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
- Publication number
- CN102775430B CN102775430B CN201210230903.XA CN201210230903A CN102775430B CN 102775430 B CN102775430 B CN 102775430B CN 201210230903 A CN201210230903 A CN 201210230903A CN 102775430 B CN102775430 B CN 102775430B
- Authority
- CN
- China
- Prior art keywords
- maf
- porous material
- mpba
- polymer porous
- coordination polymer
- 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.)
- Expired - Fee Related
Links
Landscapes
- 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210230903.XA CN102775430B (en) | 2012-08-29 | 2012-08-29 | Coordination polymer porous material MAF-X8 and preparing method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210230903.XA CN102775430B (en) | 2012-08-29 | 2012-08-29 | Coordination polymer porous material MAF-X8 and preparing method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102775430A CN102775430A (en) | 2012-11-14 |
| CN102775430B true CN102775430B (en) | 2015-06-24 |
Family
ID=47120561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210230903.XA Expired - Fee Related CN102775430B (en) | 2012-08-29 | 2012-08-29 | Coordination polymer porous material MAF-X8 and preparing method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102775430B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2012
- 2012-08-29 CN CN201210230903.XA patent/CN102775430B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| 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 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102775430A (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102775430B (en) | Coordination polymer porous material MAF-X8 and preparing method and application thereof | |
| Zhang et al. | Zeolitic imidazole framework templated synthesis of nanoporous carbon as a novel fiber coating for solid-phase microextraction | |
| Gao et al. | Development and application of vortex-assisted membrane extraction based on metal–organic framework mixed-matrix membrane for the analysis of estrogens in human urine | |
| CN106770544B (en) | Ni-MOF ultrathin nanometer band, synthetic method and its application | |
| Abolghasemi et al. | Periodic mesoporous organosilica with ionic liquid framework as a novel fiber coating for headspace solid-phase microextraction of polycyclic aromatic hydrocarbons | |
| Zheng et al. | In situ growth of IRMOF-3 combined with ionic liquids to prepare solid-phase microextraction fibers | |
| Saraji et al. | Mesoporous carbon–zirconium oxide nanocomposite derived from carbonized metal organic framework: a coating for solid-phase microextraction | |
| Liu et al. | Magnetic porous carbon-based solid-phase extraction of carbamates prior to HPLC analysis | |
| CN110918075A (en) | Preparation and application of metal organic framework magnetic nano porous carbon material | |
| CN109261141A (en) | A kind of ZIF-8 is nanocrystalline and its preparation method and application | |
| CN103399064A (en) | Oxidized graphene/hydrotalcite/Nafion composite film modified electrode and preparation method thereof | |
| Xie et al. | In-situ exfoliation of graphitic carbon nitride with metal-organic framework via a sonication-assisted approach for dispersive solid-phase extraction of perfluorinated compounds in drinking water samples | |
| Alizadeh et al. | Electrocatalytic oxidation of salicylic acid at a carbon paste electrode impregnated with cerium-doped zirconium oxide nanoparticles as a new sensing approach for salicylic acid determination | |
| Tashakkori et al. | Molecularly imprinted polymer based on magnetic ionic liquid for solid-phase extraction of phenolic acids | |
| CN104557718B (en) | A kind of preparation method and applications of RHO zeolite type 2-ethyl imidazol(e) zinc porous material | |
| CN108993419A (en) | A kind of ultrasonic wave secondary solvent thermal method prepares the method and application of Ni-MOF adsorbent material | |
| Shu et al. | Role of counteranions in sol–gel-derived alkoxyl-functionalized ionic-liquid-based organic–inorganic hybrid coatings for SPME | |
| Xu et al. | Designed 3D N-doped magnetic porous carbon spheres for sensitive monitoring of biogenic amine by simultaneous microwave-assisted derivatization and magnetic-solid phase extraction | |
| CN111474248A (en) | Method for determining four preservatives in cosmetics | |
| Jia et al. | Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds | |
| CN114713196A (en) | Preparation and application of metal organic framework derived bimetallic oxide magnetic carbon material | |
| Zheng et al. | Highly water-dispersible hydroxyl functionalized covalent organic frameworks as matrix for enhanced MALDI-TOF MS identification and quantification of quaternary ammonium salts in water and fruits | |
| Sabale et al. | Understanding time dependence on zinc metal–organic framework growth using in situ liquid secondary ion mass spectrometry | |
| CN112295552B (en) | Hierarchical pore UiO-66 solid-phase micro-extraction fiber prepared by in-situ etching method and application thereof | |
| CN105536783A (en) | A preparing method of an ordered mesoporous carbon-supported Ru nanometer catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150624 Termination date: 20160829 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |