CN112151352B - Mass spectrum sample injection ionization device and working method thereof - Google Patents
Mass spectrum sample injection ionization device and working method thereof Download PDFInfo
- Publication number
- CN112151352B CN112151352B CN202011013024.2A CN202011013024A CN112151352B CN 112151352 B CN112151352 B CN 112151352B CN 202011013024 A CN202011013024 A CN 202011013024A CN 112151352 B CN112151352 B CN 112151352B
- Authority
- CN
- China
- Prior art keywords
- metal layer
- inner cylinder
- electric field
- inert metal
- inert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007924 injection Substances 0.000 title claims abstract description 41
- 238000002347 injection Methods 0.000 title claims abstract description 41
- 238000001819 mass spectrum Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 146
- 229910052751 metal Inorganic materials 0.000 claims abstract description 146
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 239000004065 semiconductor Substances 0.000 claims abstract description 49
- 238000005192 partition Methods 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000007789 sealing Methods 0.000 claims abstract description 15
- 230000005684 electric field Effects 0.000 claims description 74
- 150000002500 ions Chemical class 0.000 claims description 43
- 230000009471 action Effects 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 24
- 238000004949 mass spectrometry Methods 0.000 claims description 17
- 238000004458 analytical method Methods 0.000 claims description 16
- 238000005036 potential barrier Methods 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 10
- 230000002093 peripheral effect Effects 0.000 claims description 8
- 239000002923 metal particle Substances 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 7
- 238000005273 aeration Methods 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 9
- 239000012491 analyte Substances 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000284 extract Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 24
- 239000012159 carrier gas Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000000065 atmospheric pressure chemical ionisation Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/68—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
-
- 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
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
- H01J49/147—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers with electrons, e.g. electron impact ionisation, electron attachment
Abstract
The invention relates to a mass spectrum sample injection ionization device and a working method thereof. The device comprises an inner cylinder and an outer cylinder which are coaxially arranged. The inner cylinder comprises a hollow conductive tube, a sealing plate for sealing an opening at one end of the conductive tube, a first conical opening arranged at the opening at the other end of the conductive tube and a heating resistance wire arranged on the inner wall of the conductive tube. The outer cylinder comprises a hollow shell, a plurality of partition electrodes which are sequentially arranged on the inner wall of the shell in parallel, a second conical opening which is arranged at the opening at one end of the shell, and a focusing assembly which is arranged at the opening at the other end of the shell. The partition electrode comprises a metal substrate, a semiconductor layer and an inert metal layer which are sequentially arranged. The invention can realize the direct ionization of the sample in the atmospheric pressure environment, does not need reagents or consumable materials, directly extracts the analyte from the environmental sample, and sends the sample into the vacuum environment of the mass spectrum after ionization, so that the ionization can be completed while the mass spectrum is sampled, and the material structure damage caused by the pressure condition change can be avoided.
Description
Technical Field
The invention relates to the technical field of mass spectrometry, in particular to a mass spectrometry sample injection ionization device and a working method thereof.
Background
Mass spectrometry is a device for analyzing the composition of matter and its content. Typically, mass spectrometry equipment contains four main parts of a sample injection system, an ionization source, an analyzer, and a detector. Mass spectrometry in the analysis of volatile organic compounds or certain gaseous substances, it is necessary to introduce the gaseous substances from an external atmospheric pressure environment into a vacuum environment inside the mass spectrum for analysis. During transport of these analytes into the vacuum environment at the original location, the structure may have been broken down due to changes in air pressure. In addition, the existing common electron ionization source can only work in a vacuum environment, so that substances cannot be directly ionized at an original position, and the partial ionization technology realizes ionization under the atmospheric pressure, but all the auxiliary materials of a substrate or a sample are needed.
Mass spectrometry analyzes charged materials by constructing a special electromagnetic field in a vacuum environment, and the object to be measured needs to undergo two steps: 1. introducing a substance from an external atmospheric pressure environment into an internal vacuum environment, and electrifying an object to be tested. Common ionization sampling methods include atmospheric pressure chemical ionization source (APCI), desorption Electrospray (DESI), matrix assisted desorption ionization source (MALDI), and the like. The atmospheric pressure chemical ionization source firstly ionizes reagents such as acetone, and electrons are transferred to a sample through reagent ions to complete the ionization process. The desorption point sprays, and by spraying out tiny droplets of the charged reagent, the charged droplets strike the surface of the object to be detected, so that the substance on the surface of the object to be detected is separated and ionized. The matrix auxiliary ionization source is to mix the object to be detected with the matrix, irradiate the surface of the mixed matrix by laser, and separate and ionize the object to be detected from the matrix under the assistance of the matrix. The existing mass spectrum atmospheric pressure sample injection ionization technology needs auxiliary reagent participation, and complicated sample treatment and reagent proportioning work are needed before ionization.
The solid metal contains a large amount of electrons, but since the energy of these electrons is lower than the potential barrier of the solid surface, there is no way for electrons to escape the surface of the metal solid in a general state. The electrons want to break through the solid surface, there are three methods: 1. through external input, electrons acquire enough high energy so as to escape from the solid surface; 2. by lowering the potential barrier of the solid surface, electrons are allowed to escape beyond the potential barrier to the solid surface; 3. at the same time, the ionization energy is increased and the barrier of the solid surface is lowered, so that electrons can escape. External electron donating input energy modes comprise electron energy increase by photon energy transfer to electrons; increasing electron energy by increasing temperature; electrons or ions with certain energy are bombarded on the solid surface, and the energy is transferred to the electrons, etc. The method for lowering the potential barrier of the solid surface generally applies a certain electric field to the solid, under the action of the electric field, the square potential barrier with infinite width on the solid surface gradually tends to the triangular potential barrier, and the height of the potential barrier gradually becomes lower and the width gradually becomes narrower along with the increase of the electric field. When the barrier width is reduced to be comparable to the electron wavelength in the metal, tunneling occurs, allowing electrons to escape the metal surface across the barrier.
Disclosure of Invention
The invention aims to provide a mass spectrum sample introduction ionization device and a working method thereof, wherein the mass spectrum sample introduction ionization device can realize direct ionization of a sample in an atmospheric pressure environment, reagents and consumables are not needed, analytes are directly extracted from the environmental sample, and the samples are sent into a vacuum environment of a mass spectrum after ionization, so that ionization can be completed while mass spectrum sample introduction is performed, and material structural damage caused by pressure condition change can be avoided.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a mass spectrum sample injection ionization device comprises an inner cylinder and an outer cylinder which are coaxially arranged.
The inner cylinder comprises a hollow conductive torch, a sealing plate for sealing an opening at one end of the conductive cylinder, a first conical opening arranged at the opening at the other end of the conductive cylinder and a heating resistance wire arranged on the inner wall of the conductive cylinder.
The outer cylinder comprises a hollow shell, a plurality of partition electrodes, a second conical opening and a focusing assembly, wherein the partition electrodes are sequentially arranged on the inner wall of the shell in parallel; the partition electrode comprises a metal substrate, a semiconductor layer and an inert metal layer which are sequentially arranged.
Further, one end of the conductive cylinder provided with the sealing plate is provided with a ventilation catheter communicated with the inner cavity of the conductive cylinder; the shell is provided with a gas pipe hole; the airway tube extends outwardly from the tracheal opening and is sealed between the airway tube and the tracheal opening.
Further, the focusing assembly comprises an insulating ring arranged at the opening at the other end of the shell, a focusing electrode arranged on the inner peripheral wall of the insulating ring and a focusing filter cone arranged on the outer side of the insulating ring; the width of the focusing electrode is smaller than that of the insulating ring; the focusing filter cone is provided with a rear end outlet; the focusing electrode, the focusing filter cone, the inner cylinder and the outer cylinder are coaxially arranged.
Furthermore, the first conical opening and the second conical opening are both in a truncated cone shape, and the diameters of the first conical opening and the second conical opening gradually decrease from inside to outside.
Further, the heating resistance wire is spiral, and the heating resistance wire is tightly attached to the inner wall of the inner cylinder.
Further, slits are arranged between adjacent partition electrodes; the metal substrate is arranged on the inner wall of the outer cylinder, the semiconductor layer is plated on the inner wall of the metal substrate, and the inert metal layer is arranged on the inner wall of the semiconductor layer; the semiconductor layer is a semiconductor layer containing nano metal particles.
Further, the inner cylinder is arranged in the outer cylinder through the supporting ring; the outer end of the first conical opening of the inner cylinder extends out of the second conical opening of the outer cylinder, and a sample injection gap is arranged between the outer peripheral wall of the outer end of the first conical opening and the inner peripheral wall of the outer end of the conical opening; a gap is reserved between the sealing plate of the inner cylinder and the insulating ring.
Further, the ventilation duct is connected with an air pump.
Further, the device also comprises a substrate voltage dividing circuit and an inert layer voltage dividing circuit; the substrate voltage dividing circuit comprises a plurality of substrate voltage dividing resistors which are sequentially connected in series between a power supply and ground; the inert layer voltage dividing circuit comprises a plurality of inert layer voltage dividing resistors which are sequentially connected in series between a power supply and the ground; the metal substrate of each partition electrode is connected to different potential points of the substrate voltage dividing circuit through a wire, the focusing electrode is connected with the last stage of the substrate voltage dividing circuit through a wire, and the voltage of the metal substrate of each partition electrode and the voltage of the focusing electrode between the second conical opening and the insulating ring are gradually reduced; the inert metal layers of the partition electrodes are respectively connected to different potential points of the inert layer voltage dividing circuit through a lead, and the potential of the inner cylinder is the same as that of the inert metal layer of the last stage; on the same segmented electrode, the voltage of the metal substrate is higher than that of the inert metal layer.
The invention also relates to a working method of the mass spectrum sample injection ionization device, which comprises the following steps:
(1) Sample injection ionization of gaseous and volatile substances
The air pump is not required to be started, and under the low pressure effect of analysis equipment connected with the rear end outlet, an object to be detected enters the area between the inner cylinder and the outer cylinder from the sample injection gap; the object to be detected is a gas molecule.
After the voltage of the substrate voltage division circuit and the inert layer voltage division circuit is set, as the voltage of the metal substrate is higher than the voltage of the inert metal layer, a gradient electric field is formed in the semiconductor layer, and electrons in the semiconductor layer are accelerated by the gradient electric field and enter the inert metal layer from the semiconductor layer; meanwhile, as the potential barrier on the surface of the inert metal layer is reduced due to the voltage applied on the inert metal layer, electrons can escape from the inert metal layer and enter the area between the inner cylinder and the outer cylinder; when the gas molecules entering between the inner cylinder and the outer cylinder encounter electrons escaping from the inert metal layer, the gas molecules interact with the electrons, and the outermost layer electrons of the gas molecules are lost to become positively charged ions.
In the axial direction of the inner cylinder and the outer cylinder, the gradually reduced potential of the inert metal layer forms a gradient electric field, and the gradient electric field is an axial electric field; under the action of the airflow and the gradient electric field, the object to be detected gradually moves to the outlet at the rear end; in the radial direction, the inner cylinder and the inert metal layer are both positive potentials to form a radial electric field, and an object to be detected can be simultaneously repelled by the inner cylinder and the inert metal layer and is gathered in an annular space formed by the inert metal layer and the inner cylinder to form a focusing effect; under the combined action of the radial electric field and the axial electric field, ions of an object to be detected gradually move from a sample injection gap to a rear end outlet, when the ions reach the vicinity of a focusing electrode, the ions are focused on a central axis, and then are discharged from the rear end outlet under the action of the electric field and the air flow and enter analysis equipment.
(2) Sample injection ionization of difficult volatile substances
The air pump pumps air into the inner cylinder, and the air is heated under the action of the heating resistance wire and is sprayed out from the first conical opening; after the heated gas is purged to the surface of the to-be-tested object which is difficult to volatilize, part of the substances are changed into gaseous state under the action of air flow and temperature to fall off from the surface of the to-be-tested object, and then are sucked into the area between the inner cylinder and the outer cylinder from the sample injection gap.
After the voltage of the substrate voltage division circuit and the inert layer voltage division circuit is set, as the voltage of the metal substrate is higher than the voltage of the inert metal layer, a gradient electric field is formed in the semiconductor layer, and electrons in the semiconductor layer are accelerated by the gradient electric field and enter the inert metal layer from the semiconductor layer; meanwhile, as the potential barrier on the surface of the inert metal layer is reduced due to the voltage applied on the inert metal layer, electrons can escape from the inert metal layer and enter the area between the inner cylinder and the outer cylinder; when the gas molecules entering between the inner cylinder and the outer cylinder encounter electrons escaping from the inert metal layer, the gas molecules interact with the electrons, and the outermost layer electrons of the gas molecules are lost to become positively charged ions.
In the axial direction of the inner cylinder and the outer cylinder, the gradually reduced potential of the inert metal layer forms a gradient electric field, and the gradient electric field is an axial electric field; under the action of the airflow and the gradient electric field, the object to be detected gradually moves to the outlet at the rear end; in the radial direction, the inner cylinder and the inert metal layer are both positive potentials to form a radial electric field, and an object to be detected can be simultaneously repelled by the inner cylinder and the inert metal layer and is gathered in an annular space formed by the inert metal layer and the inner cylinder to form a focusing effect; under the combined action of the radial electric field and the axial electric field, ions of an object to be detected gradually move from a sample injection gap to a rear end outlet, when the ions reach the vicinity of a focusing electrode, the ions are focused on a central axis, and then are discharged from the rear end outlet under the action of the electric field and the air flow and enter analysis equipment.
According to the technical scheme, the method can realize direct ionization of the sample in the atmospheric pressure environment, reagents and consumables are not needed, the analyte is directly extracted from the environmental sample, and the sample is sent into a vacuum environment of a mass spectrum after ionization, so that ionization can be completed while mass spectrum sample injection, and material structural damage caused by pressure condition change can be avoided. The invention can be used for mass spectrometry of volatile organic compounds and gaseous samples and simultaneous sample injection and ionization.
Drawings
FIG. 1 is a schematic diagram of the operation of the present invention;
FIG. 2 is a cross-sectional view of a mass spectrometry ionization device of the present invention;
FIG. 3 is a schematic structural view of the inner barrel;
FIG. 4 is a schematic structural view of the outer tub;
FIG. 5 is a schematic view of the structure of the outer barrel focus electrode;
FIG. 6 is a schematic view of the structure of the outer barrel partition electrode;
FIG. 7 is a schematic diagram II of the structure of the outer barrel partition electrode;
fig. 8 is an enlarged view of a portion a in fig. 7.
Wherein:
11. the device comprises a first conical port, 12, a conductive torch, 13, a heating resistance wire, 14, an air duct, 21, a shell, 22, a second conical port, 23, an insulating ring, 24, a rear end outlet, 25, a focusing filter cone, 26, an air pipe hole, 31, a focusing electrode, 41, a partition electrode, 42, a metal substrate, 43, a semiconductor layer, 44, an inert metal layer, 51, an inner cylinder, 52, an outer cylinder, 53, a support ring, 54, a sample injection slot, 61, an air pump, 62, a substrate voltage dividing resistor, 62, an analysis device, 63, an inert layer voltage dividing resistor, 64 and a substrate voltage dividing resistor.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
the mass spectrum sample injection ionization device as shown in fig. 1-8 comprises an inner cylinder 51 and an outer cylinder 52 which are coaxially arranged. The inner cylinder has the functions of a carrier gas channel and an electrode, and the inner wall of the outer cylinder is provided with a partition electrode to form an ion source.
As shown in fig. 3, the inner cylinder 51 includes a hollow conductive cylinder 12, a sealing plate for sealing an opening at one end of the conductive cylinder 12, a first conical opening 11 provided at the opening at the other end of the conductive cylinder 12, and a heating resistance wire 13 provided on the inner wall of the conductive cylinder 12. The conductive torch 12, the sealing plate and the first conical opening 11 are all made of conductive metal materials, and the conductive metal materials are any one of conductive metals such as copper, stainless steel, nickel, iron and the like. As shown in fig. 3, the heating resistance wire 13 is spiral, and the heating resistance wire 13 is closely attached to the inner wall of the inner cylinder 51, so as to improve heat exchange performance.
As shown in fig. 4, the outer cylinder 52 includes a hollow housing 21, a plurality of partition electrodes 41 arranged in parallel in this order on the inner wall of the housing 21, a second conical opening 22 mounted at an opening at one end of the housing 21, and a focusing assembly mounted at an opening at the other end of the housing 21. The housing 21 is made of a non-conductive material with good insulation properties, such as polytetrafluoroethylene, polyethylene, glass, ceramic, etc.
As shown in fig. 1-4, the end of the conductive cylinder 12 provided with the sealing plate is provided with an aeration conduit 14 communicated with the inner cavity of the conductive cylinder 12; the shell 21 is provided with an air pipe hole 26; the airway tube 14 extends outwardly from the tracheal hole 26 and seals between the airway tube 14 and the tracheal hole 26. The conductive torch is made of a material with good electric conductivity and heat transfer performance. The ventilation duct 14 is communicated with the inner cylinder 51, and when the substances difficult to volatilize are measured, the ventilation duct 14 is externally connected with the air pump 61, air is fed into the inner cylinder 51, the air in the inner cylinder 51 is heated and discharged from the first conical opening 11, and the air is blown to the surface of the substances to be measured to assist the gasification of the substances difficult to volatilize.
As shown in fig. 4 and 5, the focusing assembly includes an insulating ring 23 installed at an opening at the other end of the housing 21, a focusing electrode 31 installed on an inner circumferential wall of the insulating ring 23, and a focusing filter cone 25 installed at an outer side of the insulating ring 23. The width of the focusing electrode 31 is smaller than that of the insulating ring 23, so that distortion of a focusing electric field caused by electrical connection between the focusing electrode 31 and the partition electrode 41 due to sample pollution, water vapor and the like can be prevented, and the focusing effect is prevented from being influenced. The focusing filter cone 25 is provided with a rear end outlet 24; the focusing electrode 31, the focusing filter cone 25, the inner cylinder 51, and the outer cylinder 52 are coaxially arranged.
Specifically, the insulating ring 23 separates the focus filter cone 25 from the housing 21 to form physical isolation, and prevents the partition electrode 41 mounted on the inner wall of the housing 21 from being electrically connected to the focus filter cone 25 due to contamination of the analysis sample, moisture, or the like, to damage the shape of an electric field or to cause safety accidents such as leakage. The focusing electrode 31 is positioned at the rear end of the partition electrode 41, the focusing electrode 31 is connected with positive potential, the whole surface forms an equipotential surface, and a gradient potential pointing to the axle center from the electrode surface is formed. Ions are collected in an annular space formed by the front end inert metal layer and the inner cylinder 51, and after reaching the focusing electrode 31, the ions in the annular space are further compressed to the vicinity of the axis to form a dot ion cluster, and then discharged from the rear end outlet 24. The ions further focused by the focusing electrode 31 have a process of moving from the surrounding space to the axis, so that after the ions are further focused, the ions are distributed in the space near the axis, but the radial velocity is not 0, and after leaving the focusing electrode 31, the ions may diverge again, and the focusing filter cone 25 filters out the ions with a larger radial initial velocity near the axis by providing a rear end outlet 24, so as to ensure that the ions can still be distributed in a more compact space after being discharged from the ionization source. To improve the resolution of the mass spectrometry apparatus.
As shown in fig. 1-4, the first conical opening 11 and the second conical opening 22 are both in a truncated cone shape, and the diameters of the two conical openings gradually decrease from inside to outside. The first conical opening 11 is connected with the inner cylinder 51, and the inner cylinder 51 has a wider ion channel, so that the carrier gas flow speed is low under the same flow condition, and the carrier gas can be fully heated by the heating resistance wire 13. When the heated carrier gas is ejected from the tapered outlet, a high-temperature, high-speed carrier gas purge should be used in order to change the difficult-to-volatilize substance into a gaseous state. By reducing the diameter and changing the airway cross-section, the carrier gas passing through the first conical orifice 11 is accelerated to exit at the same flow rate. The second conical opening 22 is connected with the outer cylinder 52, the second conical opening 22 and the first conical opening 11 form a slit, the cross section area of the air channel is smaller due to the existence of the slit, so that the gaseous analyte can be pumped into the ionization source faster under the same air inlet flow rate, and after entering the ionization source, the outer cylinder 52 and the inner cylinder 51 form an air flow channel with larger cross section area again to reduce the air flow speed, so that the air flow can be fully ionized.
As shown in fig. 6-8, the partition electrodes 41 are annular, the partition electrodes 41 are distributed in parallel in the housing, the partition electrodes 41 are independent, and slits are arranged between adjacent partition electrodes 41 to ensure electrical isolation. Each of the partition electrodes 41 includes a metal substrate 42, a semiconductor layer 43, and an inert metal layer 44, which are disposed in this order. The metal substrate 42 is arranged on the inner wall of the outer cylinder 52, the semiconductor layer 43 is plated on the inner wall of the metal substrate 42, and the inert metal layer 44 is arranged on the inner wall of the semiconductor layer 43; the semiconductor layer 43 is a semiconductor layer containing nano-metal particles. The metal substrate and the inert metal layer of each partition electrode may be individually set to an electric potential. The existence of the surface inert metal layer prevents the contact between air and the semiconductor layer, avoids the influence of air on the performance of the semiconductor layer, and prolongs the service life of the partition electrode.
Specifically, the slits provided between the respective partition electrodes 41 are such that each partition electrode is insulated from the others, and thus ions are guided to move toward the rear end by providing gradually decreasing potentials on different inert metal layers to construct a gradient potential. The three-layer structure of each segmented electrode 41 ensures that the electrode can still emit enough electrons under normal pressure. The metal substrate 42 provides support for the electrodes, the semiconductor layer 43 is arranged on the upper layer of the metal substrate 42, and the semiconductor layer 43 comprises a semiconductor material arranged on the upper layer of the metal substrate 42 and metal particles doped in the semiconductor material. The semiconductor material is doped with metal particles, and the metal particles can transfer electrons at a relatively high speed under the condition of a high electric field, but the pure semiconductor material is easy to be electrically corroded when discharged in the atmospheric environment, so that an inert metal layer 44 is arranged on the semiconductor layer 43. After the connection potential, the metal substrate 42 will provide free electrons to the subsequent electrode layer, which free electrons from the metal substrate 42 enter the semiconductor layer 43 under the guidance of the metal particles, since the metal substrate 42 has a higher potential than the inert metal layer 44, an accelerating electric field is formed in the semiconductor layer 43, the electrons are accelerated in the accelerating electric field and move towards the inert metal layer 44, and reach the vicinity of the inert metal layer 44, and have a higher kinetic energy, and furthermore, since the inert metal layer 44 itself also applies a potential, the barrier of the metal surface is lowered, electrons escape from the surface of the inert metal layer 44 under the combined action of the low barrier and the high electron kinetic energy, enter the region between the outer cylinder 52 and the inner cylinder 51, in which region an electric field is also formed, since the surface potential of the inner cylinder 51 is lower than the potential of the inert metal layer 44, pulling electrons move from the inert metal layer 44 onto the inner cylinder 51, and meet the analyte during the electron movement, so that the analyte is ionized.
As shown in fig. 1 and 2, the inner cylinder 51 is placed in the outer cylinder 52 through a support ring 53; the outer end of the first conical opening 11 of the inner cylinder 51 extends out of the second conical opening 22 of the outer cylinder 52, and a sample injection gap 54 is arranged between the outer peripheral wall of the outer end of the first conical opening 11 and the inner peripheral wall of the outer end of the second conical opening 22; a gap is left between the sealing plate of the inner cylinder 51 and the insulating ring 23. By providing the support ring 53 between the inner and outer cylinders, the coaxiality of the inner cylinder 51 and the outer cylinder 52 can be ensured, the space distance between the two layers of electrodes is ensured to be uniform, and the uniformity of the electric field is further ensured. The first conical opening 11 extends from the second conical opening 22 to ensure that the carrier gas meets the surface of the material which is difficult to volatilize after being sprayed from the first conical opening 11, and is sucked into the second conical opening 22. If the first conical opening 11 does not extend beyond the second conical opening 22, the second conical opening 22 will suck a large amount of carrier gas, even if the sucked gas does not contain the sample to be analyzed. The gap between the seal plate of the inner barrel 51 and the insulator ring 23 focuses ions from the annular space to a region of movement on the central axis which allows space for radial migration of ions while moving axially.
As shown in fig. 1, the apparatus further includes a substrate voltage dividing circuit and an inert layer voltage dividing circuit; the substrate voltage dividing circuit comprises a plurality of substrate voltage dividing resistors 64 which are sequentially connected in series between a power supply and ground; the inert layer voltage dividing circuit comprises a plurality of inert layer voltage dividing resistors 63 which are sequentially connected in series between a power supply and the ground; the metal substrate 42 of each partition electrode 41 is respectively connected to different potential points of the substrate voltage dividing circuit through a wire, the focusing electrode 31 is connected with the last stage of the substrate voltage dividing circuit through a wire, and the voltage of the metal substrate 42 of each partition electrode between the second conical opening 22 and the insulating ring 23 and the voltage of the focusing electrode 31 are gradually reduced; the inert metal layers 44 of each partition electrode are respectively connected to different potential points of the inert layer voltage division circuit through a lead, and the potential of the inner cylinder 51 is the same as that of the inert metal layer 43 of the last stage; on the same partition electrode 41, the voltage of the metal substrate 42 is higher than that of the inert metal layer 43. The substrate voltage dividing circuit and the inert layer voltage dividing circuit provide uniform and interrelated gradient potentials for the partition electrode and the inner cylinder.
