CN201628700U - Time-of-flight mass spectrometer with wide dynamic range - Google Patents
Time-of-flight mass spectrometer with wide dynamic range Download PDFInfo
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- CN201628700U CN201628700U CN2010201338686U CN201020133868U CN201628700U CN 201628700 U CN201628700 U CN 201628700U CN 2010201338686 U CN2010201338686 U CN 2010201338686U CN 201020133868 U CN201020133868 U CN 201020133868U CN 201628700 U CN201628700 U CN 201628700U
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Abstract
The utility model provides a time-of-flight mass spectrometer with a wide dynamic range, which comprises an ion source, an ion extraction pulse electrode, an ion extraction lens, an orthogonal-injection time-of-flight mass spectrum analyzer, an ion selection repulsion electrode, an MCP ion detector, a high-speed data acquisition card and corresponding software. A method for broadening a detection concentration dynamic range realized by the spectrometer includes steps that pulse voltage with adjustable pulse amplitude, duty ratio and frequency, namely ion extraction pulse, is applied to the ion extraction pulse electrode; pulse voltage with adjustable delay, pulse width and amplitude, namely ion selection repulsion pulse, is applied to the ion selection repulsion electrode in the orthogonal-injection time-of-flight mass spectrum analyzer; and the ion extraction pulse and the ion selection repulsion pulse are applied asynchronously. The time-of-flight mass spectrometer with a wide dynamic range can increase the time-of-flight mass spectrum detection concentration dynamic range to more than six orders of magnitude, and can be applied to occasions that ingredients with larger differences in terms of concentrations of to-be-detected samples are required to be detected simultaneously.
Description
Technical field
The utility model relates to the analytical instrument detection technique, particularly a kind of time-of-flight mass spectrometer of wide dynamic range.
Background technology
Time of-flight mass spectrometer (time-of-flight mass spectrometer, TOFMS) according to different ions in a vacuum the size of flight time judge its mass-to-charge ratio, analysis speed is fast, and can carry out the detection of single electric charge.The dynamic range that time of-flight mass spectrometer is measured concentration is one of major parameter index of time of-flight mass spectrometer.In actual applications, because the component in the sample is very complicated, usually need measure some content difference simultaneously and surpass the above component of 6 orders of magnitude, yet because time of-flight mass spectrometer adopts the method for ion counting, for example use time-digital quantizer (time-to-digitalconverter, TDC) carry out data acquisition, and TDC is because the existence in dead time, can not be in same sense cycle, therefore measure two ions that mass-to-charge ratio is identical simultaneously, for the big component of concentration, as a plurality of ions (for example 2ns) when arriving detecting device simultaneously in the very short time, detecting device may think to have only an ion, and this just causes the error of very big measurement.How can obtain the information of a plurality of ions when detecting single ion again, be time-of-flight mass spectrometer major issue anxious to be solved.The present method of existing several raising ion detection efficient dynamic ranges all can increase the cost of instrument, increases the complexity of instrument.
The utility model content
The shortcoming that the purpose of this utility model is to overcome prior art provides a kind of simple in structure, realization convenience, lower-cost time-of-flight mass spectrometer with wide dynamic range with not enough.
The purpose of this utility model is achieved through the following technical solutions: a kind of time-of-flight mass spectrometer of wide dynamic range, comprise ion gun, ion is drawn pulsed electrode, the ion extraction lens, vertical introduction-type flying time mass spectrum analysis device, ion is selected the repulsion electrode, MCP (Microchannel Plate) ion detector, high-speed data acquisition card and corresponding software, described ion gun is arranged at the front end that ion is drawn pulsed electrode, described ion is drawn the front end that pulsed electrode is arranged at the ion extraction lens, the rear end of ion extraction lens is oppositely arranged with vertical introduction-type flying time mass spectrum analysis device, in vertical introduction-type flying time mass spectrum analysis device, ion is set and selects repulsion electrode and MCP ion detector, high-speed data acquisition card is used to gather ion detection signal, is arranged at the relative position of outlet with vertical introduction-type flying time mass spectrum analysis device intermediate ion passage.
Described ion gun can be any ion gun, comprises the electrospray ionization source under the electron bombardment ionization source that can produce ion continuously, chemical ionization source, glow discharge ion gun, the atmospheric pressure, or the ion gun of pulsed, as laser ionization source etc.
Described ion is drawn pulsed electrode, makes ion that ion gun produces obtain kinetic energy at this under to the electrode effect, and this has determined the kinetic energy size of ion to electrode institute making alive amplitude; Described ion is drawn pulsed electrode can be different to different ion gun forms.
Described ion extraction lens is conventional electrostatic lens.
Described vertical introduction-type flying time mass spectrum analysis device can be conventional vertical introduction-type flying time mass spectrum analysis device; Ion selects repulsion electrode and MCP ion detector to be arranged at wherein.
Described MCP ion detector is the ion detector that conventional biplate MCP forms.
Described high-speed data acquisition card be TDC or high speed analogue-to-digital converters (Analog-Digital Converter, ADC).
Utilize the method for the raising detectable concentration dynamic range that the time-of-flight mass spectrometer of above-mentioned wide dynamic range realizes to comprise the steps:
(1) draw at ion and apply pulse amplitude, the duty pulse voltage of frequency adjustable when on the pulsed electrode, promptly ion is drawn pulse.The size of pulse voltage amplitude has determined ion concentration kinetic energy, has also just determined at last to produce in the ion that detected by the MCP ion detector and the ion gun ratio of ion; Pulse duty factor determines two kinds of differences to draw the time scale that the kinetic energy pattern is applied, i.e. detection time of variable concentrations component ion, be used to regulate the dynamic range width of instrument; Pulsed frequency is adjustable continuously from 0.1Hz～1KHz.
(2) ion in vertical introduction-type flying time mass spectrum analysis device selects to apply on the repulsion electrode pulse voltage of delay, pulsewidth and adjustable amplitude value, and promptly ion is selected the repulsion pulse.When this pulse applies and the analyzer modulating pulse have certain delay, the delay of this pulse what and pulsewidth and amplitude size depend on the mass-to-charge ratio and the flying speed of the ion that required repulsion is removed.
(3) the described ion of step (1) is drawn the described ion of pulse and step (2) to select the repulsion pulse is asynchronous applying.
Described step (3) specifically can be:
When (3-1) the ion concentration scope difference that generates when while ionization was big, instrument was drawn the hocket detection of high and low density component ion of pulse duty factor according to ion.When being in detection low concentration group segregant pattern, draw at ion and to apply low level in the pulse, ion obtains lower kinetic energy, make ion flight path in the flying time mass spectrum analysis device all drop on the MCP ion detector just, at this moment, ion in the flying time mass spectrum analysis device is selected will apply pulse voltage on the repulsion electrode, and the repulsion of high concentration component ion selectivity is gone out the MCP ion detector.
(3-2) when being in detection high concentration component ion mode, draw at ion and to apply high level on the pulsed electrode, ion obtains higher kinetic energy, and the ion in the flying time mass spectrum analysis device is selected not apply pulse voltage on the repulsion electrode, make the flight path of ion in the flying time mass spectrum analysis device depart from the MCP ion detector, have only a certain proportion of ion to arrive the MCP ion detector and detected, prevent that MCP is saturated.This ion draws that pulse voltage amplitude is big more, and detected ion number percent is more little, and pulse duty factor is more little, and it is few more to detect high concentration component ion institute's time spent.
Time-of-flight mass spectrometer of this wide dynamic range and the method that improves the detectable concentration dynamic range thereof can be promoted to from 100% to 0.0001% with the time-of-flight mass spectrometer dynamic range 6 more than the order of magnitude, can be applied to each bigger component of concentration difference in the testing sample needs the occasion that detects simultaneously, as the detection of organic micro-pollutant in the atmosphere etc.
