CN108421541A - A kind of preparation method and application of carbonization Zn bases MOFs extraction coatings - Google Patents
A kind of preparation method and application of carbonization Zn bases MOFs extraction coatings Download PDFInfo
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- CN108421541A CN108421541A CN201810216394.2A CN201810216394A CN108421541A CN 108421541 A CN108421541 A CN 108421541A CN 201810216394 A CN201810216394 A CN 201810216394A CN 108421541 A CN108421541 A CN 108421541A
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- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 238000000605 extraction Methods 0.000 title claims abstract description 54
- 238000003763 carbonization Methods 0.000 title claims abstract description 37
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000003795 desorption Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004458 analytical method Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 239000000523 sample Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000000284 extract Substances 0.000 claims abstract description 5
- 238000002474 experimental method Methods 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims description 22
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 22
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- 230000004224 protection Effects 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- -1 methyl formyls Amine Chemical class 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 claims description 7
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004021 humic acid Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 13
- 231100000719 pollutant Toxicity 0.000 abstract description 13
- 239000000835 fiber Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- UXFSPRAGHGMRSQ-UHFFFAOYSA-N 3-isobutyl-2-methoxypyrazine Chemical compound COC1=NC=CN=C1CC(C)C UXFSPRAGHGMRSQ-UHFFFAOYSA-N 0.000 description 14
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000002470 solid-phase micro-extraction Methods 0.000 description 7
- 238000010276 construction Methods 0.000 description 6
- 230000001419 dependent effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000540 analysis of variance Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009672 coating analysis Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses the preparation method and application that a kind of carbonization Zn bases MOFs extracts coating, the preparation method includes：Synthesize 8 coatings of ZIF, carbonization；The application is：A kind of analysis method of aromatic series odor pollutant in water body is established, specially：By the Zn bases MOFs extraction coating material of carbonization in 20 50 DEG C of extraction temperature, 20 80min of extraction time, 0.5 4min of desorption time, 200 270 DEG C of desorption temperature, salinity 0 37%, under the conditions of carry out extraction experiments, the effect of extracting difference of the front and back extraction coating and commercialization fiber coat of comparison carbonization, and probe into the thermal stability and chemical stability of synthetic coating.Material preparation of the present invention is simple, easy to operate, of low cost, method for building up favorable reproducibility.Therefore, the present invention is used to detect the aromatic series Taste and odor compounds in polluted-water, has good economy and environmental benefit.
Description
Technical field
The present invention relates to inorganic material and water-treatment technology field, and in particular to a kind of carbonization Zn bases MOFs carbonizations coating
Preparation method and application.
Background technology
The basic principle of solid phase micro-extraction technique is the method by physics or chemistry, by the painting with extraction function
Layer material is immobilized on certain matrix surface.Coating carries out direct or indirect contact with sample, target analytes is enriched with dense
Contracting, then by coating be placed directly within injection port thermal desorption, with sample introduction after sampling device combination or solvent desorption, to sample
In object accurately analyzed.Up to the present, most popular is fiber type solid phase microextraction.This method is divided into
Two step of extraction process and desorption process：(1) extraction process：Solid phase micro-extraction stainless steel protection sheath is inserted into sample bottle, is released
Coating part extracts sample, after a period of time, withdraws in extraction coating to stainless steel needle tubing, that is, completes to extract
Journey.(2) desorption process：Using the target substance on thermal desorption desorption coating in gas chromatographic analysis, i.e., it will be completed and extract
The extracting fiber of journey is inserted into the vaporizer of gas chromatographic sample introduction mouth, depresses handle, extraction coating is made to be exposed to high temperature carrier gas
In, extract is desorbed, and is directly entered gas chromatographic analysis.
Currently, commercialization solid-phase micro-extraction fibre has been successfully applied to the measurement of Taste and odor compounds in a variety of surrounding mediums.But
It is that in extraction process, commercialization solid-phase micro-extraction fibre is there are some disadvantages, for example high temperature is unstable etc..
Metal organic frame (MOFs) is the porous material of high-sequential, with adjustable pore structure and chemical work(
Energy.It can be used for hydrogen storage, gas separation, catalysis, sensor technology, imaging etc..In addition, MOFs in gases/vapors and
Liquid phase adsorption removal harmful substance etc. shows huge potential application, such as SCC, NCC, dyestuff, PPCPs, phenols, SOx,
NOx, VOCs etc..Currently, MOFs char-forming materials are because it is with higher specific surface area, can modulation pore passage structure, it is higher
Thermal stability and chemical stability gradually cause more and more extensive concern.