The gradient voltage constructed by each substrate voltage dividing resistor 64 is connected to the metal substrate of each partition electrode through a wire, the voltage of the metal substrate of each partition electrode between the second taper port and the rear end outlet gradually decreases, and the last stage of the substrate voltage dividing circuit is connected to the focusing electrode. The gradient voltage built by each inert layer voltage dividing resistor 63 is respectively connected to the inert metal layers of each partition electrode, the voltage of each inert metal layer of each partition electrode between the second conical opening and the rear end outlet is gradually reduced, and the electric potential of the conductive torch is the same as that of the inert metal layer of the last stage. On the same partition electrode, the voltage of the metal substrate is higher than that of the inert metal layer, a gradient electric field is formed in the semiconductor layer, electrons in the semiconductor material are accelerated by the gradient electric field, meanwhile, the potential barrier on the surface of the inert metal layer is reduced due to the voltage applied to the inert metal layer, and electrons escape from the inert metal layer due to the simultaneous action of the two factors. Since the potential of the conductive torch is the same as that of the last inert metal layer, and the potential of the inert metal layer gradually decreases from the inlet to the outlet, the potential of the conductive torch is smaller than or equal to that of the inert metal layer, but is larger than zero.
The invention also relates to a working method of the mass spectrum sample injection ionization device, which comprises the following steps:
(1) Sample injection ionization of gaseous and volatile substances
The gaseous substance can be directly injected without opening the air pump 61, and the object to be detected is sucked into the area between the inner cylinder 51 and the outer cylinder 52 from the injection slit 54 under the action of the low pressure characteristic of the analysis equipment 62 connected with the rear end outlet 24; the object to be detected is a gas molecule.
After the voltage of the substrate voltage division circuit and the inert layer voltage division circuit are set, since the voltage of the metal substrate 42 is higher than the voltage of the inert metal layer 44, a gradient electric field is formed in the semiconductor layer 43, and electrons in the semiconductor layer 43 are accelerated by the gradient electric field and enter the inert metal layer 44 from the semiconductor layer 43; meanwhile, as the potential barrier on the surface of the inert metal layer 44 is reduced due to the voltage applied to the inert metal layer 44, electrons can escape from the inert metal layer 44 and enter the area between the inner cylinder 51 and the outer cylinder 52; when the gas molecules entering between the inner cylinder 51 and the outer cylinder 52 encounter electrons escaping from the inert metal layer 44, the gas molecules interact with the electrons, and the gas molecules lose the outermost electrons to become positively charged ions.
In the axial direction of the inner cylinder 51 and the outer cylinder 52, the potential of the inert metal layer 44 gradually decreases to form a gradient electric field, which is an axial electric field; under the action of the airflow and the gradient electric field, the object to be detected gradually moves to the rear end outlet 24; in the radial direction, the inner cylinder 51 and the inert metal layer 44 are both at positive potential to form a radial electric field, and an object to be detected is simultaneously repelled by the inner cylinder 51 and the inert metal layer 44 and is gathered in an annular space formed by the inert metal layer 44 and the inner cylinder 51 to form a focusing effect; under the combined action of the radial electric field and the axial electric field, ions of the object to be detected gradually move from the sample injection slit 54 to the rear end outlet 24, when the ions reach the vicinity of the focusing electrode 31, the ions are focused on the central axis, and then are discharged from the rear end outlet 24 under the action of the electric field and the air flow, and enter the analysis equipment 62.
(2) Sample injection ionization of difficult volatile substances
The difficult volatile substances are difficult to form gaseous steam to be inhaled into the mass spectrum sample injection ionization device, and the carrier gas purging auxiliary is needed. The air pump pumps air into the inner cylinder, and the air is heated under the action of the heating resistance wire and is sprayed out from the first conical opening; after the heated gas is purged to the surface of the to-be-tested object which is difficult to volatilize, part of the substances are changed into gaseous state under the action of air flow and temperature to fall off from the surface of the to-be-tested object, and then are sucked into the area between the inner cylinder and the outer cylinder from the sample injection gap.
After the voltage of the substrate voltage division circuit and the inert layer voltage division circuit is set, as the voltage of the metal substrate is higher than the voltage of the inert metal layer, a gradient electric field is formed in the semiconductor layer, and electrons in the semiconductor layer are accelerated by the gradient electric field and enter the inert metal layer from the semiconductor layer; meanwhile, as the potential barrier on the surface of the inert metal layer is reduced due to the voltage applied on the inert metal layer, electrons can escape from the inert metal layer and enter the area between the inner cylinder and the outer cylinder; when the gas molecules entering between the inner cylinder and the outer cylinder encounter electrons escaping from the inert metal layer, the gas molecules interact with the electrons, and the outermost layer electrons of the gas molecules are lost to become positively charged ions.
In the axial direction of the inner cylinder and the outer cylinder, the gradually reduced potential of the inert metal layer forms a gradient electric field, and the gradient electric field is an axial electric field; under the action of the airflow and the gradient electric field, the object to be detected gradually moves to the outlet at the rear end; in the radial direction, the inner cylinder and the inert metal layer are both positive potentials to form a radial electric field, and an object to be detected can be simultaneously repelled by the inner cylinder and the inert metal layer and is gathered in an annular space formed by the inert metal layer and the inner cylinder to form a focusing effect; under the combined action of the radial electric field and the axial electric field, ions of an object to be detected gradually move from a sample injection gap to a rear end outlet, when the ions reach the vicinity of a focusing electrode, the ions are focused on a central axis, and then are discharged from the rear end outlet under the action of the electric field and the air flow and enter analysis equipment.
The existing atmospheric pressure ionization source generally utilizes an auxiliary reagent and auxiliary carrier gas, and the outlet of the auxiliary carrier gas and the sample inlet of the sample are two separated structures, so that the positions of two gas paths are required to be placed and set before the sample is analyzed by the separated structures, thereby ensuring the reliability of sample injection. The structure provided by the invention ensures that the auxiliary gas and the sample injection are in the same device, and the auxiliary gas and the sample injection do not need to be arranged in advance before use. The invention adopts a coaxial double-layer electrode structure formed by the coaxially arranged inner cylinder and outer cylinder, and has the functions of a gas channel and a constraint potential, so that mass spectrum sample injection and electrodes are combined together, and the analysis flow of atmospheric pressure mass spectrum is greatly simplified. The structural design of the inner cylinder enables the auxiliary carrier gas to help the vaporization of the difficult volatile substances when the difficult volatile substances are analyzed.
The traditional electron emission adopts a needle point discharge or a planar electrode discharge mode in vacuum. Because the discharge area is concentrated, the electric corrosion is easy to generate, and the passivated needle tip cannot be effectively discharged. Other flat-plate type discharge structures are easy to oxidize due to the fact that the discharge part is directly exposed to air, and the formation resistance of the surface oxide layer is further discharged. The partition electrode with the three-layer flat plate structure adopted by the invention enables stable discharge of the electrode under the atmospheric pressure to be possible. By coating the semiconductor material with the inert metal, the ionization source can continuously work in the atmospheric environment because no tip exists and passivation phenomenon does not exist, and meanwhile, the inert metal layer is not easy to generate an oxidation structure.
On the same cross section, the non-uniformity of the field intensity necessarily causes ionized ions to be attracted to a strong field from a place with small field intensity, so that the ions are aggregated, molecular ion reaction is extremely easy to generate in the aggregation of the ions in a local area, the original ion structure is damaged, and the final analysis generates errors; therefore, the electric field between the inner cylinder 51 and the outer cylinder 52 should ensure that the field strength of the electric field is equal in the radial direction. In order to ensure uniformity of field intensity in the radial direction, the invention adopts good conductor materials with good conductivity to manufacture the inert metal layer 44 and the inner cylinder 51, so that the surface of each inert metal layer 44 and the surface of the inner cylinder 51 are equipotential surfaces, thereby ensuring uniformity of the ionization device in terms of potential. Meanwhile, since the inner cylinder 51 and the outer cylinder 52 need to be ensured to be coaxial, so as to ensure that the distances from the surface of the inner cylinder 51 to the surface of the inert metal layer 44 are equal on any radial section, two or more support rings 53 are placed between the inner cylinder 51 and the outer cylinder 52 to limit the relative displacement between the inner cylinder 51 and the outer cylinder 52, so that the uniformity of the electric field size in the same radial section can be basically ensured after the uniformity of the electric potential and the relative distance is ensured at the same time.
In the analysis of the substances which are difficult to volatilize, the gasification of the substances to be measured needs to be assisted by the action of the carrier gas. The carrier gas must be maintained at a temperature to ensure sample vaporization efficiency, and in order to ensure that the gas flow exiting from the first conical port 11 has a sufficiently high temperature, the heating power of the heating resistance wire 13 for heating the carrier gas should satisfy the following conditions: power > flow rate temperature difference 1.32. The carrier gas flow rate is generally set to be about 0.016L/s, and the room temperature (25 ℃ C.) air is raised to 80 ℃ C., the power supplied to the heating resistor wire 13 should be greater than: 0.016 x (80-25) x 1.32=1.16 kW. To ensure a certain flow rate of the heated air at the time of injection, the length of the first tapered opening 11 should be 2 to 4 times the minimum diameter of the first tapered opening 11. Meanwhile, in order to prevent too small a sample amount from entering the sample ionization source from the sample slit 54, the flow rate of the carrier gas ejected from the first cone 11 should be set smaller than the flow rate of the sucked gas in the sample slit 54. Since the carrier gas has a certain diffusion effect after exiting the first conical outlet 11, in order to reduce the excessive carrier gas sucked into the sample slot 54, it is necessary that the first conical outlet 11 extends out of the second conical outlet 22 by a distance greater than the minimum diameter of the second conical outlet 22.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A mass spectrum advances kind ionization device, its characterized in that: comprises an inner cylinder and an outer cylinder which are coaxially arranged;
the inner cylinder comprises a hollow conductive torch, a sealing plate for sealing an opening at one end of the conductive cylinder, a conical opening I arranged at the opening at the other end of the conductive cylinder, a heating resistance wire arranged on the inner wall of the conductive cylinder and a ventilation catheter penetrating through the side wall of the conductive cylinder;
the outer cylinder comprises a hollow shell, a plurality of partition electrodes, a second conical opening, a focusing assembly and a gas pipe hole, wherein the partition electrodes are sequentially arranged on the inner wall of the shell in parallel, the second conical opening is arranged at an opening at one end of the shell, the focusing assembly is arranged at an opening at the other end of the shell, and the gas pipe hole is used for allowing a ventilation pipe to pass through; the partition electrode comprises a metal substrate, a semiconductor layer and an inert metal layer which are sequentially arranged.
2. The mass spectrometry ionization device according to claim 1, wherein: one end of the conductive cylinder provided with a sealing plate is provided with an aeration conduit communicated with the inner cavity of the conductive cylinder; the shell is provided with a gas pipe hole; the airway tube extends outwardly from the tracheal opening and is sealed between the airway tube and the tracheal opening.
3. The mass spectrometry ionization device according to claim 1, wherein: the focusing assembly comprises an insulating ring arranged at the opening at the other end of the shell, a focusing electrode arranged on the inner peripheral wall of the insulating ring and a focusing filter cone arranged on the outer side of the insulating ring; the width of the focusing electrode is smaller than that of the insulating ring; the focusing filter cone is provided with a rear end outlet; the focusing electrode, the focusing filter cone, the inner cylinder and the outer cylinder are coaxially arranged.
4. The mass spectrometry ionization device according to claim 1, wherein: the first conical opening and the second conical opening are both in a truncated cone shape, and the diameters of the first conical opening and the second conical opening are gradually reduced from inside to outside.
5. The mass spectrometry ionization device according to claim 1, wherein: the heating resistance wire is spiral, and the heating resistance wire is closely attached to the inner wall of the inner cylinder.
6. The mass spectrometry ionization device according to claim 1, wherein: slits are arranged between adjacent partition electrodes; the metal substrate is arranged on the inner wall of the outer cylinder, the semiconductor layer is plated on the inner wall of the metal substrate, and the inert metal layer is arranged on the inner wall of the semiconductor layer; the semiconductor layer is a semiconductor layer containing nano metal particles.
