CN1862760A - Chemical ioning method based on dielectric blocking discharge and mass ion source - Google Patents
Chemical ioning method based on dielectric blocking discharge and mass ion source Download PDFInfo
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- CN1862760A CN1862760A CN 200610011548 CN200610011548A CN1862760A CN 1862760 A CN1862760 A CN 1862760A CN 200610011548 CN200610011548 CN 200610011548 CN 200610011548 A CN200610011548 A CN 200610011548A CN 1862760 A CN1862760 A CN 1862760A
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 title description 2
- 230000000903 blocking effect Effects 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000012495 reaction gas Substances 0.000 claims abstract description 25
- 238000000451 chemical ionisation Methods 0.000 claims abstract description 16
- 238000001819 mass spectrum Methods 0.000 claims abstract description 14
- 230000004888 barrier function Effects 0.000 claims description 42
- 150000002500 ions Chemical class 0.000 claims description 41
- 238000004949 mass spectrometry Methods 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001282 iso-butane Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000005416 organic matter Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000012491 analyte Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000065 atmospheric pressure chemical ionisation Methods 0.000 description 2
- 238000010265 fast atom bombardment Methods 0.000 description 2
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 2
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001184 proton transfer reaction mass spectrometry Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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Abstract
This invention relates to chemical ionization base on medium resisting discharging and mass spectrum ion source, it belongs to chemical engineering technique field. It especially relates to active base group ionization to organic matter molecular based on medium resisting discharging technique and mass spectrum ion source used for organic matter detecting. The features are that the medium resisting discharging device is used to ionize the reaction gas that can be used to chemical ionization, the reaction gas is ionized to generate ion and the reaction ion is ion-molecular react with the measuring organic matter to make the organic matter ionization, so mass spectrum can be used t realize detecting. The discharging voltage is 220V-10000V, frequency is 50 Hz to 50MHz, and reaction gas flow velocity is 10ml/min-1000ml/min. The corresponding mass spectrum is also provided. The measuring organic matter can be ionized in this invention, and it can be realized in atmospheric pressure environment, the device volume is small, energy consumption is low.
Description
The technical field is as follows:
a chemical ionization method based on dielectric barrier discharge and a mass spectrometry ion source belong to the technical field of chemical engineering, and particularly relate to a mass spectrometry ion source technology for ionizing organic molecules based on active groups generated by dielectric barrier discharge and further detecting the organic.
Background art:
at present, mass spectrometry is commonThe ionization method mainly comprises the following steps: electron ionization source (EI), chemical ionization source (CI), fast atom bombardment source (FAB), electrospray ionization source (ESI), atmospheric pressure chemical ionization source (APCI), laser desorption source (LD), and the like. Wherein the electron ionization source and the chemical ionization source are mainly used for ionizing the volatile organic samples. The electron ionization source ionizes the sample by electron bombardment, the structure is simple and easy to realize, and the provided structural information is rich. But molecular ions are likely not available for poorly stable organics. The chemical ionization source requires a reactant gas that is ionized and then undergoes an ion-molecule reaction with the sample molecules to ionize the sample. The method is a soft ionization mode, does not generate great damage to sample molecules, is easy to obtain molecular ions, and is an effective supplement for electron ionization. The commonly used reaction gases mainly include methane, isobutane, ammonia gas and the like, and the ionization of the reaction gases is usually electron ionization. A novel chemical ion source, Proton Transfer Reaction (PTR) ion source mass spectrum, appeared in the nineties of the 20 th century, and the mass spectrum is based on H3O+Reacting with the analyte to ionize the analyte. Ion affinity greater than H3O+Can abstract H from volatile organic compounds such as (VOC)3O+The proton transfer occurs to ionize the VOC, which is: . This method greatly improves the sensitivity of VOC analysis. The mass spectrometry ion source mainly comprises two parts: h3O+An ion generation chamber and a drift tube. H3O+The ion generating chamber mainly generates high-density reaction ions H3O+There are two main ways commonly used at present: radioactive ion sources and hollow cathode discharge ion sources. The radioactive ion source mainly uses radioactive elements (241Am, etc.) to generate H from β rays generated by radiation3O+This method is a radiological hazard and there is a potential for contamination of the electrodes. The hollow cathode discharge mainly realizes gas discharge under the condition of low pressure to ionize water vapor to generate H3O+. The disadvantage of this structure is that the water vapor comes into contact with the electrodes, which may also result inAnd (4) electrode contamination. PTR-MS, although very sensitive to VOCs, has not been widely used because the equipment is also relatively complex.
Dielectric barrier discharge (dielectric barrier discharge) is a gas discharge that can be realized at normal pressure, belongs to non-equilibrium plasma, and can also generate a large amount of charged particles and other active groups. The structure of dielectric barrier discharge is characterized in that at least one layer of insulating barrier dielectric exists, and the distance between electrodes (discharge channel) is small. The dielectric barrier layer separates the electrode from the reaction gas and does not cause contamination of the electrode. When a sufficiently high ac voltage is applied to the discharge electrode, the gas between the electrodes breaks down even under atmospheric pressure to form a so-called dielectric barrier discharge. The discharge is uniform and stable, and is actually composed of a large number of fine fast pulse discharge channels. The discharge has the advantages of being realized under atmospheric pressure, small in size, low in energy consumption (several watts) and low in gas temperature (about 600K). There is no report of using the ion in mass spectrometry ionization, and the application of the ion in chemical ionization can greatly promote the development of mass spectrometry work.
The invention content is as follows:
the invention aims to provide a novel chemical ionization method, which utilizes ions in plasma generated by dielectric barrier discharge to perform ion-molecule reaction with sample molecules to ionize the sample molecules, and also provides a corresponding mass spectrum ion source.
The method is characterized in that a dielectric barrier discharge device is utilized to ionize reaction gas which can be used for chemical ionization, so that the reaction gas is ionized to generate reaction ions, and the reaction ions and organic matters to be detected generate ion-molecule reaction to ionize the organic matters, thereby realizing detection by mass spectrum; the voltage of the dielectric barrier discharge is 220V-10000V, the frequency is 50Hz-50MHz, and the flow rate of the reaction gas is 10ml/min-1000 ml/min.
The reaction gas is one of methane, isobutane, ammonia gas and steam, or a mixed gas of methane, isobutane, ammonia gas, steam and inert gas.
The organic is a volatile organic or a halogenated hydrocarbon.
The mass spectrometry ion source designed according to the method comprises an ionization chamber and a reaction chamber, and is characterized in that the ionization chamber is a dielectric barrier discharge device which comprises two discharge electrodes, a discharge channel is arranged between the two electrodes, and at least one layer of insulating barrier medium is arranged between the two electrodes.
The discharge electrodes are flat plate electrodes, and two layers of insulating barrier media are arranged between the two electrodes.
The discharge electrodes may also be two concentric circles with two layers of insulating barrier medium between the two electrodes concentric with the electrodes.
The height of the discharge channel is 0.5mm-10 mm. The length of the discharge channel is 0.5cm-20 cm. The insulating medium is quartz, glass, ceramic or plastic. The thickness of the insulating medium is 0.5mm-5 mm.
Experiments prove that the method can effectively ionize the organic matter to be tested, can be realized under atmospheric pressure, and has the advantages of small equipment volume, low energy consumption and the like.
Description of the drawings:
FIG. 1 is a schematic view of an ion source configuration;
fig. 2 is a structural view of a dielectric barrier discharge cell, in which fig. 2a is a flat electrode type structure and fig. 2b is a cylindrical electrode type structure.
The specific implementation mode is as follows:
the following describes the embodiments of the present invention in detail with reference to the accompanying drawings.
Designing an ion source:
as shown in the integral design of the ion source shown in FIG. 1, the ion source mainly comprises two parts, namely a discharge chamber and a reaction chamber. The discharge chamber is mainly a cavity for realizing dielectric barrier discharge, and the reaction gas discharges in the cavity to generate required ions (such asH3O+) And an active group. The reaction chamber mainly ionizes sample molecules by ion-molecule reaction, and the ionized molecular ions are introduced into a mass spectrum for detection.
As shown in fig. 2, the structure of the dielectric barrier discharge cell is characterized by at least one layer of insulating barrier dielectric and a small distance (discharge channel) between the electrodes. However, the separation of the electrode from the reaction gas cannot be guaranteed by one layer of barrier medium, which is easy to cause the pollution of the electrode. The invention utilizes double-layer barrier medium to separate the electrode (1) from the discharge gas, thereby avoiding the pollution of the electrode. The most common structure of dielectric barrier discharge is a flat plate type, as shown in fig. 2a, a suitable dielectric is selected to be inserted between two flat plate electrodes as a barrier layer, and the commonly used barrier dielectric (2) mainly comprises (quartz, ceramic, common glass, etc.). The other structure is a cylinder, as shown in fig. 2b, the two electrodes are concentrically arranged, and a medium barrier layer is arranged in the middle. When an alternating voltage with a certain frequency is applied between the two electrodes, uniform discharge is realized in the discharge channel (3). The generated reaction gas ions enter the reaction chamber to generate ion-molecule reaction.
The ion source utilizes ions required by chemical reaction generated by dielectric barrier discharge to carry out chemical ionization, has good response to a plurality of organic matters, and can obtain good molecular ion peaks. The method is mainly characterized in that the method can be used for detecting various organic molecules in gas or solution and can be used as a detection means of gas chromatography. The ion source has the following advantages: the method has the advantages of multiple selectable reaction gas types, no electrode pollution, long service life, high sensitivity, easy operation and good repeatability, and can be operated under normal pressure.
The effect of the present invention will be further described below by taking several examples of reaction gases for practical use.
The first embodiment selects water vapor as reaction gas, and the reaction gas is introduced into a discharge chamber, the discharge chamber adopts a cylindrical structure, double-layer medium is adopted, the height of a discharge channel (3) is 2mm, the length of a discharge area is 10cm, a barrier medium (2) is quartz (0.5mm), stable discharge is generated under the conditions that the discharge voltage is 3000V and the frequency is 20kHz, the flow rate of the water vapor is 10ml/min, and the method usesThe nanoampere meter can measure the outlet current of the discharge chamber as follows: 10nA, indicating that a certain amount of H was obtained3O+An air sample containing volatile organic compounds to be tested is introduced into the reaction chamber. H produced by electric discharge3O+Namely, the ion exchange reaction is carried out with volatile organic compounds in the air, so as to lead the volatile organic compounds to be ionized, thereby realizing the detection by mass spectrum. The ion source has high sensitivity (ppbv grade), wide linear range (more than three orders of magnitude), good reproducibility, relatively simple spectrogram and easy analysis on volatile organic matters (acetone, formaldehyde, benzene and the like).
Selecting ammonia gas as reaction gas, introducing the reaction gas into a discharge chamber, wherein the discharge chamber adopts a flat plate type structure and double-layer media, the height of a discharge channel (3) is 0.5mm, the length of a discharge area is 3cm, glass is used as a barrier medium (2) (5mm), stable discharge is generated under the conditions that the discharge voltage is 220V and the frequency is 50MHz, the flow rate of the ammonia gas is 300ml/min, and hexachlorobenzene is introduced into the reaction chamber. NH generated by discharge4 +Namely, the hexachlorobenzene is ionized through ion-molecule reaction, so that the detection is realized by mass spectrum.
Selecting methane gas as reaction gas, introducing the reaction gas into a discharge chamber, wherein the discharge chamber adopts a flat plate type structure, double layers of media are adopted, the height of a discharge channel (3) is 10mm, the length of a discharge area is 20cm, alumina ceramic is used as a barrier medium (2) (1mm), stable discharge is generated under the conditions that the discharge voltage is 10000V and the frequency is 50Hz, the flow rate of methane is 1000ml/min, and porphyrin is introduced into the reaction chamber. Ions generated by the discharge are subjected to ion-molecule reaction with porphyrin molecules to be ionized, so that the detection is realized by mass spectrometry.
Selecting argon as reaction gas, introducing the reaction gas into a discharge chamber, wherein the discharge chamber is of a cylindrical structure, the height of a discharge channel (3) is 3mm, the length of a discharge area is 0.5cm, quartz is used as a barrier medium (2) (1mm), stable discharge is generated under the conditions that the discharge voltage is 4000V and the frequency is 30kHz, the flow rate of argon is 500ml/min, and bromobenzene is introduced into the reaction chamber. The discharge chamber outlet current that can be measured with the nanoampere meter is: 20nA, Ar produced by discharge+Namely, the bromobenzene undergoes ion-molecule reaction to be ionized, thereby the mass spectrometry is usedAnd detecting.
And fifthly, selecting a mixed gas of argon and methane (90% argon) as a reaction gas, introducing the reaction gas into a discharge chamber, wherein the discharge chamber is of a flat plate type structure, the length of a discharge area is 5cm, the height of a discharge channel (3) is 3mm, a polytetrafluoroethylene plate is a barrier medium (2) (2mm), stable discharge is generated under the conditions that the discharge voltage is 5000V and the frequency is 27MHz, the gas flow rate is 400ml/min, and the methyl tin is introduced into the reaction chamber. Ions generated by the discharge are subjected to ion-molecule reaction with the methyl tin to be ionized, so that the detection is realized by mass spectrum.
Claims (10)
1. The chemical ionization method based on dielectric barrier discharge is characterized in that a dielectric barrier discharge device is utilized to ionize reaction gas for chemical ionization, the reaction gas is ionized to generate reaction ions, and the reaction ions and organic matters to be detected are subjected to ion-molecule reaction to ionize the organic matters, so that the detection is realized by mass spectrum; the voltage of the dielectric barrier discharge is 220V-10000V, the frequency is 50Hz-50MHz, and the flow rate of the reaction gas is 10ml/min-1000 ml/min.
2. The method of chemical ionization based on dielectric barrier discharge according to claim 1 wherein the reactive gas is one of methane, isobutane, ammonia, water vapor, or a mixture of methane, isobutane, ammonia, water vapor and an inert gas.
3. Method for chemical ionization based on dielectric barrier discharge according to claim 1 characterized in that the organic is a volatile organic or a halogenated hydrocarbon.
4. A mass spectrometry ion source designed for chemical ionization method based on dielectric barrier discharge according to claim 1 comprising an ionization chamber and a reaction chamber, wherein said ionization chamber is a dielectric barrier discharge device comprising two discharge electrodes with a discharge channel therebetween, and at least one layer of insulating barrier medium between said two electrodes.
5. The mass spectrometry ion source of claim 4, wherein the discharge electrode is a plate electrode with two layers of insulating barrier medium therebetween.
6. The mass spectrometry ion source of claim 4, wherein the discharge electrodes are two concentric circles with two layers of insulating barrier medium between the two electrodes concentric with the electrodes.
7. The mass spectrometry ion source of claim 4, 5 or 6, wherein the height of the discharge channel is in the range of 0.5mm to 10 mm.
8. The mass spectrometry ion source of claim 4, 5 or 6, wherein the discharge channel length is from 0.5cm to 20 cm.
9. The mass spectrometry ion source of claim 4, 5 or 6, wherein the insulating medium is quartz, glass, ceramic or plastic.
10. The mass spectrometry ion source of claim 4, 5 or 6, wherein the thickness of the insulating medium is in the rangeof 0.5mm to 5 mm.
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| CN102683151A (en) * | 2012-05-15 | 2012-09-19 | 中国科学院合肥物质科学研究院 | Chemical ionization mass spectrometer for selectively controlling reaction ions |
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