CN107342210A - The Proton-Transfer Reactions ion gun of protonation water is provided using excitation state proton-electron collaboration transfer reaction - Google Patents
The Proton-Transfer Reactions ion gun of protonation water is provided using excitation state proton-electron collaboration transfer reaction Download PDFInfo
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- CN107342210A CN107342210A CN201710552505.2A CN201710552505A CN107342210A CN 107342210 A CN107342210 A CN 107342210A CN 201710552505 A CN201710552505 A CN 201710552505A CN 107342210 A CN107342210 A CN 107342210A
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- proton
- transfer
- excitation state
- electron
- ion gun
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- 238000006276 transfer reaction Methods 0.000 title claims abstract description 39
- 230000005284 excitation Effects 0.000 title claims abstract description 20
- 230000005588 protonation Effects 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 49
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 7
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 description 6
- 230000005684 electric field Effects 0.000 description 4
- 238000001184 proton transfer reaction mass spectrometry Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 150000005826 halohydrocarbons Chemical class 0.000 description 3
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000005945 translocation Effects 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Proton-Transfer Reactions ion gun involved in the present invention, it is a kind of new ion gun, it is to cooperate with transfer reaction using excitation state proton-electron to provide the Proton-Transfer Reactions ion gun of protonation water.It is by vacuum-ultraviolet light light source chamber (1), H3O+Generation cavity (2), Proton-Transfer Reactions chamber (3), gaseous state halogenated hydrocarbons and vapor sample feeding pipe (4) and VOCs sample feeding pipes (5) composition.The ion gun excites dichloromethane or methylene bromide using vacuum-ultraviolet light；The proton-electron that gas phase occurs with hydrone for the excitation state halogenated hydrocarbons of generation cooperates with transfer reaction to produce H3O+, H3O+The VOCs ions that Proton-Transfer Reactions generation protonation occurs further are collided with VOCs.The H of the Proton-Transfer Reactions ion gun generation of the present patent application3O+Concentration is high, stability is strong, stray ion is few, can improve current VOCs and monitor mass spectrometric level of sensitivity on-line.
Description
Art
The present invention relates to a kind of ion gun, the trace gas such as volatile organic matter in ionizable air, for it in gas
Highly sensitive on-line checking in phase.
Background technology
Volatile organic matter (VOCs) is a kind of important atmosphere pollution, and it is not only involved in city photochemical reaction and promoted
The formation of secondary organic aerosol and gray haze, a part of VOCs still belong to carcinogen and are directly detrimental to health.Meanwhile VOCs
As a kind of primary product of human metabolism, the VOCs for monitoring characteristics of contaminated respiratory droplets gas or skin release is expected to develop into non-invade
Enter the new tool of formula health diagnosis.Therefore, VOCs highly sensitive on-line checking has a wide range of applications market and urgent
Application demand.The common instrument medium sensitivity highest for being presently used for VOCs on-line monitorings is Proton transfer reaction mass spectrometry instrument
(PTR-MS), sensitivity is up to pptv magnitudes.Its core is Proton-Transfer Reactions (PTR) ion gun, usually using determinand
Molecule and protonation water (H3O+) occur PTR reaction mode ionize test substance.Wherein, caused H3O+Ion stream concentration
It is a principal element for influenceing determinand ionizing efficiency and instrument detection sensitivity.
Commercialized PTR ion guns often form H with hollow cathode discharge3O+Ion, because discharge process is one non-steady
Determine process, need 200-500V voltages to excite and maintain to discharge, this process can produce many foreign ions, in addition hollow cathode discharge
Vertical electric field can also cause H3O+Certain loss.2003, Hanson etc. reported one kind and uses alpha radiator241Am
Radiation produces H3O+PTR ion guns, H caused by this method3O+Ion stream is stable and the pollution of foreign ion is small, but radioactivity
The application of material makes this method potential safety hazard be present.2006, Inomata etc. reported a kind of plane electrode direct-current discharge and carrys out shape
Into H3O+PTR ion guns, direct-current discharge can be prevented due to the backflow of analyte and caused interfering ion, but because of its generation
H3O+Ion stream concentration is low and PTR-MS sensitivity is decreased.2011, Chinese invention patent application prospectus
CN201110020412.8 discloses a kind of PTR ion guns based on microwave discharge, but because microwave discharge also needs higher electricity
Pressure is excited and maintained, therefore equally exists the problem of stray ion is more.In a word, ionization source produces H3O+Concentration it is not high enough or not
Stable that PTR-MS detection sensitivity can be caused not high enough or unstable, foreign ion can uprise instrument test limit, ionization source
Potential safety hazard be present is compromised the operator of instrument.
Ours experimental studies have found that：Under the exciting of vacuum-ultraviolet light, excitation state dichloromethane or methylene bromide can be with
Transfer reaction is cooperateed with what proton and electronics occurred for water vapour, generates substantial amounts of H3O+Water ion, its concentration are higher than current hollow the moon
It is more than 2 magnitudes of pole electric discharge.Therefore, excitation state dichloromethane or methylene bromide cooperate with the proton-electron that water vapour occurs turns
Moving reaction can be as a kind of new H3O+Production method.
The content of the invention
Trace V OCs is stably detected in order to sensitive, the present invention provides a kind of anti-using the collaboration transfer of excitation state proton-electron
H should be generated3 +O Proton-Transfer Reactions ion gun (PCET-PTR), it excites dichloromethane or methylene bromide and water using light
The collaboration transfer reaction of steam generation proton and electronics produces H3O+, its reaction mechanism mechanism of reaction is as follows：
CH2Cl2+hv→[CH2Cl+-Cl-]*
[CH2Cl+-Cl-]*+2H2O→[2H2O-CH2Cl+-Cl-]
[2H2O-CH2Cl+-Cl-]→H3 +O+Cl-+HCl+CH2O
Caused H3 +The VOCs ions of Proton-Transfer Reactions generation protonation occur with VOCs molecules for O ion streams, are VOCs
Detection provide ion gun.H caused by this method3O+Concentration is high, foreign ion is few, safety and environmental protection, makes the instrument using the ion gun
Utensil has high sensitivity and stability.
The technical scheme that patent of the present invention uses is：1st, the vacuum-ultraviolet light as caused by VUV radiant excites dichloro
Methane or methylene bromide produce excitation state halo hydrocarbon molecule；2nd, excitation state halo hydrocarbon molecule cooperates with vapor generation proton-electron
Transfer reaction produces H3O+；3、H3O+The VOCs ions that Proton-Transfer Reactions generation protonation occurs are collided with VOCs.
The beneficial benefit of the present invention is the H formed using excitation state proton-electron collaboration transfer reaction3O+Ion gun concentration
It is higher, more stable, stray ion is less, safer so that using the instrument of the ion gun have higher sensitivity and
Lower test limit.
Brief description of the drawings
Fig. 1 is the outside drawing of structure of the present invention, respectively 1, vacuum-ultraviolet light light source chamber, 2, H3O+Generation cavity, 3, proton turn
Move reaction chamber, 4, gaseous state halogenated hydrocarbons and water vapour sample feeding pipe, 5, VOCs sample feeding pipes.
Fig. 2 is the sectional structural map of the present invention, and critical piece has：6th, vacuum UV lamp, 7, magnesium fluoride window, 8, light tight
Baffle plate, 9, H3O+Draw and accelerate electrode, 10, the combination of Proton-Transfer Reactions coordination electrode, 11, ion source outlet.
Embodiment
Transfer reaction is cooperateed with to generate H using excitation state proton-electron3 +The main part of O PTR ion guns is purple by vacuum
Outer radiant room 1, gaseous state halogenated hydrocarbons and vapor sample feeding pipe 4, H3O+Generation cavity 2, VOCs sample feeding pipes 5, Proton-Transfer Reactions chamber 3
Five parts are formed.Embodiment is：
First, in vacuum-ultraviolet light source chamber 1, after vacuum ultraviolet photon is produced by vacuum UV lamp 6, perfluorinated magnesium window 7
Into H3O+Generation cavity 2；
2nd, the mixed gas of gaseous state halogenated hydrocarbons and vapor is directly entered H by stainless steel tube 53O+Generation cavity 2, its flow by
Noticeable degree；
3rd, into H3O+The gaseous state halogenated hydrocarbons of generation cavity 2 irradiates the halo hydrocarbon molecule for producing excitation state through vacuum-ultraviolet light,
The proton-electron that excitation state occurs with vapor afterwards cooperates with transfer reaction, generates substantial amounts of H3O+Ion, be added in Ion Extraction and
The low voltage electric field on electrode 9 is accelerated to make the H of generation3O+Enter Proton-Transfer Reactions chamber 3 after accelerated；
4th, into the H of Proton-Transfer Reactions chamber 33O+Obtained under electric field controls caused by Proton-Transfer Reactions coordination electrode 10
Specific translational speed is obtained, and the VOCs with entering Proton-Transfer Reactions chamber 3 by sample feeding pipe 5 collides, it is anti-through proton translocation
The VOCs ions protonated accordingly should be generated, VOCs is atmospheric pressure direct injected, and its flow is adjusted by needle-valve；
5th, the VOCs ions of protonation flow out matter after electric field controls caused by Proton-Transfer Reactions coordination electrode combination 10
The ion source outlet 11 of sub- transfer reaction chamber 3, form ion gun.
Claims (6)
1. transfer reaction is cooperateed with using excitation state proton-electron to provide the Proton-Transfer Reactions ion gun of protonation water by vacuum
Ultraviolet source room (1), H3O+Generation cavity (2), Proton-Transfer Reactions chamber (3), gaseous state halogenated hydrocarbons and vapor mixed gas sample introduction
Manage (4) and VOCs sample feeding pipes (5) composition；It is characterized in that by vacuum-ultraviolet light light source chamber (1), H3O+Generation cavity (2), proton turn
Move reaction chamber (3) three parts composition ion gun.
2. according to claim 1 cooperate with transfer reaction to provide the proton turn of protonation water using excitation state proton-electron
Move reactive ion source, it is characterised in that：The vacuum-ultraviolet light light source chamber (1), H3O+Generation cavity (2) and Proton-Transfer Reactions chamber
(3) it is sequentially connected and connects, and on the same axis.
3. according to claim 1 cooperate with transfer reaction to provide the proton turn of protonation water using excitation state proton-electron
Move reactive ion source, it is characterised in that：The material that is excited is dichloromethane or methylene bromide.
4. according to claim 1 cooperate with transfer reaction to provide the proton turn of protonation water using excitation state proton-electron
Move reactive ion source, it is characterised in that：Exciting light sources are vacuum ultraviolet light source.
5. according to claim 1 cooperate with transfer reaction to provide the proton turn of protonation water using excitation state proton-electron
Move reactive ion source, it is characterised in that：The H3O+Excitation state proton-electron collaboration transfer reaction area occurs in generation cavity (2)
Air pressure is 50Pa a to atmospheric pressure.
6. according to claim 1 cooperate with transfer reaction to provide the proton turn of protonation water using excitation state proton-electron
Move reactive ion source, it is characterised in that：The H3O+There is shading baffle at the ion outlet of generation cavity (2), avoid VUV
Light enters Proton-Transfer Reactions chamber (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710552505.2A CN107342210B (en) | 2017-07-07 | 2017-07-07 | Proton transfer reaction ion source for providing protonated water by utilizing excited proton electron cooperative transfer reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710552505.2A CN107342210B (en) | 2017-07-07 | 2017-07-07 | Proton transfer reaction ion source for providing protonated water by utilizing excited proton electron cooperative transfer reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107342210A true CN107342210A (en) | 2017-11-10 |
| CN107342210B CN107342210B (en) | 2024-01-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710552505.2A Active CN107342210B (en) | 2017-07-07 | 2017-07-07 | Proton transfer reaction ion source for providing protonated water by utilizing excited proton electron cooperative transfer reaction |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060284075A1 (en) * | 2005-02-28 | 2006-12-21 | Honeywell International Inc. | No-fragmentation micro mass spectrometer system |
| CN106024572A (en) * | 2016-07-22 | 2016-10-12 | 中国科学院合肥物质科学研究院 | Organic matter detection device and detection method of bipolar proton transfer reaction mass spectrometer |
| CN106158574A (en) * | 2015-04-09 | 2016-11-23 | 中国科学院生态环境研究中心 | Photoinduction ion source Proton transfer reaction mass spectrometry instrument |
| CN106373857A (en) * | 2016-10-28 | 2017-02-01 | 中国科学院生态环境研究中心 | Laser desorption ionization ion source assisted by protonated reinforcement matrix |
| CN207602515U (en) * | 2017-07-07 | 2018-07-10 | 中国科学院生态环境研究中心 | The Proton-Transfer Reactions ion source that protonation water is provided is reacted using excited state chemistry |
-
2017
- 2017-07-07 CN CN201710552505.2A patent/CN107342210B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060284075A1 (en) * | 2005-02-28 | 2006-12-21 | Honeywell International Inc. | No-fragmentation micro mass spectrometer system |
| CN106158574A (en) * | 2015-04-09 | 2016-11-23 | 中国科学院生态环境研究中心 | Photoinduction ion source Proton transfer reaction mass spectrometry instrument |
| CN106024572A (en) * | 2016-07-22 | 2016-10-12 | 中国科学院合肥物质科学研究院 | Organic matter detection device and detection method of bipolar proton transfer reaction mass spectrometer |
| CN106373857A (en) * | 2016-10-28 | 2017-02-01 | 中国科学院生态环境研究中心 | Laser desorption ionization ion source assisted by protonated reinforcement matrix |
| CN207602515U (en) * | 2017-07-07 | 2018-07-10 | 中国科学院生态环境研究中心 | The Proton-Transfer Reactions ion source that protonation water is provided is reacted using excited state chemistry |
Non-Patent Citations (1)
| Title |
|---|
| ZHEN LI 等: "Doping-assisted low-pressure photoionization mass spectrometry for the real-time detection of lung cancer-related volatile organic compounds" * |
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| CN107342210B (en) | 2024-01-26 |
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