CN110702495B - Method for enriching and analyzing benzene series in air based on MOFs (metal-organic frameworks) material - Google Patents

Method for enriching and analyzing benzene series in air based on MOFs (metal-organic frameworks) material Download PDF

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CN110702495B
CN110702495B CN201910964675.0A CN201910964675A CN110702495B CN 110702495 B CN110702495 B CN 110702495B CN 201910964675 A CN201910964675 A CN 201910964675A CN 110702495 B CN110702495 B CN 110702495B
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林兴桃
赵靖强
周星园
孙格
谢亚勃
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Beijing University of Technology
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Abstract

A method for enriching and analyzing benzene series in air based on MOFs material belongs to the technical field of analysis and test methods. Mixing MOFs and a white support in a mass ratio of 1: 10-1: 20, uniformly mixing, weighing the mixture, filling the mixture into a glass tube, and blocking two ends of the glass tube by using glass wool to obtain an MOFs sampling tube; and activating the filled MOFs sampling tube at the temperature of 200-250 ℃ for 20-30 min under the helium flow rate of 50-100 mL/min. After activation, putting the mixture into a dryer for storage for later use; the activated MOFs sampling tube is connected with an atmosphere sampling instrument, and air is collected at the normal temperature at the flow rate of 500mL/min for 20-45 min; after the MOFs sampling tube collects air, the air is directly placed into a thermal desorption instrument and is analyzed by thermal desorption-gas chromatography-mass spectrometry. The method is simple to operate, time-saving and labor-saving, avoids pollution of organic solvents, and is high in selectivity.

