical formula of the coordination polymer porous material MAF-X8 is [Zn (mpba)], wherein the [Zn (mpba)] represents negative ions obtained by removing protons of an organic ligand 2-(3,5-Dimethyl-1H-pyrazol-4-yl) benzoic acid (H2mbpa). MAF-X8 crystals are in an orthorhombic system, an Ibca space group, and in a three-dimensional frame structure with a single-dimensional pore passage formed through the bridging of mbpa2-ligands and quadridentate Zn2+ ions and with a pore rate of 50%, the Langmuir specific surface is larger than 1300m2/g, and good ghermal stability and chemical stability are provided. Particularly, the coordination polymer porous material MAF-X8 can be conveniently manufactured into thin films to be applied in solid phase micro extraction (SPME), and shows high accumulation ability and adsorption selectivity to non-polar benzene series, and has short adsorption and desorption time, low detection limit, wide linear range and the like simultaneously.
Description
Technical field
The present invention relates to microporous coordination polymer field of porous materials, be specifically related to a kind of ligand polymer porous material MAF-X8 and preparation method thereof.
Background technology
Porous coordination polymer (PCPs) is a kind of crystalline material be made up of metal ion and organic ligand; there is the advantages such as specific surface area is large, density is low, aperture size is adjustable, channel surfaces modifiability is strong, the storage of gas and liquid can be widely used in, be separated, the field (US 5862796 such as heterogeneous catalyst; US 6624318; US6930193; US 7196210; US 20080121105).
Although conventional poly carboxylic acid organic ligand coordination mode is various, is beneficial to and forms abundant network structure, the PCPs constructed with it major part stability is lower.In recent years, have a lot of research to show, the PCPs that the part with imidazoles or pyrazole group is constructed has higher heat/chemical stability usually, and special optomagnetic and adsorption property, causes the concern of international research person.In addition, it should be noted that current most PCPs becomes regular film due to very difficult direct growth, is carry out applying with the form of a large amount of powder substantially, and this limits its application at the more wide spectrum such as microdevice, sensing and analyzing and testing undoubtedly.
Such as, solid-phase microextraction (SPME) a kind ofly integrates sample extraction, separation, the efficient sample pre-treatments of concentrated whole process and beneficiation technologies, and be easy to and the coupling of the analytical instrument such as gas-chromatography, high performance liquid chromatography, so at environment, biological, medicine, the fields such as food are widely used.The core of this technology is solid phase coated material and the coating solution technology of probe, but owing to lacking ripe sorbing material, it is lower that the homemade probe of the probe of current commercialization and laboratory is still faced with enriching quantity, thermostability and poor chemical stability, poor reproducibility, time of equilibrium adsorption is longer, also the problem such as selective or poor anti jamming capability.Facing to the sample substrate interference become increasingly complex and higher trace ultratrace analysis requirement, the efficient adsorption material seeking a kind of performance more superior seems most important.
Accordingly, we devise a kind of double function ligand simultaneously with carboxyl and pyrazolyl, constructed a kind of novel porous ligand polymer, have good chemistry and thermostability with zine ion.And this ligand polymer is easily prepared into high-quality thin film, can be used for preparing high efficiency SPME probe.
Summary of the invention
The object of the present invention is to provide a kind of ligand polymer porous material MAF-X8 based on pyrazoles Zinc dibenzoate.
Another object of the present invention is the preparation method providing above-mentioned porous material.
A further object of the invention is the application providing above-mentioned porous material.
The object of the invention is achieved by the following technical programs:
A kind of ligand polymer porous material MAF-X8, its chemical formula is [Zn (mpba)], wherein mpba
2-represent organic ligand 4-(3,5-Dimethyl-pyrazol-4-base) phenylformic acid (H
2mpba) negatively charged ion after proton is sloughed.Porous material MAF-X8 of the present invention crystallization is at rhombic system, and Ibca spacer passes through mpba
2the Zn of-part bridging four-coordination
2+(the widest and the narrowest place is respectively the one-dimensional channels that has that ion is formed
with
) three-dimensional frame structure, hole ratio is 50%.Methyl on part has blocked Zn atom completely and part has been blocked coordination O atom thus improve the hydrophobicity in duct.
The preparation method of ligand polymer porous material MAF-X8 of the present invention:
By H
2mpba, zinc nitrate and solvent join in hydrothermal reaction kettle in the lump, are heated to 120 ° of C and react and obtain MAF-X8 monocrystalline or powdered sample in 3 days.Described solvent is the mixed solution of N,N-dimethylacetamide (DMA) and methyl alcohol.
The preparation method of the film of ligand polymer porous material MAF-X8 of the present invention:
By H
2mpba, zinc nitrate and solvent join in hydrothermal reaction kettle in the lump, and reaction solution is put in the substrate that surperficial acid activation is crossed are heated to 120 ° of C and react and obtain MAF-X8 film in 1 day.
Be specially: by H
2mpba (0.1mmol), Zn (NO
3)
26H
2o (0.1mmol), DMA (1.5mL) and methyl alcohol (4.5mL) join in the reactor of band polytetrafluoroethylsubstrate substrate together, and reaction solution is put in the substrate (as stainless steel needle) that surperficial acid activation is crossed, airtightly be heated to 120 ° of C and keep 1 day, can in substrate surface growth MAF-X8 film.Then appropriate methanol wash substrate surface is used and drying.
MAF-X8 material of the present invention can by absorption guest molecule in storage, separation, catalysis, sensing, molecular recognition or heat exchange material.Especially, described polymer materials can be prepared into film and is applied in solid-phase microextraction.
Compared with prior art, the present invention has following beneficial effect:
(1) the MAF-X8 thermostability of design and synthesis of the present invention is fabulous, can be stabilized to 450 ° of C; Water stability is also fine, even if also can not destroy its skeleton construction under being exposed to saturated vapor; And the most heat/water stability of PCPs that general poly carboxylic acid is constructed is poor;
(2) MAF-X8 of the present invention's synthesis has very large hole ratio and specific surface area, the specific surface of this material and hole ratio utilize low temperature nitrogen to adsorb and use Langmuir and Dubinin-Raduskhvich Equation for Calculating to obtain respectively, and its Langmuir specific surface area is greater than 1300m
2g
-1;
(3) the present invention synthesis MAF-X8 to nonpolar benzene homologues (as benzene (B), toluene (T), ethylbenzene (E), dimethylbenzene (X), be called for short BTEX) there is very high accumulation ability, under equal conditions, enriching quantity is 18 to 157 times of commercial PDM S coated material respectively, is 2 to 8 times of commercial PDM S/DVB coated material;
(4) MAF-X8 of the present invention's synthesis is to nonpolar benzene homologues time of equilibrium adsorption very short (7 minutes), desorption time is very very short (0.5 minute) also, have detection line low, the advantages such as linearity range is wide, very applicable being applied to efficiently is analyzed fast and is detected simultaneously;
(5) MAF-X8 of the present invention's synthesis has very strong adsorption selectivity and immunity from interference, under equal conditions, the phenol compound of adsorb polar hardly, even if when the amount of polarity chaff interference substantially exceeds the amount of determinand BTEX, it is still highly stable to the adsorptive capacity of the latter, substantially not by the impact of a large amount of chaff interference.And under comparable conditions, commercial PDMS or PDMS/DVB material result is very different, as obviously reduced along with the increase of chaff interference the enriching quantity of BTEX.
Accompanying drawing explanation
Fig. 1 is the structure of novel porous materials MAF-X8 of the present invention;
Fig. 2 is the X-ray powder diffraction figure of MAF-X8 of the present invention, comprises the powder of former synthesis, the powder scraped off from film and various powder after Overheating Treatment;
Fig. 3 is the thermogravimetric curve figure of MAF-X8 of the present invention;
Fig. 4 is MAF-X8 of the present invention nitrogen adsorption isotherm when 77K;
The scanning electron microscope (SEM) photograph of Fig. 5 film prepared by MAF-X8 of the present invention;
The SPME probe of Fig. 6 prepared by MAF-X8 of the present invention is to the adsorption equilibrium curve of BTEX;
The SPME probe of Fig. 7 prepared by MAF-X8 of the present invention compares with the enriching quantity of commercial PDM S and PDMS/DVB probe;
The SPME probe of Fig. 8 prepared by MAF-X8 of the present invention compares with commercial PDMS and PDMS/DVB probe adsorption selectivity.
Embodiment
Explain the present invention further below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
Embodiment 1 pyrazoles Zinc dibenzoate porous material MAF-X8 single crystal preparation
By part H
2mpba (0.022g, 0.1mmol), Zn (NO
3)
26H
2o (0.030g, 0.1mmol), N, N-N,N-DIMETHYLACETAMIDE (DMA, 0.1mL), ethanol (2.5mL), water (2.5mL) and trimethylbenzene (1.0mL) join in hydrothermal reaction kettle in the lump, be heated to 120 ° of C to react and within 3 days, obtain colourless MAF-X8 monocrystalline, productive rate is 54%.
The preparation of a large amount of powder of embodiment 2 pyrazoles Zinc dibenzoate porous material MAF-X8
By H
2mpba (0.0108g, 0.5mmol), Zn (NO
3)
26H
2o (0.150g, 0.5mmol), DMA (3.0mL), methyl alcohol (9mL) joins in hydrothermal reaction kettle in the lump, is heated to 120 ° of C and reacts 1 day, to be cooled to room temperature, by DMA and methanol wash, obtain white to pale yellow powder, productive rate 62%.Gained powder 200 ° of C heating 30min removing guest molecules under nitrogen atmosphere, can obtain not containing the MAF-X8 of object.The X-ray diffractogram of product is shown in Fig. 2.
Embodiment 3 is containing guest molecule and not containing the structural characterization of the MAF-X8 of object
Single crystal X-ray diffraction data are collected on Bruker Smart APEX CCD diffractometer, graphite monochromator, uses
ray, collects data with ω scan mode, and absorption correction adopts SADABS program.Utilize direct method to resolve, then obtain whole non-hydrogen atom coordinate with difference Fourier function method and method of least squares, finally by method of least squares, structure is revised.Organic hydrogen atom of compound is obtained by theoretical hydrogenation method, and the hydrogen of object water molecules is by finding out in difference Fourier figure.Evaluation work uses SHELXTL program to complete on PC.Detailed axonometry data are in table 1.Structure is shown in Fig. 1.
Table 1
[a]R
1=∑||F
o|-|F
c||/∑|F
o|.
[b]wR
2=[∑w(F
o 2-F
c 2)
2/∑w(F
o 2)
2]
1/2.
The thermostability of embodiment 4 embodiment 1,2 gained Porous coordination polymer MAF-X8 characterizes
The thermostability of porous material is obtained by thermogravimetry.Thermogravimetric curve figure is shown in Fig. 3.
The gas adsorption character of embodiment 5 embodiment 2 gained Porous coordination polymer MAF-X8 characterizes
Put into hyaloid QC by with this porous material removing object, then under 77K condition, measure its nitrogen adsorption isotherm at ASAP 2020M adsorption instrument.N
2adsorption isothermal line is the absorption of I type, and Langmuir specific surface area is 1306m
2g
-1, BET specific surface area is 1161m
2g
-1, its adsorption isotherm line chart is shown in Fig. 4.
Embodiment 6 take MAF-X8 as the preparation of the SPME probe of coating
First one end of stainless steel needle is immersed in chloroazotic acid and make its surface active in 15 minutes, then use pure water washes clean.Then H
2mpba (22mg, 0.1mmol), Zn (NO
3)
26H
2o (30mg, 0.1mmol), N, N-N,N-DIMETHYLACETAMIDE (1.5mL) and methyl alcohol (4.5mL) join in the reactor of band polytetrafluoroethylsubstrate substrate together, and the stainless steel needle of above-mentioned activation is vertically put into still, airtightly be heated to 120 ° of C and keep 1 day, the probe of MAF-X8 film in surface growth can be obtained.Then use appropriate methanol wash draw point surperficial and aging in gas-chromatography.The SEM Electronic Speculum figure of film is shown in Fig. 5.
The time of equilibrium adsorption of the SPME probe of embodiment 7 embodiment 6 gained, enriching quantity and adsorption selectivity characterize
First BTEX or BTEX without concentration ratio and phenol compound is configured, the aqueous solution of (specifically comprising 2-chlorophenol (CP), p-cresol (P), 2-nitrophenols (PC), 2,4 dichloro phenol (DCP), 2,4,6-Trichlorophenol (TCP)).Then carry out headspace extraction with prepared SPME probe, then carry out thermal desorption and separation detection on gas chromatograph-mass spectrometer (GC-MS), qualitative by chromatographic peak retention time, use peak area quantification.Also to the PDMS(100 μm of commercialization under similarity condition) and PDMS/DVB(65 μm) probe also tests, to carry out the contrast of enriching quantity and adsorption selectivity with prepared MAF-X8 probe.Time of equilibrium adsorption is shown in Fig. 6, and enriching quantity and adsorption selectivity are shown in Fig. 7,8 respectively.
Claims (4)
1. a ligand polymer porous material MAF-X8, its chemical formula is [Zn (mpba)], wherein mpba
2-represent organic ligand 4-(3,5-Dimethyl-pyrazol-4-base) phenylformic acid H
2mpba sloughs the negatively charged ion after proton, described porous material crystallization at rhombic system,
ibcaspacer, a=13.9249, b=23.653, c=23.637 pass through mpba
2-the Zn of part bridging four-coordination
2+the three-dimensional frame structure with one-dimensional channels that ion is formed.
2. the preparation method of ligand polymer porous material MAF-X8 described in claim 1, it is characterized in that comprising the steps: 4-(3,5-Dimethyl-pyrazol-4-base) phenylformic acid, zinc nitrate and solvent join in the lump in hydrothermal reaction kettle, be heated to 120 DEG C of reactions and obtain MAF-X8 monocrystalline or powdered sample in 3 days.
3. the preparation method of the film of ligand polymer porous material MAF-X8 described in claim 1, it is characterized in that comprising the steps: 4-(3,5-Dimethyl-pyrazol-4-base) phenylformic acid, zinc nitrate and solvent join in hydrothermal reaction kettle in the lump, and reaction solution is put in the substrate that surperficial acid activation is crossed be heated to 120 DEG C of reactions and obtain MAF-X8 film in 1 day.
4. preparation method as claimed in claim 2 or claim 3, is characterized in that described solvent is the mixed solution of N,N-dimethylacetamide and methyl alcohol.
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| CN104650123B (en) * | 2015-02-13 | 2016-06-29 | 哈尔滨工业大学 | A kind of preparation method of organic-metallic thin film |
| CN104650122B (en) * | 2015-02-13 | 2016-06-29 | 哈尔滨工业大学 | A kind of preparation method of organic-metallic thin film |
| CN105037403B (en) * | 2015-07-08 | 2017-04-19 | 中山大学 | Coordination polymer porous material MAF-49, preparation method therefor and application thereof |
| CN107200850B (en) * | 2017-05-22 | 2020-07-28 | 云南师范大学 | Porous coordination polymer with aromatic molecule recognition function, preparation and application |
| KR20220025053A (en) * | 2019-07-03 | 2022-03-03 | 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 | Metal-organic framework material containing pyrazolyl benzoate ligand and method for preparing same |
| CN115340680B (en) * | 2022-08-11 | 2023-05-12 | 东南大学 | Zinc coordination polymer based on pyrazole carboxylic acid ligand, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101830857A (en) * | 2010-04-20 | 2010-09-15 | 中山大学 | Sodalite porous coordination polymer material as well as preparation method and application thereof |
| CN102161671A (en) * | 2011-02-23 | 2011-08-24 | 中山大学 | Coordination polymer material with multistage pore passage structure and preparation method thereof |
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| CN101830857A (en) * | 2010-04-20 | 2010-09-15 | 中山大学 | Sodalite porous coordination polymer material as well as preparation method and application thereof |
| CN102161671A (en) * | 2011-02-23 | 2011-08-24 | 中山大学 | Coordination polymer material with multistage pore passage structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| Hydrothermal synthesis, crystal structure, thermal and photoluminescent properties of Zn(II) and Cd(II) coordination polymers with 3-methyl-5-(pyridin-4-yl)benzoic acid;Qingfu Zhang et al.;《Inorganic Chemistry Communications》;20120710;第24卷;第195—199页 * |
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