7. A mass spectrometry ionization device according to claim 3, wherein: the inner cylinder is arranged in the outer cylinder through a supporting ring; the outer end of the first conical opening of the inner cylinder extends out of the second conical opening of the outer cylinder, and a sample injection gap is arranged between the outer peripheral wall of the outer end of the first conical opening and the inner peripheral wall of the outer end of the conical opening; a gap is reserved between the sealing plate of the inner cylinder and the insulating ring.
8. The mass spectrometry ionization device according to claim 2, wherein: the ventilation duct is connected with an air pump.
9. The mass spectrometry ionization device according to claim 1, wherein: the device also comprises a substrate voltage division circuit and an inert layer voltage division circuit; the substrate voltage dividing circuit comprises a plurality of substrate voltage dividing resistors which are sequentially connected in series between a power supply and ground; the inert layer voltage dividing circuit comprises a plurality of inert layer voltage dividing resistors which are sequentially connected in series between a power supply and the ground; the metal substrate of each partition electrode is connected to different potential points of the substrate voltage dividing circuit through a wire, the focusing electrode is connected with the last stage of the substrate voltage dividing circuit through a wire, and the voltage of the metal substrate of each partition electrode and the voltage of the focusing electrode between the second conical opening and the insulating ring are gradually reduced; the inert metal layers of the partition electrodes are respectively connected to different potential points of the inert layer voltage dividing circuit through a lead, and the potential of the inner cylinder is the same as that of the inert metal layer of the last stage; on the same segmented electrode, the voltage of the metal substrate is higher than that of the inert metal layer.
10. The working method of the mass spectrum sample injection ionization device according to any one of claims 1 to 9, wherein the working method is characterized in that: the method comprises the following steps:
(1) Sample injection ionization of gaseous and volatile substances
The air pump is not required to be started, and under the low pressure effect of analysis equipment connected with the rear end outlet, an object to be detected enters the area between the inner cylinder and the outer cylinder from the sample injection gap; the object to be detected is a gas molecule;
after the voltage of the substrate voltage division circuit and the inert layer voltage division circuit is set, as the voltage of the metal substrate is higher than the voltage of the inert metal layer, a gradient electric field is formed in the semiconductor layer, and electrons in the semiconductor layer are accelerated by the gradient electric field and enter the inert metal layer from the semiconductor layer; meanwhile, as the potential barrier on the surface of the inert metal layer is reduced due to the voltage applied on the inert metal layer, electrons escape from the inert metal layer and enter the area between the inner cylinder and the outer cylinder; when the gas molecules entering between the inner cylinder and the outer cylinder meet electrons escaping from the inert metal layer, the gas molecules interact with the electrons, and the outermost layer electrons of the gas molecules are lost to become positively charged ions;
in the axial direction of the inner cylinder and the outer cylinder, the gradually reduced potential of the inert metal layer forms a gradient electric field, and the gradient electric field is an axial electric field; under the action of the airflow and the gradient electric field, the object to be detected gradually moves to the outlet at the rear end; in the radial direction, the inner cylinder and the inert metal layer are both positive potentials to form a radial electric field, and an object to be detected can be simultaneously repelled by the inner cylinder and the inert metal layer and is gathered in an annular space formed by the inert metal layer and the inner cylinder to form a focusing effect; under the combined action of the radial electric field and the axial electric field, ions of an object to be detected gradually move from a sample injection gap to a rear end outlet, when the ions reach the vicinity of a focusing electrode, the ions are focused on a central shaft, and then are discharged from the rear end outlet under the action of the electric field and the air flow and enter analysis equipment;
(2) Sample injection ionization of difficult volatile substances
The air pump pumps air into the inner cylinder, and the air is heated under the action of the heating resistance wire and is sprayed out from the first conical opening; after the heated gas is purged to the surface of the to-be-tested object which is difficult to volatilize, under the action of air flow and temperature, part of substances are changed into gas state to fall off from the surface of the to-be-tested object, and then are sucked into a region between the inner cylinder and the outer cylinder from a sample injection gap;
after the voltage of the substrate voltage division circuit and the inert layer voltage division circuit is set, as the voltage of the metal substrate is higher than the voltage of the inert metal layer, a gradient electric field is formed in the semiconductor layer, and electrons in the semiconductor layer are accelerated by the gradient electric field and enter the inert metal layer from the semiconductor layer; meanwhile, as the potential barrier on the surface of the inert metal layer is reduced due to the voltage applied on the inert metal layer, electrons escape from the inert metal layer and enter the area between the inner cylinder and the outer cylinder; when the gas molecules entering between the inner cylinder and the outer cylinder meet electrons escaping from the inert metal layer, the gas molecules interact with the electrons, and the outermost layer electrons of the gas molecules are lost to become positively charged ions;
in the axial direction of the inner cylinder and the outer cylinder, the gradually reduced potential of the inert metal layer forms a gradient electric field, and the gradient electric field is an axial electric field; under the action of the airflow and the gradient electric field, the object to be detected gradually moves to the outlet at the rear end; in the radial direction, the inner cylinder and the inert metal layer are both positive potentials to form a radial electric field, and an object to be detected can be simultaneously repelled by the inner cylinder and the inert metal layer and is gathered in an annular space formed by the inert metal layer and the inner cylinder to form a focusing effect; under the combined action of the radial electric field and the axial electric field, ions of an object to be detected gradually move from a sample injection gap to a rear end outlet, when the ions reach the vicinity of a focusing electrode, the ions are focused on a central axis, and then are discharged from the rear end outlet under the action of the electric field and the air flow and enter analysis equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011013024.2A CN112151352B (en) | 2020-09-24 | 2020-09-24 | Mass spectrum sample injection ionization device and working method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011013024.2A CN112151352B (en) | 2020-09-24 | 2020-09-24 | Mass spectrum sample injection ionization device and working method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112151352A CN112151352A (en) | 2020-12-29 |
