CN103611510A - Preparation method of non-woven fabric micro-solid phase extraction bag based on MIL-101 adsorbent - Google Patents
Preparation method of non-woven fabric micro-solid phase extraction bag based on MIL-101 adsorbent Download PDFInfo
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Abstract
The invention relates to a preparation method of a non-woven fabric micro-solid phase extraction bag based on an MIL-101 adsorbent. The preparation method comprises the specific steps of preparing an MIL-101 porous adsorption material by a hydrothermal method, fully washing, purifying and activating, and packaging in a non-woven fabric pocket by a hot bonding method to manufacture a novel micro-solid phase extraction device. The preparation method has the advantages of simple process and easiness in operation. Adsorption experiments prove that the MIL-101 porous adsorbent prepared by the preparation method provided by the invention has the advantages of regular structure and large pore volume, and the micro-solid phase extraction bag has good adsorption performance. In the method, a non-woven fabric material for preparing the extraction bag has no limitation, and any non-woven fabric after gene modification can be adopted according to research needs and actual applications.
Description
Technical field
The present invention relates to a kind of preparation of micro-SPE bag, this device is the perforated nonwoven fabrics bag for extracting that is packaged with novel absorption material MIL-101, this bag for extracting adopts the mode of heat bonding to encapsulate, and develops a kind of novel fast simple micro-SPE method with this.
Background technology
MIL-101 is the rigid backbone porous adsorbing material with special cage structure that a class is formed by self assembly effect by metal ion and organic ligand.The well-regulated pore passage structure of MIL-101 tool, (BET specific area is up to 4500m for the specific area of super large
2/ g), the remarkable advantages such as good heat endurance and solvent stability, therefore, have been widely used in sample adsorbing domain.The present invention adopts this novel porous adsorbing material of MIL-101 as adsorbent, prepares micro-SPE bag.
Nonwoven, refers to non-weaving cloth, or is adhesive-bonded fabric.Be a kind of fabric that does not need to spin cotton and weave cloth and form, this fabric just carries out orientation or random support row by textile staple or long filament, forms fibre net structure, then adopts the method reinforcing such as mechanical, hot sticky or chemical to form.Non-weaving cloth has been broken through traditional weaving principle, have that technological process is short, speed of production is fast, the features such as output is high, cost is low, purposes is wide, raw material sources are many, therefore, in recent years, nonwoven textile industry has obtained great development, ends 1998, and global nonwoven consumption figure has reached 2,400,000 tons.
Micro-solid phase extraction techniques is a kind of Sample Pretreatment Technique Used, and this method has that to consume solvent few, highly sensitive, the advantage such as easily is automated.Traditional SPE method mainly contains following three kinds of extraction patterns, the first is to adopt the autonomous solid-phase extraction column of loading of commercialization or laboratory to extract, the second is to adopt commercial solid-phase micro-extraction fibre to extract, and the third is Dispersive solid phase extraction.
Adopt solid-phase extraction column to carry out sample extraction, sorbing material need to be loaded in plastics or glass column, the filler of conventional solid-phase extraction column mainly comprises silica type filler, alundum (Al2O3) filler, Fo Luoli tripoli-magnesium silicate filler etc.When determining adsorption, sample solution need to be poured in solid-phase extraction column and adsorb, after sample solution drains off completely, then adopt the component that a large amount of organic solvents adsorbs adsorbent to carry out wash-out.Therefore, this SPE method not only use amount of adsorbent is large, and in extraction process, needs to consume a large amount of organic solvents, is not a kind of green, the analytical method of environmental protection.Meanwhile, because the liquid rate of outflow is slower, the method is also more consuming time.
Existing commercialization solid-phase micro-extracting device mainly scribbles the fixedly vitreous silica fibre abstraction head of phase by handle and surface and forms, and vitreous silica fiber is hidden in syringe needle conventionally, can promote injector push rod quartz fibre is stretched out in syringe needle while needing.This extracting head is all that fixing phase coating is coated with and is steeped on quartz fibre as extracting fiber, these fixedly phase coating mainly comprise dimethyl silicone polymer, polyacrylate, carbon molecular sieve/vinyl benzene or carbon molecular sieve/molecular template resin, polyethylene glycol/dimethyl silicone polymer.But this type coating is all, by photocuring or heating means, high polymer is fixed on to quartz fibre surface, so mechanical strength and heat endurance are all poor.Vitreous silica fibre abstraction head stretches out and retracts in the syringe needle of being everlasting, and coating easy fracture is peeled off, and quartz fibre frangibility, and this has greatly limited the scope of application and the life-span of extracting head.In addition, commercial solid-phase micro-extraction fibre is more expensive, the price of a fiber conventionally hundreds of to several thousand yuan not etc., use cost is higher.
Dispersive solid phase extraction is directly adsorbent to be immersed in sample solution to be determined, extracts enrichment component to be detected by adsorbent.After adsorption process finishes, adopt centrifugal mode that solid absorbent is separated with sample solution, adopt again subsequently the component that the solvent of particular polarity adsorbs adsorbent to carry out wash-out, and measure.The method does not need preparation or builds any extraction equipment, but in once complete extraction process, need to be through repeatedly centrifugal, and need by mode ultrasonic or concussion, solid absorbent to be disperseed again after each centrifugal, therefore in actual mechanical process, extremely waste time and energy.
The object of the invention is to overcome above shortcomings in existing method and technology, a kind of novel micro-solid-phase extraction device is provided, and the preparation method of this micro-solid-phase extraction device is provided.Therefore,, by invention and the use of this device, both can effectively simplify the preparation process of extraction equipment, in extraction process, effectively reduce the use amount of organic solvent, reduce and pollute, can reach time saving and energy saving, realize the object that the rapid analysis of sample is measured simultaneously.
Summary of the invention
For realizing technical scheme provided by the present invention, be:
With hydro-thermal method, prepare MIL-101 porous adsorbing material, through washing fully, purify, after activation, adopt the method for heat bonding, be packaged in nonwoven bag for extracting, be made into novel micro-solid-phase extraction device.
Through adsorption experiment, show, this method is prepared MIL-101 porous adsorbent tactical rule, and pore capacities is large, and micro-SPE bag absorption property is good.
Wherein, the hydrothermal synthesis method of porous adsorbing material MIL-101 is: by 0.325 gram of chromic nitrate, 0.410 gram of terephthalic acid (TPA) is dissolved in 20 milliliters of high purity waters, add 1 milliliter of hydrofluoric acid solution, after within ultrasonic 10 minutes, making it dissolve, mixed solution is placed in to 35 milliliters of polytetrafluoroethylene (PTFE) reactors, and 220 ℃ are reacted 8 hours.Question response still is cooling, adopts water/ethanolic solution to wash resulting metallic organic framework sorbing material, 200 ℃ of dry for standby.
The preparation method of perforated nonwoven fabrics bag for extracting: perforated nonwoven fabrics is converted into suitable size, cuts redundance, adopt electric sealing machine by the opening heat-sealing of perforated nonwoven fabrics, only surplus next opening, for loading MIL-101 porous adsorbent.
The preparation of the nonwoven bag for extracting based on MIL-101 sorbing material: take appropriate metallic organic framework sorbing material, and loaded in perforated nonwoven fabrics bag for extracting, after filling finishes, adopt electric sealing machine by the openend heat bonding of perforated nonwoven fabrics bag for extracting.
The using method of MIL-101 nonwoven bag for extracting: in advance above-mentioned bag for extracting is cleaned with the solvent (as methyl alcohol, water, n-hexane etc.) of particular polarity before use, and dried.When carrying out micro-SPE experiment, this bag for extracting is directly soaked in sample solution to be detected, sample solution is carried out to mechanical agitation simultaneously, the metallic organic framework adsorbent in bag for extracting can be contacted fully with sample solution, realize the absorption to target components to be measured.After adsorption process finishes, bag for extracting is taken out with tweezers, with filter paper, surperficial liquid is blotted, be then soaked in the solvent of some milliliters (as methyl alcohol, water, n-hexane etc.), object is carried out to wash-out.Eluent can directly be measured (gas chromatography, liquid chromatography, spectra methods etc.), determines the content of target components.
In the present invention, nonwoven cloth material for the preparation of bag for extracting is without any restrictions, therefore, can adopt the nonwoven through any base group modification or modification according to research needs and practical application, and by similar method, can prepare micro-SPE bag of the coated MIL-101 adsorbent of other nonwoven.
Not only manufacturing process is simple to adopt the prepared SPME bag of method of the present invention, making and use cost are minimized, and in the process of using, also need not centrifuge, the expensive experiment equipment such as vortex mixed instrument, oscillator, the quantity of solvent that sorption and desorption process consumes is less, therefore, both can save certain equipment cost, time cost and human cost, also can reduce the pollution of experimental waste liquid to environment simultaneously.
The specific embodiment
For better understanding the present invention, below in conjunction with embodiment, the present invention is done further and described in detail, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment:
The MIL-101 porous adsorbing material of preparing with hydro-thermal method, the method for employing heat bonding, is packaged in nonwoven bag for extracting, is made into novel micro-solid-phase extraction device:
The hydrothermal synthesis method of porous adsorbing material MIL-101 is: by 0.325 gram of chromic nitrate, 0.410 gram of terephthalic acid (TPA) is dissolved in 20 milliliters of high purity waters, add 1 milliliter of hydrofluoric acid solution, after within ultrasonic 10 minutes, making it dissolve, mixed solution is placed in to 35 milliliters of polytetrafluoroethylene (PTFE) reactors, and 220 ℃ are reacted 8 hours.Question response still is cooling, adopts water/L alcoholic solution to wash resulting metallic organic framework sorbing material, 200 ℃ of dry for standby.
Perforated nonwoven fabrics is converted into suitable size, and cuts redundance.Adopt electric sealing machine that the opening of perforated nonwoven fabrics is thermally bonded to only surplus next opening.Take MIL-101 porous adsorbing material prepared by 0.5mg hydro-thermal method, and loaded in nonwoven " pocket ", and openend is adopted to use the same method and carry out heat bonding, obtained the micro-SPE bag of a kind of novel nonwoven based on MIL-101 adsorbent.
Claims (4)
1. a MIL-101 adsorbent, it is characterized in that: it is the green solid particle that adopts hydro-thermal method to prepare, and this solid particle needs first with distilled water, repeatedly clean, to remove unreacted slaine, with ethanol, repeatedly clean again, remove unreacted terephthalic acid (TPA).
2. a MIL-101 adsorbent for high-specific surface area, good adsorption characteristic, is characterized in that: MIL-101 adsorbent claimed in claim 1 is impregnated in hot ethanol solution, and stirred for several hour, ultrasonic a few hours, centrifugal afterwards, 200 ℃ of high-temperature roasting a few hours.
3. the purification method of the MIL-101 adsorbent of high-specific surface area according to claim 2, good adsorption characteristic, is characterized in that: described ultrasonic step is that low energy is ultrasonic.
4. the SPE bag of MIL-101 absorbent preparation according to claim 2, is characterized in that: described nonwoven cloth material is without any restrictions, can be according to actual needs and application select the nonwoven through any base group modification or modification.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877942A (en) * | 2014-03-31 | 2014-06-25 | 中国石油大学(华东) | Micro solid phase extraction probe made by MIL-101 type metal organic framework (MOF) material and preparation method of probe |
| CN104475026A (en) * | 2014-11-12 | 2015-04-01 | 天津工业大学 | Novel preparation and application methods of water treatment film doped with MTN-zeolite-configuration composite material |
| US9421517B2 (en) | 2015-01-20 | 2016-08-23 | Chung Yuan Christian University | Metal-organic framework polymer for solid-phase microextraction |
| CN110534835A (en) * | 2019-09-17 | 2019-12-03 | 常州大学 | Supercritical CO2The method of fluid recovery waste and old lithium ionic cell electrolyte |
-
2013
- 2013-12-06 CN CN201310673614.1A patent/CN103611510A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877942A (en) * | 2014-03-31 | 2014-06-25 | 中国石油大学(华东) | Micro solid phase extraction probe made by MIL-101 type metal organic framework (MOF) material and preparation method of probe |
| CN103877942B (en) * | 2014-03-31 | 2016-06-01 | 中国石油大学(华东) | The micro-Solid-Phase Extraction probe of MIL-101 type MOF material and preparation method |
| CN104475026A (en) * | 2014-11-12 | 2015-04-01 | 天津工业大学 | Novel preparation and application methods of water treatment film doped with MTN-zeolite-configuration composite material |
| US9421517B2 (en) | 2015-01-20 | 2016-08-23 | Chung Yuan Christian University | Metal-organic framework polymer for solid-phase microextraction |
| CN110534835A (en) * | 2019-09-17 | 2019-12-03 | 常州大学 | Supercritical CO2The method of fluid recovery waste and old lithium ionic cell electrolyte |
| CN110534835B (en) * | 2019-09-17 | 2022-04-22 | 常州大学 | Supercritical CO2Method for recovering waste lithium ion battery electrolyte by using fluid |
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Application publication date: 20140305 |