Description

Method for enriching and analyzing benzene series in air based on MOFs (metal-organic frameworks) material
Technical Field
The invention belongs to the technical field of analysis and test methods, and particularly relates to a method for enriching and analyzing benzene series in air by using metal-organic frameworks (MOFs).
Background
Benzene, toluene, xylene and other benzene series are common indoor air pollutants. The long-term exposure to benzene series can cause teratogenesis, carcinogenesis and mutagenesis. The most commonly used enrichment materials for benzene series determination in air are mainly activated carbon and Tenax-TA. Both have good adsorption properties, but have poor selectivity to benzene series.
The metal organic framework material is a novel porous nano material, combines organic ligands and metal ions in an autonomous assembly mode, has the characteristics of large pores, large specific surface area, good thermal stability, designable structure and the like, and is widely applied to the fields of gas adsorption, substance separation and purification, catalysis and the like.
UiO-66 is a Zr-centered terephthalic acid (H) developed by Norwegian Oslo university in 20082BDC) is a rigid metal organic framework material of organic ligands. The UiO-66 has better thermal stability and larger specific surface area, and because the UiO-66 has a benzene ring structure, the UiO-66 is used as an adsorbing material of the sampling tube to enrich benzene series in air, and the selectivity of the analysis method is expected to be improved.
Disclosure of Invention
The invention provides a novel enrichment material-MOFs material of an air sampling tube, and establishes an analysis method for measuring benzene series in air by thermal desorption-gas chromatography-mass spectrometry. The method comprises the following steps:
(1) preparation of MOFs sampling tube
Mixing MOFs and a white support in a mass ratio of 1: 10-1: 20, uniformly mixing, weighing the mixture, filling the mixture into a glass tube, and blocking two ends of the glass tube by using glass wool to obtain an MOFs sampling tube; and activating the filled MOFs sampling tube at the temperature of 200-250 ℃ for 20-30 min under the helium flow rate of 50-100 mL/min. After activation, putting the mixture into a dryer for storage for later use;
(2) sampling
The activated MOFs sampling tube is connected with an atmosphere sampling instrument, and air is collected at the normal temperature at the flow rate of 500mL/min for 20-45 min;
(3) analysis of
After the MOFs sampling tube collects air, the air is directly placed into a thermal desorption instrument and is analyzed by thermal desorption-gas chromatography-mass spectrometry.
Further preferably: in the step (3) of the method, a second-order desorption mode is adopted, and the desorption gas is helium; in the first stage, a sample tube is desorbed at the desorption temperature of 150-200 ℃, the desorption time is 20-30 min, the desorption flow rate is 40-60 mL/min, and the corresponding cold trap trapping temperature after desorption is-10-0 ℃; in the second stage, cold trap desorption is carried out, wherein the desorption temperature is 250-300 ℃, the desorption time is 2-5 min, the temperature rise rate is 40-60 ℃/s, and the shunt at the trap outlet is 0-9 mL/min, wherein when the temperature is 0, the shunt is not carried out; and (3) shunting by adopting a six-way valve, wherein the temperature of the six-way valve is 230-250 ℃, and the temperature of a transmission line is 230-250 ℃.
Further preferably: the method comprises the following steps of (3) gas chromatography conditions: the gas chromatography column used was an HP-5MS column (30 m.times.0.25 mm, 0.25 μm thick) with helium as the carrier gas at a flow rate of 1mL/min and an initial temperature of 50 deg.C for 5min, and was ramped up to 250 deg.C at a rate of 10 deg.C/min for 5 min.
The mass spectrum adopts EI ionization, electron energy is 70eV, transmission line temperature is 250 ℃, ion source temperature is 250 ℃, mass scanning range m/z is 50-500, and a full scanning mode is adopted.
The MOFs described in the invention is selected from UiO66, and the white support is preferably selected from 102 acid-washed white supports.
When the analysis is carried out in the step (3), quantitative analysis is carried out, firstly, the same method is adopted to carry out quantitative test on a standard substance, namely the benzene series standard substance to be tested, and a working curve of quantitative standard is prepared as a basis, preferably, the mass is taken as a horizontal coordinate, and the peak area is taken as a vertical coordinate; the test substance is then quantified according to the curve described above.
The benzene series is one or more of benzene, toluene, o-xylene, m-xylene and p-xylene.
The method is simple to operate, time-saving and labor-saving, avoids pollution of organic solvents, is high in selectivity, is suitable for determination of benzene series in air, and is accurate in measurement and high in accuracy.
Drawings
FIG. 1 is a GC-MS spectrum of benzene, toluene, o-, m-, p-xylene;
FIG. 2 is a GC-MS spectrogram of a MOFs sampling tube enriching benzene series in air;
FIG. 3 is a GC-MS spectrum of benzene series in air enriched by Tenax-TA sampling tube.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples. The white support in the following examples is a 102 acid-washed white support from Tianjin Borui bond chromatography technology, Inc. with a particle size of 60-80 mesh.
Example 1: preparation of MOFs sampling tube
Mixing MOFs and a white support in a mass ratio of 1: 10mg of the mixture was weighed out and filled into a glass tube, and both ends were plugged with glass wool. The filled MOFs sampling tubes were activated at 200 ℃ for 20min at a helium flow rate of 50 mL/min. After activation, the mixture is stored in a dryer for later use.
Example 2: determination of second order thermal desorption conditions
In the first stage, the sample tube is desorbed at the desorption temperature of 150 ℃, the desorption time is 20min, the desorption flow rate is 50mL/min, and the cold trap trapping temperature is-10 ℃; in the second stage, cold trap desorption is carried out, wherein the desorption temperature is 300 ℃, the desorption time is 5min, the temperature rise rate is 40 ℃/s, and 9mL/min of shunt is carried out at a trap outlet; the temperature of the six-way valve is 230 ℃ and the temperature of the transmission line is 250 ℃.
Example 3: drawing of working curves
Accurately weighing a certain amount of benzene, toluene, o-xylene, m-xylene and p-xylene respectively, and preparing a benzene series mixed standard stock solution by using methanol as a solvent. Wherein the concentration of benzene is 0.696mg/mL, toluene is 0.896mg/mL, p-xylene is 1.012mg/mL, m-xylene is 0.992mg/mL, and o-xylene is 1.016 mg/mL.
Accurately transferring a certain amount of benzene series mixed standard stock solution, and preparing a benzene series standard solution series by using methanol as a solvent, wherein the concentration is detailed in table 1.
TABLE 1 series of benzene series standard solutions (mg/mL)
Figure BDA0002230095270000021
Respectively transferring 10 mu L of standard solutions with different concentrations by using a micro-injector, injecting the standard solutions into an activated MOFs sampling tube, and blowing the MOFs sampling tube for 20min at the nitrogen flow rate of 500mL/min to prepare a standard series of sample tubes. And (3) performing thermal desorption-gas chromatography-mass spectrometry, and drawing a working curve by taking the mass as a horizontal coordinate and the peak area as a vertical coordinate, wherein the results are shown in table 2, the correlation coefficients of the benzene series can reach more than 0.999, and the linear correlation is good.
TABLE 2 working curves of the benzene series
Figure BDA0002230095270000022
Example 4: precision and accuracy
The accuracy determination method is as follows: and respectively injecting 10 mu L of benzene series standard solution into the activated 5 sampling tubes, purging for 20min at the nitrogen flow rate of 500mL/min, performing thermal desorption-gas chromatography-mass spectrometry, comparing with the direct injection of the benzene series standard solution, calculating the recovery rate, and inspecting the accuracy of the method. The method for determining the precision is as follows: and respectively injecting benzene series standard solutions with the same concentration into the activated 5 sampling tubes to prepare 5 standard tubes, analyzing and inspecting the in-day precision of the 5 standard tubes in the same day, and respectively analyzing and inspecting the in-day precision of the 5 standard tubes in 5 continuous days. Precision and accuracy were calculated according to equations 1, 2 and 3, respectively. The results are shown in Table 3, the relative standard deviation is between 4.7% and 8.6%, the recovery rate is 83% to 102%, and the analysis requirements can be met.
Equation 1
Figure BDA0002230095270000031
Equation 2
Figure BDA0002230095270000032
Equation 3
Figure BDA0002230095270000033
TABLE 3 precision and recovery of benzene series
Figure BDA0002230095270000034
Example 5: collection of benzene series standard gas
Collecting benzene series standard gas (wherein benzene: 20.88 mg/m) by using MOFs sampling tube3Toluene: 24.64mg/m3O-xylene: 26.06mg/m3M-xylene: 26.36mg/m3P-xylene: 26.31mg/m3)100mL, placing the sampling tube into a thermal desorption instrument, performing thermal desorption-gas chromatography-mass spectrometry according to an established method, and obtaining benzene by calculation according to a formula 4: 21.82mg/m3Toluene: 24.22mg/m3O-xylene: 21.63mg/m3P-m-xylene: 43.33mg/m3。
Equation 4
Figure BDA0002230095270000035
Example 6: actual air sample collection
By applying the method, the MOFs sampling pipe is connected with an atmospheric sampling instrument in a bedroom, air is collected for 20min at the normal temperature at the flow rate of 500mL/min, the sampling pipe is placed in a thermal desorption instrument, thermal desorption-gas chromatography-mass spectrometry is carried out according to the established method, and the content of benzene series in the air is calculated by a formula 4: benzene: 0.02mg/m3Toluene: 0.02mg/m3O-xylene: 0.06mg/m3P-xylene, m-xylene: 0.07mg/m3. FIG. 2 is a GC-MS spectrogram of a MOFs sampling tube for enriching benzene series in air, and FIG. 3 is an analysis result of a Tenax-TA sampling tube in the same place by the same method. As can be seen from a comparison of fig. 2 and 3, fig. 2 has fewer interferents and better selectivity to benzene series than fig. 3.

Claims (7)

1. A method for enriching and analyzing benzene series in air based on MOFs materials is characterized by comprising the following steps:
(1) preparation of MOFs sampling tube
Mixing MOFs and a white support in a mass ratio of 1: 10-1: 20, uniformly mixing, weighing the mixture, filling the mixture into a glass tube, and blocking two ends of the glass tube by using glass wool to obtain an MOFs sampling tube; activating the filled MOFs sampling tube at the temperature of 200-250 ℃ for 20-30 min at the helium flow rate of 50-100 mL/min; after activation, putting the mixture into a dryer for storage for later use;
(2) sampling
The activated MOFs sampling tube is connected with an atmosphere sampling instrument, and air is collected at the normal temperature at the flow rate of 500mL/min for 20-45 min;
(3) analysis of
After the MOFs sampling tube collects air, the air is directly placed into a thermal desorption instrument and is analyzed by thermal desorption-gas chromatography-mass spectrometry.
2. The method for enrichment analysis of benzene series in air based on MOFs materials according to claim 1, wherein the step (3) adopts a second-order desorption mode, and the desorption gas is helium; in the first stage, a sample tube is desorbed at the desorption temperature of 150-200 ℃, the desorption time is 20-30 min, the desorption flow rate is 40-60 mL/min, and the corresponding cold trap trapping temperature after desorption is-10-0 ℃; in the second stage, cold trap desorption is carried out, wherein the desorption temperature is 250-300 ℃, the desorption time is 2-5 min, the temperature rise rate is 40-60 ℃/s, and the shunt at the trap outlet is 0-9 mL/min, wherein when the temperature is 0, the shunt is not carried out; and (3) shunting by adopting a six-way valve, wherein the temperature of the six-way valve is 230-250 ℃, and the temperature of a transmission line is 230-250 ℃.
3. The method for enriching and analyzing the benzene series in the air based on the MOFs, according to claim 1, wherein the gas chromatography conditions in the step (3) are as follows: the gas chromatography column was HP-5MS, helium as carrier gas, at a flow rate of 1mL/min, an initial temperature of 50 deg.C, held for 5min, ramped up to 250 deg.C at a rate of 10 deg.C/min, and held for 5 min.
4. The method for enrichment analysis of benzene series in air based on MOFs materials according to claim 1, wherein the mass spectrum adopts EI ionization, electron energy is 70eV, transmission line temperature is 250 ℃, ion source temperature is 250 ℃, mass scanning range m/z is 50-500, and full scanning mode.
5. The method for enrichment analysis of benzene series in air based on MOFs material according to claim 1, wherein MOFs is selected from UiO66 and the white support is selected from 102 acid-washed white supports.
6. The method for enriching and analyzing the benzene series substances in the air based on the MOFs materials according to claim 1, wherein when the analysis is performed in the step (3), quantitative analysis is performed, firstly, a standard substance, namely the benzene series substance standard substance to be tested, is quantitatively tested by adopting the same method, a working curve of quantitative standard is prepared and used as a basis, and the mass is used as a horizontal coordinate, and the peak area is used as a vertical coordinate; the test substance is then quantified according to the curve described above.
7. The method for enrichment analysis of benzene series in air based on MOFs materials according to claim 1, wherein said benzene series is one or more of benzene, toluene, o-xylene, m-xylene and p-xylene.
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