| CN112151352B true CN112151352B (en) | 2024-01-26 |
Family
ID=73896369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011013024.2A Active CN112151352B (en) | 2020-09-24 | 2020-09-24 | Mass spectrum sample injection ionization device and working method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112151352B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114941154B (en) * | 2022-04-29 | 2023-08-04 | 同济大学 | Alkaline water electrolysis bath partition electrode and preparation method |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301369A (en) * | 1978-08-12 | 1981-11-17 | The President Of Osaka University | Semiconductor ion emitter for mass spectrometry |
| CN101097831A (en) * | 2006-06-08 | 2008-01-02 | 麦克诺塞伊可系统有限公司 | Microengineerd vacuum interface for an ionization system |
| CN101820979A (en) * | 2007-06-01 | 2010-09-01 | 普度研究基金会 | Discontinuous atmospheric pressure interface |
| US7838826B1 (en) * | 2008-08-07 | 2010-11-23 | Bruker Daltonics, Inc. | Apparatus and method for parallel flow ion mobility spectrometry combined with mass spectrometry |
| TW201232598A (en) * | 2011-01-26 | 2012-08-01 | Univ Nat Formosa | Transformation unit for transforming electrospray ionization device into atmospheric pressure chemical ionization device and ionization device using the same |
| CN103515185A (en) * | 2013-09-18 | 2014-01-15 | 东华理工大学 | Ionization device for detecting pesticide residues in juice sample through mass spectrum and detection method |
| CN105304451A (en) * | 2015-10-23 | 2016-02-03 | 浙江好创生物技术有限公司 | Electrospray ion source applied to mass spectrometer and mass spectrum analysis method |
| CN105632870A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院大连化学物理研究所 | Atmospheric pressure chemical ionization source for mass spectrum |
| CN107860618A (en) * | 2017-12-26 | 2018-03-30 | 清华大学 | Gather sampling device and detecting system |
| CN109461642A (en) * | 2018-12-07 | 2019-03-12 | 中国烟草总公司郑州烟草研究院 | A kind of ion initiation electron impact ionization source |
| CN109841467A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A method of slowing down vacuum UV lamp rate of decay in mass spectrometer |
| JP2019204721A (en) * | 2018-05-24 | 2019-11-28 | 岳石電気株式会社 | Electron beam source in mass spectrometer |
| TW202022343A (en) * | 2018-07-25 | 2020-06-16 | 加拿大商珀金埃爾默健康科學加拿大公司 | System for introducing particle-containing samples to an analytical instrument and methods of use |
-
2020
- 2020-09-24 CN CN202011013024.2A patent/CN112151352B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301369A (en) * | 1978-08-12 | 1981-11-17 | The President Of Osaka University | Semiconductor ion emitter for mass spectrometry |
| CN101097831A (en) * | 2006-06-08 | 2008-01-02 | 麦克诺塞伊可系统有限公司 | Microengineerd vacuum interface for an ionization system |
| CN101820979A (en) * | 2007-06-01 | 2010-09-01 | 普度研究基金会 | Discontinuous atmospheric pressure interface |
| US7838826B1 (en) * | 2008-08-07 | 2010-11-23 | Bruker Daltonics, Inc. | Apparatus and method for parallel flow ion mobility spectrometry combined with mass spectrometry |
| TW201232598A (en) * | 2011-01-26 | 2012-08-01 | Univ Nat Formosa | Transformation unit for transforming electrospray ionization device into atmospheric pressure chemical ionization device and ionization device using the same |
| CN103515185A (en) * | 2013-09-18 | 2014-01-15 | 东华理工大学 | Ionization device for detecting pesticide residues in juice sample through mass spectrum and detection method |
| CN105632870A (en) * | 2014-10-28 | 2016-06-01 | 中国科学院大连化学物理研究所 | Atmospheric pressure chemical ionization source for mass spectrum |
| CN105304451A (en) * | 2015-10-23 | 2016-02-03 | 浙江好创生物技术有限公司 | Electrospray ion source applied to mass spectrometer and mass spectrum analysis method |
| CN109841467A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A method of slowing down vacuum UV lamp rate of decay in mass spectrometer |
| CN107860618A (en) * | 2017-12-26 | 2018-03-30 | 清华大学 | Gather sampling device and detecting system |
| JP2019204721A (en) * | 2018-05-24 | 2019-11-28 | 岳石電気株式会社 | Electron beam source in mass spectrometer |
| TW202022343A (en) * | 2018-07-25 | 2020-06-16 | 加拿大商珀金埃爾默健康科學加拿大公司 | System for introducing particle-containing samples to an analytical instrument and methods of use |
| CN109461642A (en) * | 2018-12-07 | 2019-03-12 | 中国烟草总公司郑州烟草研究院 | A kind of ion initiation electron impact ionization source |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112151352A (en) | 2020-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10818486B2 (en) | System for minimizing electrical discharge during ESI operation | |
| EP0566022B1 (en) | Insulated needle for forming an electrospray | |
| US6949739B2 (en) | Ionization at atmospheric pressure for mass spectrometric analyses | |
| EP2606506B1 (en) | Ion transfer tube having elongate bore segments | |
| JP5016191B2 (en) | Multimode ionization source, method of generating ions using the same, and multimode ionization mass spectrometer | |
| US9570281B2 (en) | Ion generation device and ion generation method | |
| CA2696115C (en) | Low pressure electrospray ionization system and process for effective transmission of ions | |
| US8173960B2 (en) | Low pressure electrospray ionization system and process for effective transmission of ions | |
| US8637812B2 (en) | Sample excitation apparatus and method for spectroscopic analysis | |
| JP5589750B2 (en) | Ionizer for mass spectrometer and mass spectrometer equipped with the ionizer | |
| WO2004057638A2 (en) | Method and apparatus for aerodynamic ion focusing | |
| JP2010537371A (en) | Sample ionization at pressures above vacuum | |
| CN112368799A (en) | Ion generator for multiple gas flow | |
| CN112151352B (en) | Mass spectrum sample injection ionization device and working method thereof | |
| US20110260048A1 (en) | Ion Transfer Tube for a Mass Spectrometer Having a Resistive Tube Member and a Conductive Tube Member | |
| CN210897196U (en) | Electrospray ion source and mass spectrum device | |
| CN112750679A (en) | Mass spectrometry system and method | |
| CN112020760A (en) | IMR-MS device | |
| JP2011113832A (en) | Mass spectrometer | |
| CN110880446B (en) | Deep ultraviolet LED ionization source and working method thereof | |
| JP2002124208A (en) | Ionizing method for mass spectrometry and mass spectrometer | |
| JP2005243627A (en) | Mass spectrometer | |
| GB2512640A (en) | Improvements in and relating to the production and control of ions | |
| US20230162961A1 (en) | Ionizer and mass spectrometer | |
| CN116825606A (en) | Electrospray system for mass spectrometer based on porous capillary structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |