CN106158574A - Photoinduction ion source Proton transfer reaction mass spectrometry instrument - Google Patents
Photoinduction ion source Proton transfer reaction mass spectrometry instrument Download PDFInfo
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- CN106158574A CN106158574A CN201510164486.7A CN201510164486A CN106158574A CN 106158574 A CN106158574 A CN 106158574A CN 201510164486 A CN201510164486 A CN 201510164486A CN 106158574 A CN106158574 A CN 106158574A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
- H01J49/0045—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction
- H01J49/0072—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction by ion/ion reaction, e.g. electron transfer dissociation, proton transfer dissociation
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- 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
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
- H01J49/162—Direct photo-ionisation, e.g. single photon or multi-photon ionisation
Abstract
The present invention relates to a kind of photoinduction ion source Proton transfer reaction mass spectrometry instrument, this is a kind of instrument that can be analyzed volatile organic matter and monitor continuously.It is by steam supply pipe (3), VOCs sample feeding pipe (5), vacuum-ultraviolet light light source chamber (2), H3O+Generation cavity (4), Proton-Transfer Reactions chamber (6), ion migration chamber (7) and reflective TOF mass analyzer (8) composition.Its steam supply pipe (3), vacuum-ultraviolet light light source chamber (2), H3O+Generation cavity (4) three part composition photoinduction ion source.The vacuum ultraviolet light produced by VUV radiant penetrates the photoelectron that metal electrode produces；Photoelectron produces H with steam effect after accelerating3O+；H3O+Produce Proton-Transfer Reactions with VOCs collision and generate VOCs ion；The VOCs ion generated is detected by reflective TOF mass analyzer (8).The Proton transfer reaction mass spectrometry instrument stray ion of this structure is few, stable, detection limits low, safety and environmental protection.
Description
Art
The present invention relates to a kind of photoinduction ion source Proton transfer reaction mass spectrometry instrument (PTR-MS), this is that one can be to volatilizable
The instrument that property Organic substance is analyzed and monitors continuously.
Background technology
Volatile organic matter (VOCs) participates in city photochemical fog and the generation of near-earth ozone, can pass through a series of air
Physics chemical action forms secondary organic aerosol, promotes the formation of gray haze, and the part (such as triphen) in them has been
The carcinogen generally acknowledged.Its harm is of increasing concern.In an atmosphere, the mean volume fraction of VOCs is 1 × 10-9(ppbv),
Content is the lowest, and its direct detection is existed certain difficulty.Additionally, vehicle exhaust, substance combustion, plant leaf blade are breathed, food
During the discharge VOCs such as product storage is rotten, human body respiration, the composition of VOCs and quantity all change comparatively fast, traditional from
Provision of on-line analysis methodology (gas chromatography/mass spectrometry method, high performance liquid chromatography/mass spectrography etc.) is because sensitivity is low, preprocessing process is the longest
It is difficult to fully it is monitored etc. reason.PTR-MS is the sensitiveest Organic substance on-line checking mass spectrograph, has measurement
Response time short (musec order), highly sensitive (1 × 10-12, V/V), without to sample gas pretreatment, excellent without calibration etc.
Gesture, is applied to monitoring and the monitoring of above VOCs release process of Atmospheric Trace VOCs.
PTR-MS mainly includes ion source and mass analyzer two parts.The development of PTR-MS is concentrated mainly on the former, the latter
There is no much changes.Business-like PTR-MS commonly uses hollow cathode discharge to form the hydrone (H of protonation3O+) ion source,
Owing to discharge process itself is a unstable process, 200-500V voltage is needed to excite and maintain electric discharge, under this voltage conditions
Discharge process can produce a lot of foreign ion, the vertical electric field of hollow cathode discharge also can cause H in addition3O+Certain loss.
2000, electron impact ionization source was introduced PTR-MS by De Gouw etc., but still the problem of a large amount of stray ion of unresolved generation.
2003, Hanson etc. reported a kind of employing alpha radiator241Am radiation produces H3O+PTR-MS, with radiation
Property ionization source produce H3O+The pollution that ion stream is stably not required to extra electric current and heteroion is little, but answering due to radioactive substance
Potential safety hazard is there is with making this mass spectrum.2006, Inomata etc. reported a kind of plane electrode direct-current discharge to form H3O+'s
PTR-MS, direct-current discharge is possible to prevent the interfering ion produced due to the backflow of analyte, but the H produced because of it3O+Ion
Flow ratio hollow cathode discharge order of magnitude lower and make the sensitivity of PTR-MS decrease.2011, Chinese invention patent Shen
Please disclose a kind of microwave discharge ionization source and a kind of based on this ionization source by prospectus CN201110020412.8
PTR-MS, but also need higher voltage excite and maintain due to microwave discharge, the problem therefore equally existing stray ion.In a word,
Ionization source produces H3O+The instability of stream can cause the instability of PTR-MS sensitivity, and foreign ion can make instrument detection limit uprise,
There is potential safety hazard and the operator of instrument be compromised in ionization source.
Summary of the invention
For sensitive stably detection trace volatile organic matter, the present invention provides a kind of photoinduction ion source Proton-Transfer Reactions
Mass spectrograph (PIE-PTR-MS), it uses photoelectron to excite water vapour to produce the hydrone (H of protonation3O+), be allowed to can
Volatile organic matter molecular collision produces Proton-Transfer Reactions and generates volatile organic matter ion, then passes through the flight time
(TOF) mass analyzer detects volatile organic matter ion.Photoinduction ion source foreign ion is few, safety and environmental protection；With
Time, this photoinduction ion source PTR-MS additionally uses multilevel voltage ion mobility technology and reflective measuring ion technology, makes instrument
Device is highly sensitive and stable.
The vacuum ultraviolet light that patent of the present invention the technical scheme is that 1, produced by VUV radiant is penetrated metal electrode and is produced
Third contact of a total solar or lunar eclipse electronics；2, H is produced with steam effect after photoelectron accelerates3O+；3、H3O+Anti-with VOCs collision generation proton translocation
VOCs ion should be generated；4, the VOCs ion generated is detected by flight time (TOF) mass analyzer.
The useful benefit of the present invention is, uses photoinduction ion source to make the H of formation3O+Ion source is more stable, stray ion is less,
Safer, in conjunction with multilevel voltage ion mobility technology and reflective measuring ion technology, the sensitivity of instrument is higher.
Accompanying drawing explanation
Fig. 1 is the outside drawing of present configuration, respectively 1, molecular pump, 2, vacuum-ultraviolet light light source chamber, 3, steam supplies
Give pipe, 4, H3O+Generation cavity, 5, VOCs sample feeding pipe, 6, Proton-Transfer Reactions chamber, 7, ion migration chamber, 8, reflective
TOF mass analyzer.
Fig. 2 is the sectional structural map of the present invention, and critical piece has: 9, vacuum UV lamp, 10, Afluon (Asta) window, 11, from
Sub-reflecting mirror, 12, photoelectron generate and accelerate electrode, 13, Proton-Transfer Reactions control electrode, 14, polybasic ion migrates thoroughly
Mirror, 15, the ion extraction and accelerate electrode, 16, micro-channel plate detector.
Detailed description of the invention
The main part of photoinduction ionization source PTR-MS is by vacuum-ultraviolet light light source chamber 2, steam supply pipe 3, H3O+Occur
Chamber 4, VOCs sample feeding pipe 5, Proton-Transfer Reactions chamber 6, ion migration chamber 7 and reflective TOF mass analyzer 8 seven part
Constitute.First three part combines and forms photoinduction ion source.Detailed description of the invention is:
One, steam is fed directly into H by stainless steel water steam supply pipe 33O+Generation cavity 4, its flow is by noticeable degree；
Two, in vacuum-ultraviolet light source chamber 2, after the vacuum ultraviolet photon of 10.5eV is produced by vacuum UV lamp 9, perfluorinated magnesium
Window 10 enters H3O+Generation cavity 4, vacuum ultraviolet light is penetrated metal electrode and is produced photoelectron, after photoelectron is accelerated electrode acceleration
Clash into the water vapour supplied by steam supply pipe 2 and form H3O+；It is added in the sub-driving electric field of low-voltage optical and life accelerated on electrode
The H become3O+The direction of motion is consistent, makes the H of generation3O+Proton-Transfer Reactions chamber 6 is entered after Bei Jiasu.
Three, the H entered3O+Specific translational speed is obtained under Proton-Transfer Reactions controls the electric field controls that electrode 13 produces,
And collide with the VOCs being entered Proton-Transfer Reactions chamber 6 by sample feeding pipe 5, generate corresponding VOCs through Proton-Transfer Reactions
Ion, VOCs is atmospheric pressure direct injected, and its flow is regulated by needle-valve；
Four, VOCs ion enters ion migration chamber 7 after Proton-Transfer Reactions controls the electric field controls that electrode 13 produces；
Five, ion migration chamber 7 migrates lens 14 (being made up of ion focusing lenses and multiple acceleration electrode) built with polybasic ion,
VOCs ion migrates lens 14 through polybasic ion and is focused into thin ion stream, and is accelerated；
Six, the VOCs ion mass analyzed device entrance after accelerating enters reflective TOF mass analyzer 8.At reflective TOF
In mass analyzer 8, VOCs ion is successively via the effect flight one of the ion extraction and acceleration electrode 15 and ion mirror 11
The path of individual V-type, is then captured by micro-channel plate detector 16.Different according to ion mass-to-charge ratio difference then flight speed, arrive
Reach the detector time also i.e. obtains the mass spectrum of VOCs with regard to different principles.
Claims (8)
1. photoinduction ion source Proton transfer reaction mass spectrometry instrument is by steam supply pipe (3), VOCs sample feeding pipe (5), vacuum-ultraviolet light
Light source chamber (2), H3O+Generation cavity (4), Proton-Transfer Reactions chamber (6), ion migration chamber (7) and reflective TOF mass
Analyzer (8) forms, it is characterised in that by steam supply pipe (3), vacuum-ultraviolet light light source chamber (2), H3O+Generation cavity (4)
Three part composition photoinduction ion sources.
Photoinduction ion source Proton transfer reaction mass spectrometry instrument the most according to claim 1, it is characterised in that: described vacuum-ultraviolet light
Light source chamber (2), H3O+Generation cavity (4), Proton-Transfer Reactions chamber (6), ion migration chamber 7) and reflective TOF mass divide
Parser (8) is sequentially connected and connects, and on the same axis.
Photoinduction ion source Proton transfer reaction mass spectrometry instrument the most according to claim 1, it is characterised in that: described vacuum-ultraviolet light
Light source chamber (2) and H3O+It is connected by Afluon (Asta) window (10) between generation cavity (4), H3O+Generation cavity (4) and below two
Individual chamber and reflective TOF mass analyzer (8) are connected by the aperture coaxial with Afluon (Asta) window the most successively.
Photoinduction ion source Proton transfer reaction mass spectrometry instrument the most according to claim 1, it is characterised in that: described H3O+Occur
Chamber (4) and Proton-Transfer Reactions chamber (6) are respectively provided with steam supply pipe and sample feeding pipe, and direction is vertical with ion migration direction.
Photoinduction ion source Proton transfer reaction mass spectrometry instrument the most according to claim 1, it is characterised in that: described H3O+Occur
It is respectively connected with on chamber (4), Proton-Transfer Reactions chamber (6), ion migration chamber (7) and reflective TOF mass analyzer (8)
Molecular pump.
Photoinduction ion source Proton transfer reaction mass spectrometry instrument the most according to claim 1, it is characterised in that: by described VUV
The vacuum-ultraviolet light incidence H that vacuum UV lamp (9) in radiant room (2) produces3O+Generation cavity (4), vacuum-ultraviolet light with
Metal electrode effect produces photoelectron, the steam effect supplied with steam supply pipe (3) after the accelerated electric field acceleration of photoelectron
Produce H3O+, the installation direction of ultra-violet lamp (9) and H3O+Heading consistent.
Photoinduction ion source Proton transfer reaction mass spectrometry instrument the most according to claim 1, it is characterised in that: described ion migration chamber
(7) polybasic ion is set in and migrates lens.
Photoinduction ion source Proton transfer reaction mass spectrometry instrument the most according to claim 1, it is characterised in that: described steam is for (3)
The pressure giving pipe and VOCs sample feeding pipe (5) is adjustable.
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| CN201510164486.7A CN106158574A (en) | 2015-04-09 | 2015-04-09 | Photoinduction ion source Proton transfer reaction mass spectrometry instrument |
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| CN201510164486.7A CN106158574A (en) | 2015-04-09 | 2015-04-09 | Photoinduction ion source Proton transfer reaction mass spectrometry instrument |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195529A (en) * | 2017-07-07 | 2017-09-22 | 中国科学院生态环境研究中心 | A kind of ioning method and its device based on excitation state proton-electron collaboration transfer reaction |
| CN107342210A (en) * | 2017-07-07 | 2017-11-10 | 中国科学院生态环境研究中心 | The Proton-Transfer Reactions ion gun of protonation water is provided using excitation state proton-electron collaboration transfer reaction |
| CN107478711A (en) * | 2017-09-30 | 2017-12-15 | 中国科学院生态环境研究中心 | Dichloromethane induction low pressure protonation ionized aerosol mass spectrometer |
| CN108051496A (en) * | 2017-12-11 | 2018-05-18 | 中国科学院生态环境研究中心 | The method detected in real time using Excited state proton trans fer mass spectrograph progress water body Taste and odor compounds |
| CN108257846A (en) * | 2016-12-29 | 2018-07-06 | 萨默费尼根有限公司 | For the method for mass spectrographic ultraviolet light induced dissociation |
| CN109841486A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of ionic migration spectrometer |
| CN110431411A (en) * | 2017-01-31 | 2019-11-08 | 史密斯探测-沃特福特有限公司 | Method and apparatus |
| CN111640646A (en) * | 2020-06-15 | 2020-09-08 | 成都艾立本科技有限公司 | High-sensitivity proton transfer time-of-flight mass spectrometer and method for measuring ion time-of-flight by using same |
| CN112020760A (en) * | 2018-09-28 | 2020-12-01 | 爱奥尼肯分析股份有限公司 | IMR-MS device |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108257846A (en) * | 2016-12-29 | 2018-07-06 | 萨默费尼根有限公司 | For the method for mass spectrographic ultraviolet light induced dissociation |
| US10276357B2 (en) | 2016-12-29 | 2019-04-30 | Thermo Finnigan Llc | Methods of ultraviolet photodissociation for mass spectrometry |
| CN108257846B (en) * | 2016-12-29 | 2019-12-03 | 萨默费尼根有限公司 | For the method for mass spectrographic ultraviolet light induced dissociation |
| CN110431411A (en) * | 2017-01-31 | 2019-11-08 | 史密斯探测-沃特福特有限公司 | Method and apparatus |
| CN107195529B (en) * | 2017-07-07 | 2024-01-26 | 中国科学院生态环境研究中心 | Ionization method and device based on excited proton electron cooperative transfer reaction |
| CN107342210A (en) * | 2017-07-07 | 2017-11-10 | 中国科学院生态环境研究中心 | The Proton-Transfer Reactions ion gun of protonation water is provided using excitation state proton-electron collaboration transfer reaction |
| CN107195529A (en) * | 2017-07-07 | 2017-09-22 | 中国科学院生态环境研究中心 | A kind of ioning method and its device based on excitation state proton-electron collaboration transfer reaction |
| CN107342210B (en) * | 2017-07-07 | 2024-01-26 | 中国科学院生态环境研究中心 | Proton transfer reaction ion source for providing protonated water by utilizing excited proton electron cooperative transfer reaction |
| CN107478711A (en) * | 2017-09-30 | 2017-12-15 | 中国科学院生态环境研究中心 | Dichloromethane induction low pressure protonation ionized aerosol mass spectrometer |
| CN109841486A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of ionic migration spectrometer |
| CN108051496A (en) * | 2017-12-11 | 2018-05-18 | 中国科学院生态环境研究中心 | The method detected in real time using Excited state proton trans fer mass spectrograph progress water body Taste and odor compounds |
| CN112020760A (en) * | 2018-09-28 | 2020-12-01 | 爱奥尼肯分析股份有限公司 | IMR-MS device |
| CN111640646A (en) * | 2020-06-15 | 2020-09-08 | 成都艾立本科技有限公司 | High-sensitivity proton transfer time-of-flight mass spectrometer and method for measuring ion time-of-flight by using same |
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