Invention content
For the above technical problem, first technical problem that the present invention solves preparing simple, cost there is provided a kind of
The preparation method of cheap Zn bases MOFs carbonizations coating；There is provided a kind of carbonization Zn for another technical problem that the present invention solves
The application of base MOFs carbonization coatings, specially：It establishes a kind of Zn bases MOFs and is carbonized coating to aromatic series Taste and odor compounds in water body
Analysis method.
In order to solve the first technical problem mentioned above, the technical scheme is that：A kind of system of Zn bases MOFs carbonizations coating
Preparation Method includes the following steps：
Step 1：Synthesize ZIF-8 coatings
1) 1M HCl, methanol, deionized water ultrasound 30min are used respectively, and stainless steel 304 steel wire matrix is pre-processed；
2) 2.868g zinc nitrate hexahydrates and 0.72g methylimidazoles are weighed, and is dissolved in 216 milliliters of N-N-2 methyl
Formamide (DMF)；
3) solution and matrix are transferred in autoclave and are heated up 24 hours for 140 DEG C；It is anti-that solution is transferred to microwave again
It is 500-3000MHz to answer in kettle with frequency, and power is that the microwave of 5-8kW carries out the microwave treatment of a 3-5min；
4) crystal and mother liquor are detached, faint yellow brilliant material is obtained；
5) 20mL chloroformic solutions are added with matrix in obtained yellow crystals to embathe；Temperature is maintained at 25- when embathing
28℃；
6) it is rinsed with DMF solution；
7) resulting materials are placed in drying in draught cupboard and for 24 hours, that is, obtain ZIF-8 coatings；
Step 2：Carbonization
1) the ZIF-8 coatings of above-mentioned synthesis are put in tube furnace；
2) 250 DEG C of holding 6h of setting temperature program, then the 700-1000 DEG C of holding 8h that heat up, obtain carbonization MOFs coatings.
Further, step 2 carburizing temperature is to be raised to 700,800,900,1000 DEG C of holding 8h respectively；Using middle and high
Temperature carbonization can effectively improve carbonation rate, and medium and high temperature has no effect on the carbonization effect up to ZIF-8.
To solve above-mentioned second technical problem, the technical scheme is that：Establish a kind of Zn bases MOFs carbonizations coating
To the analysis method of aromatic series Taste and odor compounds in water body.
Further, it probes into SPME coating extraction process, influences the principal element of SPME extraction efficiencies, including extraction
Time, extraction temperature, desorption time, desorption temperature and salinity, establish L16(45) orthogonal experiment, and use variance analysis
Method (Analysis of Variance, ANOVA) each factor of method quantitative analysis determines the influence degree of experimental result
Has the experimental factor having a significant impact.
Further, it is determined that extraction conditions after optimization, comparison Zn bases MOFs carbonization coatings are imitated with commercial fiber coat extraction
Fruit considers influence of the humic acid to extraction conditions.
Further, this is probed into acid, alkali, polar solvent and nonpolar solvent processing Zn bases MOFs carbonization coatings respectively
The chemical stability of coating, and thermogravimetric analysis is done to the material, probe into its thermal stability.
Further, in the above scheme, the preparation method of the Zn bases MOFs carbonizations coating is：
1) hydro-thermal method synthesizes ZIF-8 coatings；
2) it is placed in N again2700,800,900,1000 DEG C of roasting in tube furnace under protection obtains MOFs carbonization coatings.
The beneficial effects of the invention are as follows：The present invention overcomes unstable disadvantage under the conditions of conventional commercial fiber high temperature, establishes
A kind of analysis method of the Zn bases MOFs carbonization coating to aromatic series Taste and odor compounds in water body.In addition, material preparation letter of the present invention
It is single, it is easy to operate, it is of low cost, have higher thermal stability and chemical stability.Therefore, the present invention is smelt for aromatic series
The detection of taste substance, this method reproducibility is preferable, and the range of linearity is wider.
