CN107126942A - A kind of preparation method and applications of metal organic nano pipe coating - Google Patents
A kind of preparation method and applications of metal organic nano pipe coating Download PDFInfo
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- CN107126942A CN107126942A CN201710313607.9A CN201710313607A CN107126942A CN 107126942 A CN107126942 A CN 107126942A CN 201710313607 A CN201710313607 A CN 201710313607A CN 107126942 A CN107126942 A CN 107126942A
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- 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
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention discloses a kind of preparation method of metal organic nano pipe coating and application, it solves the poor technical problem of heat endurance of PDMS, PDMS/DVB and PA in the prior art, the zinc metal organic nano pipe coating prepared, under the mating reaction of silicone resin layer, the heat endurance of zinc metal organic nanotube can bring up to 335 DEG C, with higher heat resistance, with longer service life, and there is higher stability, higher sensitivity and preferable selectivity to Nitro Polycyclic Aromatic Hydrocarbons.Its technical scheme is：1) one end of stainless steel wire hydrofluoric acid is corroded after setting time, cleaned, dried；2) by step 1) the corrosion section of the stainless steel wire of processing is then rapid to take out vertically into organic siliconresin；3) organic siliconresin on stainless steel wire surface is handled, forms it into one layer of uniform film；4) by the part adhesive zinc metal organic nanotube powder bed of stainless steel wire gluing, produce.
Description
Technical field
The present invention relates to abstraction technique field, and in particular to a kind of preparation method of metal-organic nano pipe coating is with answering
With.
Background technology
At present, Solid-phase Microextraction is a kind of new Sample Pretreatment Technique, maximum feature be need not use it is organic
Solvent, and collect sampling, extract and concentrate in one, it has been widely used in multiple fields.The principle of this technology is to be based on
Extraction equilibrium of the target analytes between sample and coating, its core is fiber coat.Now, many commercializations
Coating such as dimethyl silicone polymer (PDMS, its heat resisting temperature is 280 DEG C), dimethyl silicone polymer-divinylbenzene (PDMS/
DVB, its heat resisting temperature is 270 DEG C) and polyacrylate (PA, its heat resisting temperature be 320 DEG C) etc. be successfully applied to reality
The analysis of environmental sample.But, these coatings, which have also, some shortcomings, and such as heat endurance is poor (being less than 300 DEG C), and price is held high
It is expensive.When solid phase micro-extraction technique and gas chromatographic technique are combined, it is necessary to by the extraction column and analytical column after SPME
Connection, is put into gas chromatograph furnace box and carries out thermal desorption, and the thermal desorption of different materials is different with the temperature of operation.Such as, remove
When careless agent is extracted using extraction columns such as PDMS, PA, the temperature of desorption is 280 DEG C；When being detected to organophosphorus pesticide,
Extracting head is using preceding needing to carry out aging 3h at 300 DEG C.
PDMS, PDMS/DVB and PA of the prior art heat endurance are poor, and general heat resisting temperature is less than 300 DEG C, institute
With, it is difficult to detected to the higher materials of some pyrolysis eutectoid temperatures, and be not suitable for extraction column using preceding need compared with
High-temperature carries out the situation for the long period carrying out aging.
In addition, the sampling mode of Solid-phase Microextraction has direct and two kinds of head space, direct method is to be inserted directly into extraction column
Fluid sample or in air, be particularly suitable for use in clean matrix.But the selectivity of existing coating material is not good, works as base
When there is macromolecular interference in body, these macromoleculars can be extracted the measure that test substance is disturbed after column extracting.So, for waving
Hair and half volatile samples, headspace sampling apply more, and sample matrices are not straight with extraction coating when one of reason is exactly head space
Contact, it is to avoid after other materials in matrix are extracted, interference measurement.But Head space also has limitation, work as determinand
When boiling point is high, using Head space, time-consuming and sensitivity decrease, because determinand boiling point is higher, is more difficult to volatilize, thus top
Aerial testing concentration is low, it is difficult to be enriched with.If raising sample temperature, although help speed up sample to the migration rate of head space,
But the distribution coefficient of determinand between head space and fiber coat can be also reduced simultaneously.
In summary, still there is superior heat resistance, high stability, high sensitivity and high selection without a kind of in the prior art
The coating material of property.
The content of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of preparation method of metal-organic nano pipe coating,
Comprise the following steps：
1) one end of stainless steel wire hydrofluoric acid is corroded after setting time, cleaned, dried；
2) by step 1) the corrosion section of the stainless steel wire of processing is then rapid to take out vertically into organic siliconresin；
3) organic siliconresin on stainless steel wire surface is handled, forms it into one layer of uniform film；
4) by part adhesive zinc metal-organic nanotube powder bed of stainless steel wire gluing, zinc metal-organic nano is obtained
Pipe coating fiber.
Zinc metal-organic nano the pipe coating prepared includes machine silicone layer and sticked on silicone resin layer
Zinc metal-organic nanotube, under the mating reaction of organic siliconresin, the heat endurance of zinc metal-organic nanotube can be with
335 DEG C are brought up to, with higher heat resistance, with longer service life.
By verification experimental verification, zinc metal-organic nano pipe coating of preparation has higher stabilization to Nitro Polycyclic Aromatic Hydrocarbons
Property, higher sensitivity and preferably selectivity.Using direct Solid-phase Microextraction to Nitro Polycyclic Aromatic Hydrocarbons carry out extraction and
During detection, can have higher sensitivity and accuracy.
Further, a diameter of 0.3-0.35mm of the stainless steel wire, a length of 25-30cm, the length of corrosion is 1.5-
2.5cm。
Further, step 1) in, the concentration 40% (mass percent) of hydrofluoric acid, the time corroded with hydrofluoric acid is 3-
5h.A diameter of 0.12-0.18mm of stainless steel wire is eroded to, if not corroding, directly zinc metal-have is adhered to organic siliconresin
Machine nanotube makes coating, and diameter can be thicker in itself than stainless steel wire, can wipe coating off when retracting in SPME devices.Will be stainless
After steel wire corrosion certain depth, the stainless steel wire after corrosion adheres to the diameter after organic siliconresin and the stainless steel wire not being corroded
Diameter quite, the integrality of coating can be ensured by retracting when in SPME devices.
For technical problem present in above-mentioned prior art, applied the invention provides a kind of zinc metal-organic nanotube
Layer fiber, the zinc metal-organic nanotube coated fiber is prepared by above-mentioned preparation method.
Zinc metal-organic nanotube the coated fiber be may be mounted in solid-phase micro-extracting device, and test substance is carried out
Extraction.
For technical problem present in above-mentioned prior art, applied the invention provides above-mentioned zinc metal-organic nanotube
Application of the layer fiber in SPME is carried out to Nitro Polycyclic Aromatic Hydrocarbons.
Zinc metal-organic nano pipe coating of preparation has higher stability to Nitro Polycyclic Aromatic Hydrocarbons, higher sensitive
Degree and preferably selectivity.Using direct Solid-phase Microextraction Nitro Polycyclic Aromatic Hydrocarbons are extracted when, can with compared with
High sensitivity and accuracy.
For technical problem present in above-mentioned prior art, the invention provides a kind of SPME devices, its extracting head is
Zinc metal-organic nanotube the coated fiber.
For technical problem present in above-mentioned prior art, the invention provides above-mentioned SPME devices polycyclic to nitro
Aromatic hydrocarbons carries out the application in SPME.
For technical problem present in above-mentioned prior art, the invention provides utilize above-mentioned SPME devices and gas phase color
The method of Nitro Polycyclic Aromatic Hydrocarbons, comprises the following steps in spectrum-triple level Four bar mass spectrometries detection ambient water：
1) environmental water sample of collection is pre-processed；
2) zinc metal-organic nanotube coated fiber in above-mentioned SPME devices is placed on gas phase injection port, in 270-
Aging 4-6min under conditions of 290 DEG C；
3) the SPME devices after aging are subjected to SPME to pretreated ambient water；
4) injection port of gas chromatograph and then by the syringe needle of SPME devices is inserted, test substance is desorbed and examined
Survey.
Further, step 1) in, filtered during the method for environmental water sample pretreatment with 0.45 μm of filter membrane, and at 4 DEG C
Under the conditions of save backup.
Further, the condition of SPME is：Ionic strength 17-23%NaCl, w/v；44-46 DEG C of extraction temperature,
Extraction time is 45-55min.
During due to being extracted using direct Solid-phase Microextraction, extracting head is directly contacted with ambient water, in ambient water also
There are a lot of other materials, can if the extraction coating in extracting head treats the selectivity for detecting material or sensitivity not enough
The other interfering materials of absorption, or enough test substances can not be adsorbed, when being detected, it may appear that Interference Peaks, interference inspection
The accuracy of survey, or the amount of the material of absorption are less, lead to not the actual content for detecting test substance.
Experiment finds that influenceing the factor of effect of extracting also includes ionic strength, extraction temperature and extraction time etc., these because
Element can influence the completeness of extraction and the selectivity of extraction.
When being engaged using extraction conditions as above with the extracting head of the present invention, even if using direct SPME side
During method, Nitro Polycyclic Aromatic Hydrocarbons can be shown with good selectivity and sensitivity.
The present invention advantageous effects be：
Zinc metal-organic nano the pipe coating prepared includes machine silicone layer and sticked on silicone resin layer
Zinc metal-organic nanotube, under the mating reaction of silicone resin layer, the heat endurance of zinc metal-organic nanotube can
To bring up to 335 DEG C, with higher heat resistance, with longer service life.
By verification experimental verification, zinc metal-organic nano pipe coating of preparation has higher stabilization to Nitro Polycyclic Aromatic Hydrocarbons
Property, higher sensitivity and preferably selectivity.Using direct Solid-phase Microextraction to Nitro Polycyclic Aromatic Hydrocarbons carry out extraction and
During detection, can have higher sensitivity and accuracy.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not constitute the improper restriction to the application.
Fig. 1 is the heat endurance curve of Zn-MONTs materials, wherein, the heat endurance curve of (a) Zn-MONTs coatings,
(b) Zn-MONTs heat endurance curve, the heat endurance curve of (c) silicone glue；
Fig. 2 for Zn-MONTs coatings scanning electron microscope (SEM) photograph and Zn-MONTs scanning electron microscope (SEM) photograph comparison diagram, wherein, (a)
For the scanning electron microscope (SEM) photograph of Zn-MONTs coatings, (b) is Zn-MONTs scanning electron microscope (SEM) photograph；
Fig. 3 is the comparison diagram of Zn-MONTs coatings and commercialization coating.
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Term explains part：
Nitro Polycyclic Aromatic Hydrocarbons (NPAHs) are the polycyclic aromatic hydrocarbons of nitrification, result from agricultural crop straw, coal and motor vehicles etc.
Burning and air in polycyclic aromatic hydrocarbon nitrification.NPAHs has very strong toxicity, mutagenicity and carcinogenicity.In sea
NPAHs has been detected in foreign deposit, river, seawater, aquatile, soil and food.
Organic siliconresin is a class alternately links the skeleton constituted by silicon atom and oxygen atom, different organic group again with
The general designation for the polymer that silicon atom links.
" vertical " herein refers to that the two ends of stainless steel wire extend the plane institute shape of the straight line to be formed and organic siliconresin
Into angle be right angle.Organic siliconresin sebific duct mouthful is smaller, and stainless steel wire corrosion section is easy to break, and section bending will easily be corroded by being tilted into,
It can not be further used for making homemade SPME devices, so needing the corrosion section by stainless steel wire vertically into organic siliconresin
In.
" rapid to take out " herein, refers to, after the corrosion section insertion organic siliconresin of stainless steel wire, with faster speed
Degree takes out.Rapid take out can be relatively easy to form film, more disposable to obtain uniform organic siliconresin film, and slowly taking out can band
Go out very thick organic siliconresin, it is especially fast that glue is done, not disposable.
Zinc metal-organic nanotube coated fiber, is that organosilicon tree is impregnated on the stainless steel wire corroded by hydrofluoric acid
Lipid layer, the product that zinc metal-organic nano pipe powder is obtained is adhered in silicone resin layer, because traditional SPME is filled
The extracting head put is to coat solid-phase micro-extraction coating on a quartz fibre and obtain, and can be referred to as fiber head again, so, the application
It is middle that the product prepared is named as zinc metal-organic nanotube coated fiber.
Experiment material, reagent and laboratory apparatus
All reagents used are at least analyzing pure rank in experiment.4,4 '-bipyridyl and Zn (NO3)2·6H2O is purchased from
Aladdin Reagent Company；5- amino -2,4,6- triiodo M-phthalic acids are purchased from TCI Development Co., Ltds；N, N- dimethyl formyl
Amine and ethanol are purchased from Chemical Reagent Co., Ltd., Sinopharm Group；Six kinds of Nitro Polycyclic Aromatic Hydrocarbons include 3- nitrobiphenyls (3-Nbp), 9-
Nitroanthracene (9-NAnt), 9- nitros phenanthrene (9-NPt), 3- nitros fluoranthene (3-NFlu), 1-nitropyrene (1-NPy) and 6- nitros are bent
The standard items of (6-NChr) are purchased from AccuStandard companies；5 μ L microsyringes are purchased from Shanghai Gao Ge Trade Co., Ltd.s；
100- μm of PDMS, 65- μm of PDMS/DVB and 50/30- μm of DVB/CAR/PDMS commodity coating are purchased from Supelco companies.
Gas-chromatography-triple level Four bar GC-MS, DB-5MS chromatographic columns (30m × 0.25mm × 0.25 μm).Chromatogram
Column and programmed temperature：60 DEG C of initial temperature, with 15 DEG C of min-1Rise to 150 DEG C and keep 1min, then with 5 DEG C of min-1Rise to 300 DEG C, holding
4min.Carrier gas (high-pure helium) flow velocity is 2mL min-1, 280 DEG C of injector temperature, 150 DEG C of ion source temperature enters using SIM patterns
Row analysis.SEM (Zeiss, Germany company), thermogravimetric (STA449F3-QMS403C, German Nai Chi groups) Fourier
Transform infrared spectroscopy instrument (NICOLET iS10, U.S. Buddhist nun high-tensile strength company).
Zn-MONTs preparation
Zn-MONTs materials are prepared in accordance with the following methods：10mg Zn(NO3)2·6H2O, 10mg 5- amino-
2,4,6- triiodos M-phthalic acid and 10mg 4,4 '-bipyridyl be dissolved in 8ml N,N-dimethylformamide, second alcohol and water (v/v,
5:2:1) in mixed solution.Mixed solution was stirred at room temperature after half an hour, and filtering, the small beaker that then will be equipped with filtrate is put
In the hermetically sealed can equipped with ether, substantial amounts of yellow crystals can be produced after 10 days in small beaker.Crystal is filtered, then with ultrapure
Washing is clean, is dried 24 hours at 200 DEG C, you can obtain Zn-MONTs materials.
The preparation of Zn-MONTs coatings
One end (2 centimetres) of stainless steel wire (20 centimeter length) is corroded 4 hours with hydrofluoric acid.Then, the part of corrosion according to
Secondary use methanol and ultra-pure water are cleaned by ultrasonic 5 minutes, then dry.The stainless steel wire handled well vertically immerses silicone glue
In, then promptly take out.Unnecessary glue is wiped off with knife on fiber, surface is formed one layer of uniform film.On stainless steel wire
Gluing is inserted partially into ready zinc metal-organic nano pipe powder.Then, zinc metal-organic nano pipe coating
Fiber is put to be dried 24 hours in room temperature.Finally, ready-made zinc metal-organic nanotube coated fiber 5- μ L gas phases are installed on to enter
SPME (SPME) device is made in sample pin.Needed before coating first time use in 280 DEG C of conditions of gas phase injection port
Lower aging, until baseline stability.
SPME experimentations
All SPME experiments are all using directly extraction pattern (i.e. direct solid phase micro-extraction method).By 10ml environmental water samples
Product are added in vial, sealing.Vial bottle cap is pierced with the syringe needle of SPME devices, then zinc metal-organic nanotube is applied
Layer fiber is totally immersed in sample solution.Extraction is finished, and zinc metal-organic nanotube coated fiber is recovered in needle tubing, and
Pulled out from bottle, be then inserted into gas chromatographic sample introduction mouthful desorption.Every time before extraction, Zn-MONTs coated fibers are required for
Aging 5min under the conditions of 280 DEG C of gas phase injection port.
The collection of environmental sample
Snow-broth comes from the snow in the November in 2016 of Jinan on the 22nd；Lake water is picked up from Jining of Shandong Province Weishan Lake.All water samples
All need with 0.45 μm of membrane filtration, and saved backup under the conditions of 4 DEG C before analysis.
As a result with discussion
Zn-MONTs sign
It will be seen from figure 1 that the heat endurance of Zn-MONTs materials is 325 DEG C, and the heat endurance of Zn-MONTs coatings
Bring up to 335 DEG C.It can be seen that, organic siliconresin substantially increases the heat endurance of Zn-MONTs coatings, makes Zn-MONTs coatings can
To apply in the environment higher to temperature requirement, and extend the service life of Zn-MONTs coatings.Simultaneously as Zn-
The heat endurance of MONTs coatings is improved, when higher temperature is handled, its degree of decomposition reduction, to the annoyance level of detection
Reduction, improves the accuracy and sensitivity of detection.
In Fig. 2, (a) and (b) is respectively the scanning electron microscope (SEM) photograph of Zn-MONTs fiber coats and Zn-MONTs materials.From (b)
In it can be seen that prepared Zn-MONTs coatings are than more uniform, coating uniform, then without exposed organic siliconresin even
Exposed stainless steel wire, can improve effect of extracting, also without Zn-MONTs material stacking phenomenons, the repeated meeting of coating-painting interlayer
More preferably, it is more favorable to desorption in the short time complete.
Experimental condition optimizes
Several important parameters to influenceing effect of extracting, such as ionic strength, extraction time, extraction temperature and desorption time,
It is optimized using single_factor method.Influence of the NaCl concentration (0-25%) to NPAHs effect of extracting, result of the test table are investigated
It is bright：With the rise (0-20%) of NaCl concentration, NPAHs effect of extracting is improved therewith, after NaCl concentration is more than 20%, extraction
Efficiency is taken to begin to decline.Therefore, in order to adjust the ionic strength of solution in this experiment, NaCl concentration elects 20% as.
Investigate influence of the extraction temperature (25-75 DEG C) to NPAHs effect of extracting.Result of the test shows：With extraction temperature
Rise (25-45 DEG C), Zn-MONTs coatings are continuously increased to NPAHs extraction efficiencies；But when temperature is more than 45 DEG C, NPAHs
Extraction efficiency is begun to decline.Therefore in the experiment of postorder, extraction temperature elects 45 DEG C as.
Influence of the extraction time (10-60min) to NPAHs effect of extracting is investigated.Result of the test shows：NPAHs extraction
Efficiency is taken to increase with the increase of extraction time (10-50min), Zn-MONTs coatings are to NPAHs extraction efficiency in 50min
When reach extraction equilibrium.Therefore, extraction time elects 50min as in the experiment below.
Influence of the desorption time to NPAHs test effects is investigated.Result of the test shows：When desorption temperature is 280 DEG C,
5min desorption time can completely desorb NPAHs from Zn-MONTs coatings.Therefore, the extraction conditions finally chosen
For：Ionic strength 20%NaCl (w/v), 45 DEG C of extraction temperature, extraction time 50min, desorption time 5min.
Methodology parameter
With optimal conditions, the six kinds of NPAHs range of linearity is 10-5000ngL-1, coefficient correlation (R) is 0.9950-
0.9970, detection limit (S/N is 3) is 1.36-7.31ng L-1.Same Zn-MONTs coated fiber relative standard deviation be
1.7-10.2% (in a few days) and 6.4-9.8% (in the daytime)；Three same Zn-MONTs coated fiber relative standard deviations are
6.1-12.8% (in a few days).
The comparison of Zn-MONTs coatings and commercialization coating
With optimal conditions, Zn-MONTs coatings and three kinds of commercialization coatings 100 μm of PDMS, 65 μm of PDMS/ are compared
Effect of extracting of DVB and 50/30 μm of DVB/CAR/PDMS to NPAHs.Result of the test shows：Zn-MONTs is applied in this 4 kinds of coatings
Layer is optimal to 9-NAnt, 9-NPt, 3-NFlu, 1-NPy and 6-NChr effect of extracting；And for 3-Nbp, Zn-MONTs coatings
Although less than 65 μm PDMS/DVB coatings of effect of extracting, apparently higher than 100 μm of PDMS and 50/30 μm of DVB/CAR/PDMS
Coating, as shown in figure 3, wherein, in each group, be followed successively by from left to right PDMS/DVB, Zn-MONTs, DVB/CAR/PDMS and
PDMS。
The analysis of environmental sample
In order to evaluate the applicability of the above method, it have selected two kinds of environmental water sample snow-broths and lake water carried out as actual water sample
Analysis.NPAHs is not detected in snow-broth and lake water.In order to further verify the accuracy of this method, respectively to two kinds of reality
Water sample has carried out three various concentrations (100,200 and 500ng/L) recovery testu, and obtained rate of recovery scope is
71.2-114.2% (table 1).To illustrate the matrix effect of varying environment water sample do not have significant impact to this method, it was demonstrated that this hair
Zinc metal-organic nano pipe coating of bright middle preparation has good selectivity to the Nitro Polycyclic Aromatic Hydrocarbons in ambient water.More than
Test result indicates that the analysis that this method is applied to trace Nitro Polycyclic Aromatic Hydrocarbons in actual water sample is feasible.
NPAHs analysis result in the actual environment sample of table 1
a Recovery of spiked 100ng L-1
b Recovery of spiked 200ng L-1
C Recovery of spiked 500ng L-1
d Not detected
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of preparation method of metal-organic nano pipe coating, it is characterised in that：Comprise the following steps：
1) one end of stainless steel wire hydrofluoric acid is corroded after setting time, cleaned, dried；
2) by step 1) the corrosion section of the stainless steel wire of processing is then rapid to take out vertically into organic siliconresin；
3) organic siliconresin on stainless steel wire surface is handled, forms it into one layer of uniform film；
4) by part adhesive zinc metal-organic nanotube powder bed of stainless steel wire gluing, obtain zinc metal-organic nanotube and apply
Layer fiber.
2. preparation method according to claim 1, it is characterised in that：A diameter of 0.3-0.35mm of the stainless steel wire,
A length of 25-30cm, the length of corrosion is 1.5-2.5cm.
3. preparation method according to claim 1, it is characterised in that：Step 1) in, the concentration 40% of hydrofluoric acid uses hydrogen fluorine
The time of acid corrosion is 3-5h.
4. a kind of zinc metal-organic nanotube coated fiber, it is characterised in that：Zinc metal-organic nanotube the coated fiber by
Any preparation methods of claim 1-3 are prepared.
5. zinc metal-organic nanotube coated fiber described in claim 4 is in SPME is carried out to Nitro Polycyclic Aromatic Hydrocarbons
Application.
6. a kind of SPME devices, it is characterised in that：Its extracting head is that zinc metal described in claim 4-organic nano pipe coating is fine
Dimension.
7. application of the SPME devices described in claim 6 in SPME is carried out to Nitro Polycyclic Aromatic Hydrocarbons.
8. utilize SPME devices described in claim 6 and nitro in gas-chromatography-triple level Four bar mass spectrometry detection ambient water
The method of polycyclic aromatic hydrocarbon, it is characterised in that：Comprise the following steps：
1) environmental water sample of collection is pre-processed；
2) zinc metal-organic nanotube coated fiber in above-mentioned SPME devices is placed on gas phase injection port, at 270-290 DEG C
Under conditions of aging 4-6min；
3) the SPME devices after aging are subjected to SPME to pretreated ambient water；
4) injection port of gas chromatograph and then by the syringe needle of SPME devices is inserted, test substance is desorbed and detected.
9. method according to claim 8, it is characterised in that：Step 1) in, used during the method for environmental water sample pretreatment
0.45 μm of filter membrane is filtered, and is saved backup under the conditions of 4 DEG C.
10. method according to claim 8, it is characterised in that：The condition of SPME is：Ionic strength 17-23%
NaCl, w/v；44-46 DEG C of extraction temperature, extraction time is 45-55min.
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| CN108273481A (en) * | 2018-01-12 | 2018-07-13 | 山东省分析测试中心 | The preparation and its application of polyphenylene-conjugation microporous polymer solid-phase micro-extraction coating |
| CN109158086A (en) * | 2018-07-23 | 2019-01-08 | 山东省分析测试中心 | A kind of method of hypersensitive analysis underwater trace polybrominated diphenyl ethers |
| CN111939774A (en) * | 2020-08-11 | 2020-11-17 | 哈尔滨工业大学 | Method for preparing composite nanofiltration membrane by growing nano particles after etching |
| WO2020244311A1 (en) * | 2019-06-06 | 2020-12-10 | 中国科学院新疆生态与地理研究所 | Method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water |
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| CN105536746A (en) * | 2015-12-09 | 2016-05-04 | 山东省分析测试中心 | Solid-phase micro-extraction capsule and application of same in detection of phenol environmental estrogen in beverage |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108273481A (en) * | 2018-01-12 | 2018-07-13 | 山东省分析测试中心 | The preparation and its application of polyphenylene-conjugation microporous polymer solid-phase micro-extraction coating |
| CN108273481B (en) * | 2018-01-12 | 2019-04-05 | 山东省分析测试中心 | Polyphenylene-conjugation microporous polymer solid-phase micro-extraction coating preparation and its application |
| CN109158086A (en) * | 2018-07-23 | 2019-01-08 | 山东省分析测试中心 | A kind of method of hypersensitive analysis underwater trace polybrominated diphenyl ethers |
| CN109158086B (en) * | 2018-07-23 | 2021-06-15 | 山东省分析测试中心 | Method for ultrasensitively analyzing trace polybrominated diphenyl ethers in water |
| WO2020244311A1 (en) * | 2019-06-06 | 2020-12-10 | 中国科学院新疆生态与地理研究所 | Method for rapid extraction and analysis of 10 polycyclic aromatic hydrocarbons in water |
| CN111939774A (en) * | 2020-08-11 | 2020-11-17 | 哈尔滨工业大学 | Method for preparing composite nanofiltration membrane by growing nano particles after etching |
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