Action principle of the present utility model is: ion draws pulse and ion selection repulsion pulse is asynchronous applying.When detecting the low concentration group segregant, ion is drawn and is applied low level in the pulse, ion obtains lower kinetic energy, make ion flight path in the flying time mass spectrum analysis device all drop on the MCP ion detector just, at this moment, ion in the flying time mass spectrum analysis device is selected will apply pulse voltage on the repulsion electrode, and the repulsion of high concentration component ion selectivity is gone out the MCP ion detector.When detecting high concentration component ion, draw at ion and to apply high level on the pulsed electrode, ion obtains higher kinetic energy, and the ion in the flying time mass spectrum analysis device is selected not apply pulse voltage on the repulsion electrode, make the flight path of ion in the flying time mass spectrum analysis device depart from the MCP ion detector, have only a certain proportion of ion to arrive the MCP ion detector and detected, prevent that MCP is saturated.This ion draws that pulse voltage amplitude is big more, and detected ion number percent is more little, and pulse duty factor is more little, and it is few more to detect high concentration component ion institute's time spent.
The utility model has following advantage and effect with respect to prior art:
(1) to draw pulse amplitude according to ion adjustable continuously for ion concentration kinetic energy, as long as be the ratio that the scalable ion arrives the MCP ion detector by regulating ion concentration kinetic energy, adapts to the detection requirement of Different Dynamic scope.
(2) can draw pulse duty factor according to ion and realize continuous adjustable realization the detection time of different component ion.
(3) owing to regulate the parameter minimizing, MCP ion detector, anode and high-speed data acquisition card need not be made complicated multi-channel mode, have greatly reduced cost.
(4) reduced the quantity that big component ion finally arrives the MCP ion detector, avoided the generation of MCP ion detector state of saturation, prevented high-speed data acquisition card, as time-restriction in digital quantizer TDC dead time, improve the quantitative degree of accuracy of instrument.
Description of drawings
Fig. 1 is apparatus structure of the present utility model and schematic diagram.
Fig. 2 is pulse sequence figure.
Embodiment
Below in conjunction with embodiment and accompanying drawing the utility model is described in further detail, but embodiment of the present utility model is not limited thereto.
Embodiment
Fig. 1 shows principle of the present utility model and structure.As seen from Figure 1, this device comprises electron impact ion source, ion extraction lens, vertical introduction-type flying time mass spectrum analysis device three parts.
Described electron impact ion source comprises: bombardment electron beam 1, ion are drawn pulsed electrode 2, ion is drawn aperture plate 3 and formed.
Described ion extraction lens 5 is conventional electrostatic lens, and the ion 4 that electron impact ion source is produced is incorporated into vertical introduction-type flying time mass spectrum analysis device.
Described vertical introduction-type flying time mass spectrum analysis device is to add ion in the conventional vertical introduction-type flying time mass spectrum analysis device to select repulsion electrode 11.
Described vertical introduction-type flying time mass spectrum analysis device by: vertically introduce repulsion electrode 6, ion collector 7, accelerating region 8, field-free flight district 9, echo area 10, ion and select repulsion electrode 11 and MCP ion detector 13 to form.
Described ion is selected repulsion electrode 11 to be but not only can is two parallel poles.
The ion 4 that electron gun emitting electrons 1 bombarding gas molecule produces is drawn at ion under the effect of pulsed electrode 2 and is obtained certain kinetic energy, and is incorporated in the vertical introduction-type flying time mass spectrum analysis device by ion extraction lens 5 continuously.
In vertical introduction-type flying time mass spectrum analysis device, the vertical pulse voltage (frequency is generally greater than 10000 hertz) of introducing repulsion electrode 6 is introduced accelerating region 8 with ion and is picked up counting, ion enters field-free flight district 9 after quickening, and 10 reflections are detected by MCP ion detector 13 at last through the echo area.
When detecting the low concentration group timesharing, ion is as shown in Figure 2 drawn pulses low district 17, and ion is drawn 2 making alives of pulsed electrode makes ion all arrive MCP ion detector 13 just in the flight time, shown in Fig. 1 intermediate ion flight path 14.At this moment, make the MCP state that reaches capacity, need select to apply pulse voltage on the repulsion electrode 11, when high component ion arrives this electrode, be pushed and leave the right or normal track, absorbed by the instrument wall at ion in order to prevent high concentration component ion.
When detecting the high concentration component, ion is as shown in Figure 2 drawn pulse high level district 18, ion draws that institute's making alive will make all ions have higher horizontal kinetic energy on the pulsed electrode 2, its ion flight track is shown in the curve among Fig. 1 15, so that the ion that has only certain percentage arrives MCP ion detector 13 and is detected, and other ions are absorbed by the instrument wall.In this process, select repulsion electrode 11 not apply pulse voltage.
Concrete application example:
, be 60mg/m for example to the limit value that has toluene in the pollution source Air Pollutant Emission source now according to national discharge standard of air pollutants (GB16297-1996) regulation
3Be equivalent in the gas that with the air is background, to detect the small component of 14.6ppm.The concentration of component ratio difference 78%:14.6ppm of nitrogen and toluene reaches and is about 50000 times.That is: in per 50000 nitrogen molecules 1 toluene molecule is arranged.
We know from the standard electronic bombardment source fingerprint of toluene, and its characteristic peak mass-to-charge ratio is 91 and 92.At this situation, when needs detect the toluene gas of low concentration, can in the ion flight process, utilize ion to select repulsion electrode 11, mass-to-charge ratio all ions in 17～44 scopes are pushed away track.
When needs detect nitrogen, oxygen, argon gas, the contour concentration gases of carbon dioxide simultaneously, draw pulsed electrode 2 at ion and apply high voltage, dutycycle is about 1: 100, makes to have only part ion to arrive MCP ion detector 13, thereby has avoided the saturated of MCP ion detector 13.
The foregoing description is the utility model preferred implementation; but embodiment of the present utility model is not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present utility model and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within the protection domain of the present utility model.
Claims (8)
1. the time-of-flight mass spectrometer of a wide dynamic range, it is characterized in that: comprise ion gun, ion is drawn pulsed electrode, the ion extraction lens, vertical introduction-type flying time mass spectrum analysis device, ion is selected the repulsion electrode, the MCP ion detector, high-speed data acquisition card and corresponding software, described ion gun is arranged at the front end that ion is drawn pulsed electrode, described ion is drawn the front end that pulsed electrode is arranged at the ion extraction lens, the rear end of ion extraction lens is oppositely arranged with vertical introduction-type flying time mass spectrum analysis device, in vertical introduction-type flying time mass spectrum analysis device, ion is set and selects repulsion electrode and MCP ion detector, high-speed data acquisition card is used to gather ion detection signal, is arranged at the relative position of outlet with vertical introduction-type flying time mass spectrum analysis device intermediate ion passage.
2. the time-of-flight mass spectrometer of wide dynamic range according to claim 1, it is characterized in that: described ion gun comprises the electrospray ionization source under the electron bombardment ionization source that can produce ion continuously, chemical ionization source, glow discharge ion gun, the atmospheric pressure, or the ion gun of pulsed.
3. the time-of-flight mass spectrometer of wide dynamic range according to claim 2, it is characterized in that: the ion gun of described pulsed is a laser ionization source.
4. the time-of-flight mass spectrometer of wide dynamic range according to claim 1, it is characterized in that: described ion is drawn pulsed electrode, makes ion that ion gun produces obtain kinetic energy at this under to the electrode effect.
5. the time-of-flight mass spectrometer of wide dynamic range according to claim 1 is characterized in that: described ion extraction lens is conventional electrostatic lens.
6. the time-of-flight mass spectrometer of wide dynamic range according to claim 1 is characterized in that: described vertical introduction-type flying time mass spectrum analysis device is conventional vertical introduction-type flying time mass spectrum analysis device; Ion selects repulsion electrode and MCP ion detector to be arranged at wherein.
7. the time-of-flight mass spectrometer of wide dynamic range according to claim 1 is characterized in that: the ion detector that described MCP ion detector is formed for conventional biplate MCP.
8. the time-of-flight mass spectrometer of wide dynamic range according to claim 1, it is characterized in that: described high-speed data acquisition card is time-digital quantizer or high speed analogue-to-digital converters.
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| CN2010201338686U CN201628700U (en) | 2010-03-18 | 2010-03-18 | Time-of-flight mass spectrometer with wide dynamic range |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101789355A (en) * | 2010-03-18 | 2010-07-28 | 广州禾信分析仪器有限公司 | Time-of-flight mass spectrometer with wide dynamic range, implementation method and application thereof |
| CN102592937A (en) * | 2012-03-12 | 2012-07-18 | 复旦大学 | Quality analysis method based on restricted theory of relativity and mass spectroscope |
| CN105513936A (en) * | 2015-12-28 | 2016-04-20 | 广州智纯科学仪器有限公司 | Ion selection method and apparatus |
| CN107219214A (en) * | 2017-07-26 | 2017-09-29 | 大连理工大学 | A kind of spectrum combines the quantitative analysis device of element in mass spectrographic unknown sample |
| CN108664425A (en) * | 2018-05-14 | 2018-10-16 | 吉林大学 | A kind of data collecting system based on high speed analog-to-digital conversion and time-to-digital converter technology |
| CN109884159A (en) * | 2018-12-26 | 2019-06-14 | 宁波大学 | Mass spectrometric analysis method |
| CN110342455A (en) * | 2019-07-19 | 2019-10-18 | 北京卫星环境工程研究所 | A kind of minute yardstick time of-flight mass spectrometer |
| CN111223753A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Control method of ion mobility spectrometry-time-of-flight mass spectrometer |
| CN111613514A (en) * | 2020-06-24 | 2020-09-01 | 成都艾立本科技有限公司 | High-sensitivity ultraviolet light ionization time-of-flight mass spectrometer and ion time-of-flight measuring method |
-
2010
- 2010-03-18 CN CN2010201338686U patent/CN201628700U/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101789355B (en) * | 2010-03-18 | 2012-05-09 | 广州禾信分析仪器有限公司 | Time-of-flight mass spectrometer with wide dynamic range, implementation method and application thereof |
| CN101789355A (en) * | 2010-03-18 | 2010-07-28 | 广州禾信分析仪器有限公司 | Time-of-flight mass spectrometer with wide dynamic range, implementation method and application thereof |
| CN102592937A (en) * | 2012-03-12 | 2012-07-18 | 复旦大学 | Quality analysis method based on restricted theory of relativity and mass spectroscope |
| CN102592937B (en) * | 2012-03-12 | 2014-10-29 | 复旦大学 | Quality analysis method based on restricted theory of relativity and mass spectroscope |
| CN105513936A (en) * | 2015-12-28 | 2016-04-20 | 广州智纯科学仪器有限公司 | Ion selection method and apparatus |
| CN107219214B (en) * | 2017-07-26 | 2023-10-27 | 大连理工大学 | Quantitative analysis device for elements in unknown sample by spectrum combination with mass spectrum |
| CN107219214A (en) * | 2017-07-26 | 2017-09-29 | 大连理工大学 | A kind of spectrum combines the quantitative analysis device of element in mass spectrographic unknown sample |
| CN108664425A (en) * | 2018-05-14 | 2018-10-16 | 吉林大学 | A kind of data collecting system based on high speed analog-to-digital conversion and time-to-digital converter technology |
| CN111223753A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Control method of ion mobility spectrometry-time-of-flight mass spectrometer |
| CN109884159A (en) * | 2018-12-26 | 2019-06-14 | 宁波大学 | Mass spectrometric analysis method |
| CN110342455A (en) * | 2019-07-19 | 2019-10-18 | 北京卫星环境工程研究所 | A kind of minute yardstick time of-flight mass spectrometer |
| CN111613514A (en) * | 2020-06-24 | 2020-09-01 | 成都艾立本科技有限公司 | High-sensitivity ultraviolet light ionization time-of-flight mass spectrometer and ion time-of-flight measuring method |
| CN111613514B (en) * | 2020-06-24 | 2023-11-03 | 成都艾立本科技有限公司 | High-sensitivity ultraviolet ionization time-of-flight mass spectrometer and ion time-of-flight measurement method |
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| Date | Code | Title | Description |
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| C14 | Grant of patent or utility model | ||
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Granted publication date: 20101110 Effective date of abandoning: 20120509 |
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| AV01 | Patent right actively abandoned |
Granted publication date: 20101110 Effective date of abandoning: 20120509 |