CN114674624B - MOFs composite material air sampling tube and preparation method and application thereof - Google Patents
MOFs composite material air sampling tube and preparation method and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000005070 sampling Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013207 UiO-66 Substances 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 12
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 12
- 239000003463 adsorbent Substances 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000004458 analytical method Methods 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 239000011491 glass wool Substances 0.000 claims description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000003795 desorption Methods 0.000 abstract description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000012544 monitoring process Methods 0.000 abstract description 2
- 239000003570 air Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- TWADJGWUKGOPFG-UHFFFAOYSA-N 2-methoxy-5-methyl-1,3-diphenylbenzene Chemical compound COC1=C(C=2C=CC=CC=2)C=C(C)C=C1C1=CC=CC=C1 TWADJGWUKGOPFG-UHFFFAOYSA-N 0.000 description 1
- KMQPTKROOXKLQX-UHFFFAOYSA-N C1(=CC=CC=C1)C.C=1(C(=CC=CC1)C)C.C1(=CC=CC=C1)C.C1=CC=CC=C1 Chemical group C1(=CC=CC=C1)C.C=1(C(=CC=CC1)C)C.C1(=CC=CC=C1)C.C1=CC=CC=C1 KMQPTKROOXKLQX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- -1 tenax-TA Chemical compound 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/24—Suction devices
-
- 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
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Health & Medical Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses an air sampling tube made of MOFs composite material, and a preparation method and application thereof, and belongs to the technical field of environmental monitoring. The MOFs composite material air sampling tube comprises a glass tube and an adsorbent filled in the glass tube, wherein the adsorbent is MOFs composite material, the MOFs composite material is prepared by loading UiO-66 on a white carrier, the MOFs composite material is filled in cylindrical glass, two ends of the MOFs composite material are blocked, then the MOFs composite material air sampling tube is obtained by activation, the activated MOFs composite material air sampling tube is connected with a sampling pump for sampling, the sampling tube is placed in a thermal desorption instrument, and gas chromatography-mass spectrometry analysis is carried out after thermal desorption for collecting volatile organic compounds with low concentration in air, and the MOFs composite material air sampling tube is simple in operation and easy to recycle.
Description
Technical Field
The invention relates to an air sampling tube made of MOFs composite material, and a preparation method and application thereof, and belongs to the technical field of environmental monitoring.
Background
The concentration of volatile organic contaminants in air is generally low, and chromatographic measurements are usually performed after enrichment by air sampling tubes. The common adsorbents of the air sampling tube mainly comprise active carbon, tenax-TA, tenax-GC and the like, wherein the active carbon has good adsorption performance, but is not easy to desorb, and the active carbon has strong water absorption and is not suitable for a high-humidity environment; the Tenax porous polymer has weaker adsorption performance on volatile organic compounds with low boiling point.
Metal-organic frameworks (MOFs) are novel porous nano materials formed by self-assembling metal ions or metal clusters and organic ligands, and are widely applied to the fields of gas adsorption, separation and the like in recent years because the novel porous nano materials have the characteristics of large specific surface area, adjustable pore diameter, good thermal stability, designable structure and the like, and are considered as adsorption materials with very good application prospects. However, since MOFs materials have a small particle size, direct loading into the sampling tube tends to cause excessive resistance, which makes gas flow through the tube too difficult. Therefore, if MOFs material is loaded on a carrier with proper particle size to prepare MOFs composite material, the performance advantages of MOFs can be maintained, the particle size requirement of the adsorbent can be met, and the method has a pushing significance for measuring volatile organic pollutants in air.
Disclosure of Invention
The invention provides an MOFs composite material air sampling tube, a preparation method and application thereof, and the prepared MOFs composite material air sampling tube can collect low-concentration volatile organic compounds in air and can be used for measuring the volatile organic compounds in the air by combining thermal desorption-gas chromatography-mass spectrometry.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides an air sampling tube of MOFs composite material, which comprises a glass tube and an adsorbent filled in the glass tube, wherein the adsorbent is MOFs composite material, and the MOFs composite material is prepared by loading UiO-66 on a white carrier.
Further, the white carrier is an acid-washed white carrier, and the particle size is 60-80 meshes.
Further, the loading of the UiO-66 in the white carrier is 10-20%, and the loading is calculated according to the ratio of the weight increment value of the white carrier before and after loading to the weight of the composite material, namely the weight percent.
Further, the preparation method of the MOFs composite material comprises the following steps:
(1) Mixing zirconium tetrachloride and terephthalic acid, adding concentrated HCl and DMF, dissolving, adding a white carrier, uniformly mixing, performing constant-temperature reaction under a sealed condition, cooling to room temperature, and filtering to obtain white particles;
(2) And (3) soaking the white particles obtained in the step (1) in DMF, standing at a constant temperature, filtering, then soaking the white particles in acetone, standing at a constant temperature, filtering again, and then drying the white particles in vacuum to obtain the UiO-66@white carrier, namely the MOFs composite material.
Further, in the step (1), the molar ratio of the zirconium tetrachloride to the terephthalic acid is 1:1-1: 1.2, the feed liquid ratio of zirconium tetrachloride to concentrated HCl and DMF is (0.3-0.5 g): (0.3-0.5 mL): (20-30 mL). During this process, HCl provides an acidic environment, DMF is a solvent, dissolving zirconium tetrachloride and terephthalic acid.
Further, in the step (1), the temperature of the constant temperature reaction is 120-150 ℃ for 24 hours, in the step (2), when the reaction is soaked in DMF, the reaction is kept at the constant temperature of 80 ℃ for 24 hours, and when the reaction is soaked in acetone, the reaction is kept at room temperature for 3 days, and when the reaction is soaked in acetone, the reaction is kept at the constant temperature of 80 ℃ for 6 hours, and when the reaction is soaked in acetone, the reaction is kept at the room temperature for 12 hours, the reaction is kept at the constant temperature for 12 hours.
The invention also provides a preparation method of the MOFs composite material air sampling tube, which comprises the following steps:
filling the MOFs composite material into cylindrical glass, blocking two ends by glass wool, fixing by a stainless steel net, and activating to obtain the MOFs composite material air sampling tube;
the activation condition is that the activation is carried out for 20-40 min at 200-250 ℃ under the flow rate of helium of 50-150 mL/min.
The invention also provides application of the MOFs composite material air sampling tube in adsorbing, collecting and analyzing low-concentration volatile organic compounds in air, and the MOFs composite material air sampling tube is combined with thermal desorption-gas chromatography-mass spectrometry for measurement.
The invention discloses the following technical effects:
the MOFs composite material air sampling tube prepared by the invention loads MOFs materials on a white carrier with proper particle size, and is prepared into MOFs composite material, so that the performance advantages of MOFs can be maintained, the particle size requirement of an adsorbent can be met, the MOFs composite material air sampling tube can be used for collecting volatile organic compounds with low concentration in air, and the MOFs composite material air sampling tube is simple to operate and easy to recycle.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a white support;
FIG. 2 is an SEM image of a UiO-66@white support prepared in example 1 of the present invention;
FIG. 3 is a schematic structural diagram of an air sampling tube made of MOFs composite materials, wherein 1 is a stainless steel mesh, 2 is glass wool, 3 is a UiO-66@white carrier, 4 is glass wool, and 5 is a stainless steel mesh;
FIG. 4 is a GC-MS spectrum of the MOFs composite air sampling tube prepared in example 1 for collecting volatile organic compounds in air.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The invention puts the sampling tube into thermal desorption instrument to carry out thermal desorption-gas chromatography-mass spectrometry analysis, the analysis process (1) uses a second-order desorption mode, the first-stage tube is desorbed, the desorption temperature is 150-250 ℃, the desorption time is 20-40 min, and the desorption flow rate is 40-50 mL/min. The trapping temperature of the cold trap is-20-0 ℃, the temperature rising rate of the second stage is 40 ℃/s, the desorption temperature is 250-300 ℃, and the desorption time is 5min; (2) the analysis is carried out by adopting a gas chromatography-mass spectrometry technology, a gas chromatography column is HP-5MS (30 m multiplied by 0.25mm, film thickness is 0.25 mu m), helium is taken as carrier gas, the flow rate is 1mL/min, the temperature is programmed, the initial 50 ℃ is maintained for 5min, and the temperature is increased to 250 ℃ at 10 ℃/min and maintained for 5min. The mass spectrum is EI ionization, the electron energy is 70eV, the ion source temperature is 250 ℃, the transmission line temperature is 250 ℃, a full scanning mode is adopted, and the mass scanning range is between 50 and 500 m/z; (3) and (3) quantifying by adopting an external standard, taking the mass as an abscissa and the peak area as an ordinate, drawing a working curve, and quantifying the object to be measured according to the working curve.
The raw materials used in the embodiment of the invention can be purchased commercially, wherein the mass concentration of concentrated HCl is 36%, DMF and acetone are analytically pure, a white carrier is an acid washing white carrier, the particle size is 60-80 meshes, and the raw materials are purchased from Tianjin Borui fit chromatographic technology Co., ltd, and an SEM (scanning electron microscope) chart is shown in figure 1.
The technical scheme of the invention is further described by the following examples.
Example 1
a) Preparation of MOFs composite (UiO-66@white support)
2mmol (0.466 g) of zirconium tetrachloride and 2mmol (0.332 g) of terephthalic acid are mixed according to a molar ratio of 1:1, then 0.5mL of concentrated HCl (36% by mass) and 24mL of LDMF (analytically pure) are added, after ultrasonic dissolution, 1.5g of acid-washed white carrier is added, after thorough mixing, the mixture is transferred to a tetrafluoroethylene lining reactor for sealing, and the mixture is reacted at a constant temperature of 150 ℃ for 24 hours. Cooling to room temperature, and filtering to obtain white particles;
the white particles obtained were immersed in 15ml DMF (analytically pure) and kept at constant temperature of 80 ℃ for 24 hours, during which DMF was replaced every 6 hours. After filtration, the white particles were again immersed in 15mL of acetone (analytically pure) and left at room temperature for 3 days, during which time the acetone was replaced every 12 h. After filtration again, the white particles were dried under vacuum at 80℃for 12 hours to produce MOFs composite (UiO-66@white support) whose SEM image is shown in FIG. 2.
b) Preparation of MOFs composite material air sampling tube
110mg of UiO-66@white carrier is weighed and filled into a cylindrical glass tube (90 mm multiplied by 6.35 mm), both ends are blocked by glass wool, the glass wool is used for fixing, the filled MOFs composite sampling tube is activated for 30min at 200 ℃ under the flow rate of 100mL/min helium, after activation, the MOFs composite air sampling tube is stored in a dryer for standby, the structural schematic diagram of the MOFs composite air sampling tube is shown in figure 3, wherein 1 is the stainless steel mesh, 2 is the glass wool, 3 is the UiO-66@white carrier, 4 is the glass wool, and 5 is the stainless steel mesh.
Example 2
a) Preparation of MOFs composite (UiO-66@white support)
1.5mmol (0.350 g) of zirconium tetrachloride and 1.65mmol (0.274 g) of terephthalic acid are mixed according to a molar ratio of 1:1.1, then 0.3mL of concentrated HCl (with a mass concentration of 36%) and 20mL of DMF (analytically pure) are added, after ultrasonic dissolution, 1.2g of acid-washed white carrier is added, after thorough mixing, the mixture is transferred to a tetrafluoroethylene-lined reactor for sealing, and the reaction is carried out at a constant temperature of 130 ℃ for 24h. After cooling to room temperature, white particles were obtained by filtration.
The resulting white particles were immersed in 15mL of DMF (analytically pure) and left at constant temperature of 80 ℃ for 24h, during which DMF was replaced every 6 h. After filtration, the white particles were again immersed in 15mL of acetone (analytically pure) and left at room temperature for 3 days, during which time the acetone was replaced every 12 h. After filtration again, the white particles were dried under vacuum at 80℃for 12 hours to produce MOFs composite (UiO-66@white support).
b) Preparation of MOFs composite material air sampling tube
110mg of UiO-66@white carrier is weighed and filled into a cylindrical glass tube (90 mm multiplied by 6.35 mm), both ends are blocked by glass wool, the glass wool is fixed by a stainless steel net, the filled MOFs composite sampling tube is activated for 20min at 230 ℃ at a helium flow rate of 150mL/min, and the activated MOFs composite sampling tube is stored in a dryer for standby.
Example 3
a) Preparation of MOFs composite (UiO-66@white support)
1.5mmol (0.350 g) zirconium tetrachloride and 1.8mmol (0.299 g) terephthalic acid were mixed in a molar ratio of 1:1.2, then 0.4mL of concentrated HCl (36% by mass) and 30mL of LDMF (analytically pure) were added, after ultrasonic dissolution, 1.0g of an acid-washed white support was added, after thorough mixing, the mixture was transferred to a tetrafluoroethylene-lined reactor for sealing, and reacted at a constant temperature of 120℃for 24 hours. Cooling to room temperature, and filtering to obtain white particles;
the resulting white particles were immersed in 15mL of DMF (analytically pure) and left at constant temperature of 80 ℃ for 24h, during which DMF was replaced every 6 h. After filtration, the white particles were again immersed in 15mL of acetone (analytically pure) and left at room temperature for 3 days, during which time the acetone was replaced every 12 h. After filtration again, the white particles were dried under vacuum at 80℃for 12 hours to produce MOFs composite (UiO-66@white support).
b) Preparation of MOFs composite material air sampling tube
110mg of UiO-66@white carrier is weighed and filled into a cylindrical glass tube (90 mm multiplied by 6.35 mm), both ends are blocked by glass wool, the glass wool is fixed by a stainless steel net, the filled MOFs composite sampling tube is activated for 40min at the temperature of 250 ℃ at the flow rate of 50mL/min helium, and the activated MOFs composite sampling tube is stored in a dryer for standby.
Drawing of working curves
Benzene, toluene, o-xylene, p-xylene and m-xylene standard mixed solutions with concentrations of 1000, 500, 100, 50, 10 and 5mg/L respectively are prepared. Accurately transferring 1.0 mu L of standard solutions with different concentrations, respectively pumping into activated MOFs composite sampling tubes prepared in examples 1-3, and blowing for 5min at a nitrogen flow rate of 100mg/L to prepare standard tubes with different concentrations. And (3) carrying out thermal desorption-gas chromatography-mass spectrometry on standard tubes with different concentrations, and drawing a working curve by taking the mass as an abscissa and the peak area as an ordinate. The standard tubes prepared in examples 1-3 all have a linear range of 5-1000 ng for the working curve, the correlation coefficient of the regression equation is greater than 0.99, and the linearity is good.
Collection of standard gases of volatile organic compounds
100mL of a standard gas of volatile organic compounds (benzene: 18.14 mg/m) was collected by using MOFs composite sampling tubes prepared in examples 1 to 3, respectively 3 Toluene: 21.23mg/m 3 Ortho-xylene: 24.23mg/m 3 Meta-xylene: 24.70mg/m 3 Para-xylene: 24.32mg/m 3 ). The sample tube was placed in a thermal desorption instrument for thermal desorption-gas chromatography-mass spectrometry analysis, and calculated by formula 1, and the results are shown in table 1.
TABLE 1 test results for Standard gas (unit: mg/m) 3 )
| Benzene | Toluene (toluene) | Ortho-xylene | Para-m-xylene | |
| Example 1 | 20.13 | 21.10 | 19.38 | 43.61 |
| Example 2 | 19.42 | 20.87 | 19.51 | 43.27 |
| Example 3 | 20.00 | 21.22 | 19.95 | 44.24 |
Acquisition of real ambient air samples
In a conference room, the activated MOFs composite sampling tubes prepared in examples 1-3 were respectively connected with an atmospheric sampling pump, and sampled at a flow rate of 200mL/min for 50min; the results of calculation performed by the formula 1 are shown in table 2, wherein the GC-MS spectrum of the MOFs composite material air sampling tube prepared in the example 1 for collecting volatile organic compounds in air is shown in fig. 4.
TABLE 2 results of tests in actual Environment (Unit: μg/m 3 )
As can be seen from the contents of Table 2, the MOFs composite air sampling tube can be used for collecting volatile organic compounds with low concentration in air, is easy to use in combination with thermal desorption-gas chromatography-mass spectrometry, and is convenient to operate.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (5)
1. The MOFs composite material air sampling tube is characterized by comprising a glass tube and an adsorbent filled in the glass tube, wherein the adsorbent is MOFs composite material, and the MOFs composite material is prepared by loading UiO-66 on a white carrier;
the preparation method of the MOFs composite material comprises the following steps:
(1) Mixing zirconium tetrachloride and terephthalic acid, adding concentrated HCl and DMF, dissolving, adding a white carrier, uniformly mixing, performing constant-temperature reaction under a sealed condition, cooling to room temperature, and filtering to obtain white particles;
(2) Soaking the white particles obtained in the step (1) in DMF, standing at a constant temperature, filtering, then soaking the white particles in acetone, standing at a constant temperature, filtering again, and then drying the white particles in vacuum to obtain the MOFs composite material;
the molar ratio of the zirconium tetrachloride to the terephthalic acid is 1:1-1: 1.2, the feed liquid ratio of zirconium tetrachloride to concentrated HCl and DMF is (0.3-0.5) g: (0.3-0.5 mL): (20-30 mL);
in the step (1), the temperature of the constant temperature reaction is 120-150 ℃ for 24 hours, in the step (2), when the reaction is soaked in DMF, the reaction is kept at the constant temperature of 80 ℃ for 24 hours, the DMF is replaced every 6 hours during the soaking in acetone, the reaction is kept at the room temperature for 3 days, and the acetone is replaced every 12 hours during the soaking.
2. The MOFs composite air sampling tube according to claim 1, wherein the white support is an acid-washed white support with a particle size of 60-80 mesh.
3. The MOFs composite air sampling tube according to claim 1, wherein the loading of UiO-66 in the white support is 10-20%.
4. A method for preparing the MOFs composite air sampling tube according to any one of claims 1 to 3, comprising the steps of:
filling the MOFs composite material into cylindrical glass, blocking two ends by glass wool, fixing by a stainless steel net, and activating to obtain the MOFs composite material air sampling tube;
the activation condition is that the activation is carried out for 20-40 min at 200-250 ℃ under the flow rate of helium of 50-150 mL/min.
5. Use of the MOFs composite air sampling tube according to any one of claims 1 to 3 for the adsorption collection of low concentration volatile organic compounds in analysis air.
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| CN108786494A (en) * | 2018-05-31 | 2018-11-13 | 昆明理工大学 | A kind of preparation method of UiO-66 composite film materials |
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