Specific implementation mode
Embodiment 1：
The preparation of carbonization ZIF-8 coatings：
1) 1M HCl, methanol, deionized water ultrasound 30min are used respectively, and stainless steel 304 steel wire matrix is pre-processed；
2) 2.868g zinc nitrate hexahydrates and 0.72g methylimidazoles are weighed, and is dissolved in 216 milliliters of N-N-2 methyl
Formamide (DMF), with glass bar mixing；
3) solution and matrix are transferred in autoclave and are heated up 24 hours for 140 DEG C；It is anti-that solution is transferred to microwave again
It is 500MHz to answer in kettle with frequency, and power is that the microwave of 5-8kW carries out the microwave treatment of a 3min；
4) crystal and mother liquor are detached, faint yellow brilliant material is obtained；
5) 20mL chloroformic solutions are added with matrix in obtained yellow crystals to embathe；Temperature is maintained at 25 when embathing
℃；
6) it is rinsed with DMF solution；
7) resulting materials are placed in drying in draught cupboard and for 24 hours, that is, obtain ZIF-8 coatings.
8) resulting materials are put in tube furnace；In N2Under protection, 250 DEG C of holding 6h of setting temperature program are warming up to
700 DEG C of holding 8h, obtain carbonization coating material.
20 DEG C, extraction time 20min, desorption time 0.5min of extraction temperature of selection, 200 DEG C of desorption temperature, salinity 0,
The bottle cap with polytetrafluoroethylene (PTFE) is punctured when extraction, stretching coating is partially disposed in water phase and is extracted, will extraction after the completion of extraction
Coating is drawn back into stainless steel protection sheath, and GC-MS injection ports are immediately inserted into, and stretches out coating, and Thermal desorption is carried out in injection port.Choosing
Use C700Coating establishes the analysis method to 2,4,6- trichloro-benzenes oxygen ethers (TCA) and 2 methoxy 3 isobutyl pyrazine (IBMP),
Standard deviation (relative standard deviation, RSD) of two kinds of pollutants under institute's construction method is respectively
5.69% and 7.61% (n=8).This method measures the linearly dependent coefficient of 2 kinds of aromatic series odor pollutants more than 0.990.
The range of linearity is wider, across three orders of magnitude.Detection limit is down to 0.05 μ g/L.
Embodiment 2:
The preparation of carbonization ZIF-8 coatings：
1) 1M HCl, methanol, deionized water ultrasound 30min are used respectively, and stainless steel 304 steel wire matrix is pre-processed；
2) 2.868g zinc nitrate hexahydrates and 0.72g methylimidazoles are weighed, and is dissolved in 216 milliliters of N-N-2 methyl
Formamide (DMF), with glass bar mixing；
3) solution and matrix are transferred in autoclave and are heated up 24 hours for 140 DEG C；It is anti-that solution is transferred to microwave again
It is 500MHz to answer in kettle with frequency, and power is that the microwave of 5-8kW carries out the microwave treatment of a 3min；
4) crystal and mother liquor are detached, faint yellow brilliant material is obtained；
5) 20mL chloroformic solutions are added with matrix in obtained yellow crystals to embathe；Temperature is maintained at 25 when embathing
℃；
6) it is rinsed with DMF solution；
7) resulting materials are placed in drying in draught cupboard and for 24 hours, that is, obtain ZIF-8 coatings.
8) resulting materials are put in tube furnace；Under N2 protections, 250 DEG C of holding 6h of setting temperature program are warming up to
800 DEG C of holding 8h, obtain carbonization coating material.
Choose 30 DEG C, extraction time 40min, desorption time 1min of extraction temperature, 230 DEG C of desorption temperature, salinity
10%, when extraction, punctures the bottle cap with polytetrafluoroethylene (PTFE), stretches out coating and is partially disposed in water phase and is extracted, after the completion of extraction
Extraction coating is drawn back into stainless steel protection sheath, GC-MS injection ports are immediately inserted into, coating is stretched out, is pyrolyzed in injection port
Analysis.Select C800Coating establishes the analysis method to TCA and IBMP, standard deviation difference of two kinds of pollutants under institute's construction method
For 7.53% and 6.69% (n=8).The linearly dependent coefficient that this method measures 2 kinds of aromatic series odor pollutants is more than
0.990.The range of linearity is wider, across four orders of magnitude.Detection limit is down to 0.01 μ g/L.
Embodiment 3:
The preparation of carbonization ZIF-8 coatings：
1) 1M HCl, methanol, deionized water ultrasound 30min are used respectively, and stainless steel 304 steel wire matrix is pre-processed；
2) 2.868g zinc nitrate hexahydrates and 0.72g methylimidazoles are weighed, and is dissolved in 216 milliliters of N-N-2 methyl
Formamide (DMF), with glass bar mixing；
3) solution and matrix are transferred in autoclave and are heated up 24 hours for 140 DEG C；It is anti-that solution is transferred to microwave again
It is 500MHz to answer in kettle with frequency, and power is that the microwave of 5-8kW carries out the microwave treatment of a 3min；
4) crystal and mother liquor are detached, faint yellow brilliant material is obtained；
5) 20mL chloroformic solutions are added with matrix in obtained yellow crystals to embathe；Temperature is maintained at 25 when embathing
℃；
6) it is rinsed with DMF solution；
7) resulting materials are placed in drying in draught cupboard and for 24 hours, that is, obtain ZIF-8 coatings.
8) resulting materials are put in tube furnace；In N2Under protection, 250 DEG C of holding 6h of setting temperature program are warming up to
900 DEG C of holding 8h, obtain carbonization coating material.
Choose 40 DEG C, extraction time 60min, desorption time 2min of extraction temperature, 250 DEG C of desorption temperature, salinity
20%, when extraction, punctures the bottle cap with polytetrafluoroethylene (PTFE), stretches out coating and is partially disposed in water phase and is extracted, after the completion of extraction
Extraction coating is drawn back into stainless steel protection sheath, GC-MS injection ports are immediately inserted into, coating is stretched out, is pyrolyzed in injection port
Analysis.Select C900Coating establishes the analysis method to TCA and IBMP, standard deviation RSD of two kinds of pollutants under institute's construction method
Respectively 9.32% and 5.12% (n=8).The linearly dependent coefficient that this method measures 2 kinds of aromatic series odor pollutants is more than
0.992.The range of linearity is wider, across four orders of magnitude.Detection limit is down to 0.008 μ g/L.
Embodiment 4
The preparation of carbonization ZIF-8 coatings：
1) 1M HCl, methanol, deionized water ultrasound 30min are used respectively, and stainless steel 304 steel wire matrix is pre-processed；
2) 2.868g zinc nitrate hexahydrates and 0.72g methylimidazoles are weighed, and is dissolved in 216 milliliters of N-N-2 methyl
Formamide (DMF), with glass bar mixing；
3) solution and matrix are transferred in autoclave and are heated up 24 hours for 140 DEG C；It is anti-that solution is transferred to microwave again
It is 500MHz to answer in kettle with frequency, and power is that the microwave of 5-8kW carries out the microwave treatment of a 3min；
4) crystal and mother liquor are detached, faint yellow brilliant material is obtained；
5) 20mL chloroformic solutions are added with matrix in obtained yellow crystals to embathe；Temperature is maintained at 25 when embathing
℃；
6) it is rinsed with DMF solution；
7) resulting materials are placed in drying in draught cupboard and for 24 hours, that is, obtain ZIF-8 coatings.
8) resulting materials are put in tube furnace；In N2Under protection, 250 DEG C of holding 6h of setting temperature program are warming up to
1000 DEG C of holding 8h, obtain carbonization coating material.
Choose 50 DEG C, extraction time 80min, desorption time 4min of extraction temperature, 270 DEG C of desorption temperature, salinity
37%, when extraction, punctures the bottle cap with polytetrafluoroethylene (PTFE), stretches out coating and is partially disposed in water phase and is extracted, after the completion of extraction
Extraction coating is drawn back into stainless steel protection sheath, GC-MS injection ports are immediately inserted into, coating is stretched out, is pyrolyzed in injection port
Analysis.Select C1000Coating establishes the analysis method to TCA and IBMP, standard deviation RSD of two kinds of pollutants under institute's construction method
Respectively 3.62% and 4.97% (n=8).The linearly dependent coefficient that this method measures 2 kinds of aromatic series odor pollutants is more than
0.993.The range of linearity is wider, across five orders of magnitude.Detection limit is down to 0.005 μ g/L.
Comparative example 1
The preparation of ZIF-8 coatings：
1) 1M HCl, methanol, deionized water ultrasound 30min are used respectively, and stainless steel 304 steel wire matrix is pre-processed；
2) 2.868g zinc nitrate hexahydrates and 0.72g methylimidazoles are weighed, and is dissolved in 216 milliliters of N-N-2 methyl
Formamide (DMF), with glass bar mixing；
3) solution and matrix are transferred in autoclave and are heated up 24 hours for 140 DEG C；It is anti-that solution is transferred to microwave again
It is 500MHz to answer in kettle with frequency, and power is that the microwave of 5-8kW carries out the microwave treatment of a 3min；
4) crystal and mother liquor are detached, faint yellow brilliant material is obtained；
5) 20mL chloroformic solutions are added with matrix in obtained yellow crystals to embathe；Temperature is maintained at 25 when embathing
℃；
6) it is rinsed with DMF solution；
7) resulting materials are placed in drying in draught cupboard and for 24 hours, that is, obtain ZIF-8 coatings.
20 DEG C, extraction time 20min, desorption time 0.5min of extraction temperature of selection, 200 DEG C of desorption temperature, salinity 0,
ZIF-8 coatings are selected to establish the analysis method to TCA and IBMP, standard deviation difference of two kinds of pollutants under institute's construction method
For 9.63% and 9.19% (n=8).The linearly dependent coefficient that this method measures 2 kinds of aromatic series odor pollutants is more than
0.98.The range of linearity is wider, across three orders of magnitude.Detection limit is down to 0.5 μ g/L.
Comparative example 2
20 DEG C, extraction time 20min, desorption time 0.5min of extraction temperature of selection, 200 DEG C of desorption temperature, salinity 0,
Commercial fiber coat is selected to establish the analysis method to TCA and IBMP, standard deviation difference of two kinds of pollutants under institute's construction method
It Wei not 10.36% and 11.29% (n=8).The linearly dependent coefficient that this method measures 2 kinds of aromatic series odor pollutants is more than
0.95.The range of linearity is wider, across two orders of magnitude.Detection limit is down to 0.1 μ g/L.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：It is still
It can modify to the technical solution recorded in previous embodiment or equivalent replacement of some of the technical features；
And these modifications or replacements, technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (7)
1. a kind of preparation method of carbonization Zn bases MOFs extraction coatings, which is characterized in that include the following steps：
Step 1：Synthesize ZIF-8 coatings
1) 1M HCl, methanol, deionized water ultrasound 30min are used respectively, and stainless steel 304 steel wire matrix is pre-processed；
2) 2.868g zinc nitrate hexahydrates and 0.72g methylimidazoles are weighed, and is dissolved in 216 milliliters of N-N-2 methyl formyls
Amine (DMF)；
3) solution and matrix are transferred in autoclave, 140 DEG C heat up 24 hours；Solution is transferred to microwave reaction kettle again
Middle with frequency is 500-3000MHz, and power is that the microwave of 5-8kW carries out the microwave treatment of a 3-5min；
4) crystal and mother liquor are detached, faint yellow brilliant material is obtained；
5) 20mL chloroformic solutions are added with matrix in obtained yellow crystals to embathe, temperature is maintained at 25-28 DEG C when embathing；
6) it is rinsed with DMF solution；
7) resulting materials are placed in drying in draught cupboard and for 24 hours, that is, obtain ZIF-8 coatings；
Step 2：Be carbonized ZIF-8 coatings
The ZIF-8 coatings of above-mentioned synthesis are put in tube furnace, 250 DEG C of holding 6h of setting temperature program, then the 700-1000 that heats up
DEG C keep 8h, obtain carbonization ZIF-8 coatings.
2. a kind of preparation method of carbonization Zn bases MOFs extraction coatings as described in claim 1, which is characterized in that the step
Two carburizing temperatures are to be raised to 700,800,900,1000 DEG C of holding 8h respectively.
3. a kind of Zn bases MOFs carbonization extraction coatings prepared by method as claimed in claim 1 or 2, which is characterized in that be used for
Establish a kind of analysis method of aromatic series Taste and odor compounds.
4. application as claimed in claim 3, which is characterized in that the Zn bases MOFs of carbonization extracts coating in extraction temperature 20-50
DEG C, extraction time 20-80min, desorption time 0.5-4min, 200-270 DEG C of desorption temperature, salinity 0-37%, under the conditions of into
Row extraction experiments.
5. application as claimed in claim 3, which is characterized in that probe into influence of the dissolubility humic acid to extraction process.
6. application as claimed in claim 3, which is characterized in that the preparation method of the Zn bases MOFs carbonizations extraction coating is：
1) hydro-thermal method synthesizes ZIF-8 coatings；
2) it is placed in N2700,800,900,1000 DEG C of roasting in tube furnace under protection obtains carbonization Zn bases MOFs extraction coating materials
Material.
7. application as claimed in claim 6, which is characterized in that probe into influence of the dissolubility humic acid to extraction process.
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