CN109260760A - The method that solid-phase micro-extraction fibre coating is prepared as binder using inorganic phosphate - Google Patents
The method that solid-phase micro-extraction fibre coating is prepared as binder using inorganic phosphate Download PDFInfo
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- CN109260760A CN109260760A CN201811424775.6A CN201811424775A CN109260760A CN 109260760 A CN109260760 A CN 109260760A CN 201811424775 A CN201811424775 A CN 201811424775A CN 109260760 A CN109260760 A CN 109260760A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/20—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of method for preparing solid-phase micro-extraction fibre coating as binder using inorganic phosphate, it is to be dispersed in inorganic phosphate, fiber material in n,N dimethylformamide according to a certain percentage, obtains spray coating liquor；It will be sprayed in the wire carrier of rotation under spraying 0.1 ~ 1.0MPa of hydraulic coupling again；Then aging process is carried out in Muffle furnace, up to the extraction coating of firm three-dimensional net structure, have the characteristics that high mechanical strength, extract layer are secured, adsorption capacity is big, reproducible, the service life is long, the trace components enrichment analysis that can be used in the actual samples such as food, environment, drug and biochemistry.
Description
Technical field
The present invention relates to a kind of method for preparing solid-phase micro-extraction fibre coating more particularly to it is a kind of use inorganic phosphate
The method that solid-phase micro-extraction fibre coating is prepared by spraying as binder.
Background technique
Solid phase microextraction (Solid Phase Microextraction, SPME) is that last century the nineties grow up
A kind of efficiently quick new separation technology, have that accumulation ability is strong, analysis speed is fast, easy to operate and be convenient for field assay
And the advantages that Instrument crosslinking, receive the favor of analysis worker, and be widely used in food, environment, drug and biochemistry etc.
The enrichment analysis of trace components is carried out in actual sample.The core of SPME technology is solid phase micro-extracting head.How adsorptivity is prepared
Excellent and firm and durable the SPME extracting head of energy is the bottleneck of solid phase micro-extraction technique development.The solid-phase micro-extraction fibre of commercialization
Generally use quartz fibre for carrier, there are two types of preparation method is general: it is coating that one kind, which is high-molecular organic material, utilizes colloidal sol-
Gel technique preparation has certain thickness extracting head；Another kind is that inorganic carbon material is coating, and it is viscous for using organic polymer
Agent is tied, is prepared using czochralski method.Though these methods are economical, simple, the use of organic coating or binder reduces extracting head
Stability and service life (only 30 ~ 40 times), and along with the continuous reduction of effect of extracting, this is to obtaining believable experiment knot
Fruit is very unfavorable.In order to solve this problem, many scholars start to be dedicated to the system of novel extraction head in wire carrier
Preparation Method research.The technologies of preparing such as anodizing, chemical bonding and solution etches method accordingly occur.But prepared by these methods
Process is cumbersome, and the requirement to matrix and coating material is relatively high, and therefore, the type of extracting head is restricted.
Summary of the invention
The purpose of the present invention is to provide a kind of using inorganic phosphate as binder, prepares the micro- extraction of solid phase by spraying
The method for taking head, to improve the extraction efficiency of extracting head, extend Solid Phase Extraction head service life.
The method of solid phase micro-extracting head of the present invention is to be utilized adsorbent material using spraying technology using wire as carrier
Inorganic phosphate salt binder is painted in metal wire base, specifically includes the following steps:
(1) preparation of spray coating liquor
Binder inorganic phosphate, fiber material are dispersed in n,N dimethylformamide, spray coating liquor is obtained；
The mass ratio of binder inorganic phosphate and fiber material is 1:1 ~ 1:10；Inorganic phosphate and N, N-dimethylformamide
Mass ratio be 1:5 ~ 1:30.
Fiber material is graphene or molybdenum disulfide；Inorganic phosphate is chromium phosphate, basic zirconium phosphate, magnesium phosphate, aluminum phosphate, phosphorus
At least one of sour aluminium chromium.
(2) spray coating method prepares Solid Phase Extraction head
At room temperature, by wire first in phosphating solution 0.5 ~ 5h of phosphorating treatment, be roughened matrix so as to improve coating with
Binding force between matrix.Wherein wire is stainless steel wire, copper wire, and the diameter of wire is 150 ~ 250 μm；Phosphating solution is
Fe (the H of pH=1 ~ 32PO4)2、Mn(H2PO4)2 、Zn(H2PO4)2Aqueous solution.
The mixed solution of above-mentioned preparation is placed in spray gun, mixed solution is sprayed on rotation at 0.1 ~ 1.0MPa of pressure
Wire carrier on；5 ~ 15s of spray time is controlled, repetitive operation 3 ~ 8 times, obtaining coating layer thickness is 20 ~ 40 μm.
(3) aging obtains firm extraction coating
The extracting head prepared is placed in Muffle furnace and carries out aging process.Aging can be divided into a step aging, can also use two
Walk aging.The temperature of one step aging is 200 ~ 300 DEG C, 2 ~ 3h of ageing time.Two step agings be first setting aging temperature be 100 ~
180 DEG C, 0.5 ~ 1h of ageing time, then improve temperature to 200 ~ 300 DEG C, 1 ~ 2h of ageing time.
1, the structure of solid-phase micro-extraction coating
Fig. 1 is the structure (by taking aluminum phosphate chromium as an example) for the inorganic binder that the present invention uses, which during heating can
Polymerization occurs.Wherein, 2 P-OH can lose a hydrone during heating and aggregate into P-O-P key, while O=P-OH
With-O-Al/Cr-O- also can dehydration, formed O=P-O-Al/Cr key.These polymerizations make binder form three-dimensional network
Graphene or molybdenum disulfide adsorbent material are firmly combined together by structure with metal wire base, and such as prepared solid phase is micro-
Shown in the SEM figure of extracting head (Fig. 2).The structure can also more expose adsorption site, achieve the purpose that efficiently to extract.
2, thermal stability analysis
Fig. 3 is the thermogravimetric curve and differential calorimetry curve of solid-phase micro-extraction coating prepared by the present invention.It can from figure
Out, for coating only weightless 15% during environment temperature is increased to 1000 DEG C from room temperature, which occurs mainly in 200
DEG C or so.It is found referring to differential calorimetry curve, an apparent fever process has occurred at this moment, and the fever process is
Since phosphoric acid binder dehydration is formed caused by three-dimensional net structure.It can be said that it is bright after the abundant aging of extraction coating,
With good thermal stability.
3, chemical stability
Fig. 4 is to extract same sample with before impregnating after solid-phase micro-extraction coating prepared by the present invention impregnates for 24 hours at different conditions
Solution gas-chromatography peak area ratio compared with.As seen in Figure 4, extraction coating is after organic solvent and strong acid impregnate, extraction
Performance is almost without changing, but since the binder is acid binder, and after highly basic immersion, extraction ability is significantly
It reduces.It is possible thereby to illustrate that solid-phase micro-extraction coating prepared by the present invention has good chemical stability.
4, service life is tested
Fig. 5 be solid phase micro-extracting head prepared by the present invention under different access times gas-chromatography peak area ratio compared with.It can by Fig. 5
Illustrate the extracting head can in the case where extraction ability is constant at least using 160 times, extracting head service life 200 times with
On.
In conclusion the present invention with it is existing prepare the method for solid phase micro-extracting head compared with, have the advantage that
1, the present invention uses inorganic phosphate for binder, and being formed after solidification, there is the macromolecular of reticular structure, which to be coated on, is bonded
Matrix surface；And interfacial reaction, the change for improving the bond strength with matrix, and then improving occur for phosphate and matrix surface
And thermal stability, effectively extend the service life of extracting head；
2, the present invention prepares SPME extracting head by direct spraying method, can be more effective and more firmly by coating and metal
Silk carrier combines, and coating layer thickness can be precisely controlled by spray time；
3, solid-phase micro-extraction coating of the present invention have high mechanical strength, extract layer is secured, adsorption capacity is big, the reproducible, service life
The features such as long, the trace components enrichment analysis that can be used in the actual samples such as food, environment, drug and biochemistry.
Detailed description of the invention
Fig. 1 is the structure chart of aluminum phosphate chromium inorganic binder.
Fig. 2 is that the SEM of solid phase micro-extracting head prepared by the present invention schemes.
Fig. 3 is the thermogravimetric curve and differential calorimetry curve of solid-phase micro-extraction coating prepared by the present invention.
Fig. 4 is to extract same sample solution gas with before impregnating after novel solid phase micro extraction head impregnates for 24 hours at different conditions
Phase chromatographic peak area compares.
Fig. 5 be novel solid phase micro extraction head under different access times gas-chromatography peak area ratio compared with.
Specific embodiment
Below by specific embodiment to works such as preparation method, the service lifes of Solid Phase Extraction head of the present invention furtherly
It is bright.
Embodiment 1
(1) chromium phosphate, grapheme material and n,N dimethylformamide are uniformly mixed according to 1:5:18, obtain mixed solution；
(2) by wire (150 μm of diameter) first in the phosphating solution (Fe (H of pH=1 ~ 32PO4)2Solution) in phosphorating treatment 1h, make base
Body is roughened to improve the binding force between coating and matrix；
(3) mixed solution is placed in spray gun, mixed solution is sprayed on to the wire carrier of rotation under the pressure of 0.2MPa
On, spray time control is 10s, and then naturally dry, repeats the process 4 times, obtains about 30 μm of coating layer thickness；
(4) extracting head prepared is placed in Muffle furnace and carries out curing process: the first aging 0.5h at 150 DEG C is to have got rid of
Then solvent increases temperature, the aging 1h at 220 DEG C forms firm three-dimensional net structure.
(5) performance indicator: service life 200 times or more.
Embodiment 2
(1) aluminum phosphate chromium, molybdenum disulfide material and n,N dimethylformamide are uniformly mixed by 1:1:30, obtain mixed solution；
(2) by wire (150 μm of diameter) first in the phosphating solution (Mn (H of pH=1 ~ 32PO4)2Solution) in phosphorating treatment 0.5h, make
Matrix is roughened to improve the binding force between coating and matrix；
(3) mixed solution is placed in spray gun, in the wire carrier for being sprayed on rotation under the pressure of 0.1MPa, spray time
Control is 15s, and then naturally dry, repeats the process 8 times, obtains about 20 μm of coating layer thickness；
(4) extracting head prepared is placed in Muffle furnace, the aging 3h at 300 DEG C；
(5) performance indicator: service life 200 times or more.
Embodiment 3
(1) basic zirconium phosphate, grapheme material and n,N dimethylformamide are uniformly mixed by the mass ratio of 1:10:5, must be mixed molten
Liquid；
(2) by wire (150 μm of diameter) first in the phosphating solution (Zn (H of pH=1 ~ 32PO4)2Solution) in phosphorating treatment 2h, make base
Body is roughened to improve the binding force between coating and matrix；
(3) mixed solution is placed in spray gun, in the wire carrier for being sprayed on rotation under the pressure of 1.0MPa, spray time
Control is 5s, and then naturally dry, repeats the process 3 times, obtains about 40 μm of coating layer thickness；
(4) extracting head prepared is placed in Muffle furnace, first aging 1h gets rid of organic solvent at 100 DEG C, then increases
Temperature, the aging 2h at 280 DEG C.
(5) performance indicator: service life 200 times or more.
Claims (9)
1. a kind of preparation method of solid phase micro-extracting head, comprising the following steps:
(1) preparation of spray coating liquor: binder inorganic phosphate, fiber material are dispersed in n,N dimethylformamide, obtained
To spray coating liquor；
(2) spray coating method prepares Solid Phase Extraction head: the spray coating liquor of above-mentioned preparation is placed in spray gun, it will at 0.1 ~ 1.0MPa of pressure
Mixed solution is sprayed in the wire carrier of rotation；5 ~ 15s of spray time is controlled, repetitive operation 3 ~ 8 times, obtains coating layer thickness
It is 20 ~ 40 μm；
(3) coating aging obtains firm extraction: the extracting head prepared being placed in Muffle furnace and carries out aging process to get jail
Solid extraction coating.
2. a kind of preparation method of solid phase micro-extracting head as described in claim 1, it is characterised in that: in step (1), fiber material
For graphene or molybdenum disulfide.
3. a kind of preparation method of solid phase micro-extracting head as described in claim 1, it is characterised in that: in step (1), electrodeless phosphoric acid
Salt is at least one of chromium phosphate, basic zirconium phosphate, magnesium phosphate, aluminum phosphate, aluminum phosphate chromium.
4. a kind of preparation method of solid phase micro-extracting head as described in claim 1, it is characterised in that: in step (1), binder without
The mass ratio of machine phosphate and fiber material is 1:1 ~ 1:10；Inorganic phosphate and N, the mass ratio of N-dimethylformamide are 1:5
~1:30。
5. a kind of preparation method of solid phase micro-extracting head as described in claim 1, it is characterised in that: in step (2), wire is
Stainless steel wire, copper wire, the diameter of wire are 150 ~ 250 μm.
6. a kind of preparation method of solid phase micro-extracting head as described in claim 1, it is characterised in that: in step (2), spraying
Before, wire is subjected to 0.5 ~ 5h of phosphorating treatment in phosphating solution.
7. a kind of preparation method of solid phase micro-extracting head as claimed in claim 6, it is characterised in that: phosphating solution is the Fe of pH=1 ~ 3
(H2PO4)2 、Mn(H2PO4)2 、Zn(H2PO4)2Solution.
8. a kind of preparation method of solid phase micro-extracting head as described in claim 1, it is characterised in that: in step (3), aging is used
One step aging: 2 ~ 3h of aging at 200 ~ 300 DEG C.
9. a kind of preparation method of solid phase micro-extracting head as described in claim 1, it is characterised in that: in step (3), aging is used
Two step agings: first 0.5 ~ 1h of aging at 100 ~ 180 DEG C, then 200 ~ 300 DEG C are warming up to, continue 1 ~ 2h of aging.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811424775.6A CN109260760A (en) | 2018-11-27 | 2018-11-27 | The method that solid-phase micro-extraction fibre coating is prepared as binder using inorganic phosphate |
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| CN201811424775.6A CN109260760A (en) | 2018-11-27 | 2018-11-27 | The method that solid-phase micro-extraction fibre coating is prepared as binder using inorganic phosphate |
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| CN109260760A true CN109260760A (en) | 2019-01-25 |
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| CN201811424775.6A Pending CN109260760A (en) | 2018-11-27 | 2018-11-27 | The method that solid-phase micro-extraction fibre coating is prepared as binder using inorganic phosphate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842672A (en) * | 2021-09-16 | 2021-12-28 | 暨南大学 | Solid phase micro-extraction film and preparation method and application thereof |
| CN114453227A (en) * | 2022-02-09 | 2022-05-10 | 兰州交通大学 | Fiber and preparation method and application thereof |
Citations (4)
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|---|---|---|---|---|
| DE69614242T2 (en) * | 1995-09-28 | 2002-05-08 | Varian Inc | MICROEXTRACTION IN THE SOLID PHASE WITH VIBRATION |
| CN102728323A (en) * | 2012-07-11 | 2012-10-17 | 济南大学 | Preparation method of sliver-carbon nano-material composite coating metal wire solid-phase micro-extraction fiber |
| CN102872843A (en) * | 2012-10-27 | 2013-01-16 | 信阳师范学院 | Solid phase extraction column based on graphene bonded silica gel, and preparation method and application thereof |
| CN105572268A (en) * | 2015-12-16 | 2016-05-11 | 中国烟草总公司郑州烟草研究院 | Solid phase microextraction and determination method for trace benzenes in water sample |
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2018
- 2018-11-27 CN CN201811424775.6A patent/CN109260760A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| DE69614242T2 (en) * | 1995-09-28 | 2002-05-08 | Varian Inc | MICROEXTRACTION IN THE SOLID PHASE WITH VIBRATION |
| CN102728323A (en) * | 2012-07-11 | 2012-10-17 | 济南大学 | Preparation method of sliver-carbon nano-material composite coating metal wire solid-phase micro-extraction fiber |
| CN102872843A (en) * | 2012-10-27 | 2013-01-16 | 信阳师范学院 | Solid phase extraction column based on graphene bonded silica gel, and preparation method and application thereof |
| CN105572268A (en) * | 2015-12-16 | 2016-05-11 | 中国烟草总公司郑州烟草研究院 | Solid phase microextraction and determination method for trace benzenes in water sample |
Non-Patent Citations (1)
| Title |
|---|
| HONGMEI LIU,FANPENG RAN等: "《A highly thermal stable solid phase microextraction fiber prepared by an inorganic binder》", 《ANALYTICA CHIMICA ACTA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842672A (en) * | 2021-09-16 | 2021-12-28 | 暨南大学 | Solid phase micro-extraction film and preparation method and application thereof |
| CN114453227A (en) * | 2022-02-09 | 2022-05-10 | 兰州交通大学 | Fiber and preparation method and application thereof |
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Application publication date: 20190125 |