CN114300337A - Photoionization-quadrupole mass spectrometry system - Google Patents

Photoionization-quadrupole mass spectrometry system Download PDF

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Publication number
CN114300337A
CN114300337A CN202111531868.0A CN202111531868A CN114300337A CN 114300337 A CN114300337 A CN 114300337A CN 202111531868 A CN202111531868 A CN 202111531868A CN 114300337 A CN114300337 A CN 114300337A
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China
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photoionization
quadrupole mass
ionization chamber
ion
mass spectrometry
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CN202111531868.0A
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Chinese (zh)
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黄泽建
江游
陈大舟
汤桦
方向
戴新华
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National Institute of Metrology
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National Institute of Metrology
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Abstract

The invention provides a photoionization-quadrupole mass spectrometry system, which comprises a photoionization photon source, an ionization chamber, an ion focusing assembly, a quadrupole mass analyzer and an ion detector, wherein the photoionization photon source, the ionization chamber, the ion focusing assembly, the quadrupole mass analyzer and the ion detector are sequentially arranged from left to right; the ionization chamber is used for storing gas molecules to be detected; the photoionization photon source is used for emitting photons to the ionization chamber, so that the photons ionize gas molecules in the ionization chamber to obtain ions; one end of the ion focusing assembly is communicated with the ionization chamber, and the ion focusing assembly is used for focusing ions; the inlet of the quadrupole mass analyzer is communicated with the other end of the ion focusing assembly, and the quadrupole mass analyzer is used for screening ions; the ion detector is in communication with the outlet of the quadrupole mass analyser. The invention realizes ionization of volatile micromolecule gas by utilizing photons with certain energy, and mass analysis by the quadrupole rod mass analyzer, avoids using consumables such as filaments and the like, and prolongs the service life of the system.

Description

Photoionization-quadrupole mass spectrometry system
Technical Field
The invention relates to the technical field of mass spectrometry detection, in particular to a photoionization-quadrupole mass spectrometry system.
Background
Mass spectrometry is one of the most basic instruments for researching the basic composition, structural characteristics, physical and chemical properties of substances, is a necessary instrument in the fields of life science, material science, food safety, environmental protection and the like, and is the core of modern analytical instruments. It is essentially a spectroscopic method in which moving ions are separated by their mass-to-charge ratios using electric and/or magnetic fields and detected. The compound composition of the ions can be determined by measuring the exact mass of the ions. The method is mainly used for structure identification of the compound, and can provide structural information such as molecular weight, element composition, functional groups and the like of the compound. It has wide analysis range and is suitable for gas, liquid and solid; the method has the advantages of high analysis speed, high sensitivity and small sample consumption; it can be directly qualitatively analyzed; accurate quantitative analysis of complex compounds is also possible by various means of separation. Because of these characteristics of mass spectrometry, it is widely used in the fields of organic chemistry, biology, geochemistry, nuclear industry, material science, environmental science, medical hygiene, food chemistry, petrochemical industry, etc., and in the fields of space technology and special analysis such as public security work, etc.
The ion source is a key component in a mass spectrometer and its function is to ionize gaseous sample molecules introduced by the sample introduction system into ions. Ionization of sample molecules is the primary link in mass spectrometry. The performance of the ion source has great influence on multiple indexes of the instrument, and whether effective ionization of sample molecules can directly influence important indexes such as the type, detection limit and sensitivity of a detectable substance. Common ion sources are electron impact ionization (EI) and Chemical Ionization (CI) sources used in conjunction with Gas Chromatography (GC), electrospray ionization (ESI) sources used in conjunction with Liquid Chromatography (LC), Atmospheric Pressure Chemical Ionization (APCI), Atmospheric Pressure Photoionization (APPI), and other ion sources such as ultraviolet photoionization sources, matrix assisted laser desorption ion sources (MALDI), desorption electrospray ion sources (DESI), direct analysis in real time ion sources (DART), and the like.
EI sources used in conjunction with GC are most widely used for the detection of volatile small molecules. The EI source utilizes noble metal wires, such as tungsten wires and rhenium wires, and a certain intensity of current, such as 1-3A, flows through the metal wires, so that the noble metal wires generate heat and then overflow free thermal electrons. The free thermal electrons are ionized by applying a certain energy to them through an external electric field. Typically 70eV energy is applied to the electrons. Generally, ionization energy of small organic molecules is 8-10 eV, therefore, an electron of 70eV is exchanged with a molecule to enable the molecule to lose one electron and to be charged positively, the molecule ion can be further fragmented by the redundant electron energy of the electron, and thus, the ion ionized by the electron of 70eV has both molecular ions and fragment ions, so that if the mixture enters the mass spectrum together and is ionized by an EI source, the fragment ions of different substances can overlap, which brings difficulty to both qualitative and quantitative determination. In addition, the overflow of free hot electrons also results in the consumption of precious metal material, thereby affecting the lifetime of the system.
Disclosure of Invention
The invention provides a photoionization-quadrupole mass spectrometry system, which is used for solving the defects that fragment ions of different substances are possibly overlapped, qualitative and quantitative mass spectrometry of small molecules is difficult, the service life of the system is short and the like in a small molecule mass spectrometry system in the prior art.
The invention provides a photoionization-quadrupole mass spectrometry system, which comprises a photoionization photon source, an ionization chamber, an ion focusing assembly, a quadrupole mass analyzer and an ion detector, wherein the photoionization photon source, the ionization chamber, the ion focusing assembly, the quadrupole mass analyzer and the ion detector are sequentially arranged from left to right;
the ionization chamber is used for storing gas molecules to be detected;
the photoionization photon source is used for emitting photons to the ionization chamber so that the photons ionize gas molecules in the ionization chamber to obtain ions;
one end of the ion focusing assembly is communicated with the ionization chamber, and the ion focusing assembly is used for focusing ions;
the inlet of the quadrupole mass analyzer is communicated with the other end of the ion focusing assembly, and the quadrupole mass analyzer is used for screening ions;
the ion detector is communicated with an outlet of the quadrupole mass analyzer and is used for detecting the ion concentration.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, the photoionization photon source comprises a light source cavity and at least one discharge assembly, and one end of the discharge assembly is positioned in the light source cavity.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, the photoionization photon source comprises two discharge assemblies, wherein one discharge assembly is positioned at the upper part in the light source cavity, and the other discharge assembly is positioned at the lower part in the light source cavity.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, the discharge assembly comprises an anode plate and a cathode plate which are arranged in parallel side by side, and one end of each of the anode plate and the cathode plate is positioned in the light source cavity.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, the side wall surface of the light source cavity close to the ionization chamber is a light-transmitting plate.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, a first communicating structure is arranged on the side wall surface of the ionization chamber close to the photoionization photon source, a second communicating structure is arranged on the side wall surface of the ionization chamber close to the ion focusing assembly, and an air inlet structure is arranged on the side wall surface of the ionization chamber.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, the ion focusing assembly comprises at least one focusing lens, and a through hole is formed in the focusing lens.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, the ion focusing assembly comprises two or more than two focusing lenses which are arranged in parallel.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, the aperture of the through hole on the focusing lens close to the quadrupole mass analyzer is smaller than that of the through hole on the focusing lens close to the ionization chamber.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, the ion detector comprises a Faraday cup and an electron multiplier, the Faraday cup is positioned on one side of the outlet of the quadrupole mass analyzer, a third communication structure is arranged on the side wall surface of the Faraday cup close to the quadrupole mass analyzer, a fourth communication structure is arranged on the upper wall surface of the Faraday cup, and the electron multiplier is positioned above the fourth communication structure.
According to the photoionization-quadrupole mass spectrometry system provided by the invention, gas molecules to be detected are conveyed into an ionization chamber, then photons are emitted to the ionization chamber through a photoionization photon source, and the photons react with the gas molecules to be detected after reaching the ionization chamber to realize photoionization, so that the gas molecules are charged and become ions. Then the ions move to the ion focusing assembly, when the ions pass through the ion focusing assembly and reach the quadrupole mass analyzer, the ion focusing assembly focuses the ions, so that the ions conveyed to the quadrupole mass analyzer are focused ions, then the quadrupole mass analyzer screens the ions according to the mass-to-charge ratio, the ions meeting the requirements can move to the ion detector, then the ion detector detects the concentration of the ions, and further the mass spectrogram of the gas to be detected is obtained. And then realized utilizing the photon that has certain energy to come to carry out the ionization to volatile small molecule gas to carry out mass analysis through quadrupole rod mass analyzer, avoided using consumptive materials such as filament, prolonged the life of system, can be applied to some special fields under the operating condition that for example need long-term unmanned on duty.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a photoionization-quadrupole mass spectrometry system according to the present invention;
FIG. 2 is a schematic diagram of a portion of a photoionization-quadrupole mass spectrometry system provided in accordance with the present invention;
reference numerals:
1: a photoionization photon source; 2: an ionization chamber; 3: an ion focusing assembly;
4: a quadrupole mass analyser; 5: an ion detector; 11: a light source cavity;
12: a discharge assembly; 21: a first communication structure; 22: a second communicating structure;
23: an air intake structure; 31: a focusing lens; 32: a through hole;
51: a Faraday cup; 52: an electron multiplier; 53: a third communicating structure;
54: a fourth communication structure; 121: an anode plate; 122: and a cathode plate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The photoionization-quadrupole mass spectrometry system of the present invention is described below with reference to figures 1 and 2.
As shown in fig. 1 and 2, the photoionization-quadrupole mass spectrometry system comprises a photoionization photon source 1, an ionization chamber 2, an ion focusing assembly 3, a quadrupole mass analyzer 4 and an ion detector 5 which are sequentially arranged from left to right.
In particular, the ionization chamber 2 is used to store gas molecules to be detected.
The photoionization photon source 1 is used for emitting photons to the ionization chamber 2, so that the photons ionize gas molecules in the ionization chamber 2 to obtain ions.
One end of the ion focusing assembly 3 is communicated with the ionization chamber 2, and the ion focusing assembly 3 is used for focusing ions.
The inlet of the quadrupole mass analyser 4 is in communication with the other end of the ion focusing assembly 3, the quadrupole mass analyser 4 being arranged to screen ions.
An ion detector 5 communicates with the outlet of the quadrupole mass analyser 4, the ion detector 5 being for detecting the ion concentration.
When the gas ionization device is used, gas molecules to be detected are conveyed into the ionization chamber 2, then photons are emitted to the ionization chamber 2 through the photoionization photon source 1, and the photons reach the ionization chamber 2 and then react with the gas molecules to be detected to realize photoionization, so that the gas molecules are charged and become ions. Then the ions move to the ion focusing component 3, when the ions pass through the ion focusing component 3 and reach the quadrupole mass analyzer 4, the ion focusing component 3 focuses the ions, so that the ions conveyed to the quadrupole mass analyzer 4 are focused ions, then the quadrupole mass analyzer 4 screens the ions according to the mass-to-charge ratio, the ions meeting the requirements can move to the ion detector 5, and then the ion detector 5 detects the concentration of the ions, so as to obtain the mass spectrogram of the gas to be detected. And then realized utilizing the photon that has certain energy to come to carry out the ionization to volatile small molecule gas to carry out mass analysis through quadrupole rod mass analyzer 4, avoided using consumptive materials such as filament, prolonged the life of system, can be applied to some special fields under the operating condition that for example need long-term unmanned on duty.
Compared with the traditional method of ionizing gas by using free hot electrons, the method adopts photons, so that the material consumption is avoided, and the service life and the reliability are greatly improved. The method has more advantages in the aspects of service life and reliability for detecting the small molecule gas. The photons can be generated by a gas discharge lamp or other semiconductor lasers, and the use and the control are more convenient.
Further, as shown in fig. 1 and fig. 2, the photoionization photon source 1 includes a light source cavity 11 and at least one discharge assembly 12, and one end of the discharge assembly 12 is located in the light source cavity 11. When the ion source is used, inert gas is filled in the light source cavity 11, then an electric field is formed in the light source cavity 11 through the discharge assembly 12, so that the inert gas discharges to release photons with certain energy, the photons have certain speed under the action of the electric field, the photons can move into the ionization chamber 2 to ionize gas molecules, and the gas molecules are charged into ions. And further, the volatile micromolecule gas is ionized by photons with certain energy, the gas is prevented from being ionized by using the traditional free hot electrons, the consumption of materials is avoided, and the service life of the system is prolonged.
As shown in fig. 1 and fig. 2, the photoionization photon source 1 includes two discharge assemblies 12, wherein one discharge assembly 12 is located at an upper portion in the light source cavity 11, and the other discharge assembly 12 is located at a lower portion in the light source cavity 11. When the ionization chamber 2 is used, two electric fields can be formed in the light source cavity 11 through the two discharge assemblies 12, so that the inert gas can release more photons with certain energy, and further gas molecules in the ionization chamber 2 can be ionized more quickly and effectively.
As shown in fig. 1 and fig. 2, the discharge assembly 12 includes an anode plate 121 and a cathode plate 122 arranged in parallel side by side, and one end of each of the anode plate 121 and the cathode plate 122 is located in the light source cavity 11. When the light source is used, voltage is applied to the other ends of the anode plate 121 and the cathode plate 122, so that an electric field is formed in the light source cavity 11 by the anode plate 121 and the cathode plate 122, the inert gas is discharged to release photons with certain energy, and then the photons act on gas molecules, so that the gas molecules are charged to become ions, and photoionization of the gas molecules is realized.
Wherein, the side wall surface of the light source cavity 11 close to the ionization chamber 2 is a light-transmitting plate. When the light source is used, the light transmission plate enables photons to easily penetrate through the light source cavity 11, the transmittance of the photons is improved, and the photons in the light source cavity 11 can penetrate through the light transmission plate to move into the ionization chamber 2 to ionize gas molecules.
Wherein, in an optional embodiment of the present invention, the light-transmitting plate is, for example, a light-transmitting window. It should be understood that the light-transmitting plate may be any other suitable optical glass having a high transmittance for light, such as magnesium fluoride glass.
Further, as shown in fig. 1 and fig. 2, a first communicating structure 21 is disposed on a side wall surface of the ionization chamber 2 close to the photoionization photon source 1, a second communicating structure 22 is disposed on a side wall surface of the ionization chamber 2 close to the ion focusing assembly 3, and an air inlet structure 23 is disposed on a side wall surface of the ionization chamber 2. When the ionization device is used, gas molecules to be processed are conveyed into the ionization chamber 2 through the second communicating structure 22, photons generated in the light source cavity 11 enter the ionization chamber 2 through the first communicating structure 21, the photons act on the gas molecules, so that the gas molecules are charged into ions, the ionization of volatile small molecule gas by utilizing the photons with certain energy is realized, the ionization of the gas by using traditional free thermal electrons is avoided, the consumption of materials is avoided, and the service life of the system is prolonged.
In an alternative embodiment of the present invention, the first communicating structure 21, the second communicating structure 22 and the air intake structure 23 are through holes, for example. It should be understood that the first communication structure 21, the second communication structure 22 and the air intake structure 23 may be any other suitable structure, such as communication ducts.
Wherein, an electric field is arranged on the side wall surface of the ionization chamber 2 close to the ion focusing assembly 3. When the ion mass analyzer is used, ions entering the ion focusing assembly 3 are acted through an electric field, and primary screening of the ions is realized, so that only the ions meeting requirements can pass through the ion focusing assembly 3 and enter the quadrupole rod mass analyzer 4.
Further, as shown in fig. 1 and fig. 2, the ion focusing assembly 3 includes at least one focusing lens 31, and the focusing lens 31 is provided with a through hole 32. When the ion source is used, the photoionization photon source 1 emits photons into the ionization chamber 2, the photons ionize gas molecules, so that the gas molecules are charged to become ions, then the ions move to the focusing lens 31, the focusing lens 31 focuses the ions, the focused ions penetrate out of the focusing lens 31 from the through hole 32 and enter the quadrupole rod mass analyzer 4, and the ions are focused to facilitate mass analysis of the ions by the quadrupole rod mass analyzer 4.
As shown in fig. 1 and 2, the ion focusing assembly 3 includes two or more focusing lenses 31 disposed in parallel with each other. When the ion source is used, the photoionization photon source 1 emits photons to the ionization chamber 2, the photons and gas molecules act to generate ions, at the moment, the ions have a certain speed, and then the ions can pass through the plurality of focusing lenses 31 to enter the quadrupole rod mass analyzer 4, the gas molecules do not have an initial speed and can not pass through the plurality of focusing lenses 31, so that only the ions can pass through the plurality of lenses, the quadrupole rod mass analyzer 4 is guaranteed not to be interfered by the gas molecules, and the mass analysis can be accurately carried out.
Wherein the aperture of the through hole 32 on the focusing lens 31 close to the quadrupole mass analyser 4 is smaller than the aperture of the through hole 32 on the focusing lens 31 close to the ionization chamber 2. In use, the aperture size of the through hole 32 on the focusing lens 31 is inversely proportional to the distance of the focusing lens 31 from the ionization chamber 2, i.e. the aperture of the through hole 32 on the focusing lens 31 is larger the closer to the ionization chamber 2. The focusing lens 31 near the ionization chamber 2 primarily focuses the ions to the next focusing lens 31, and then the next focusing lens 31 secondarily focuses the ions until the focusing lens 31 near the quadrupole mass analyzer 4 finally focuses the ions, so that the ions enter the quadrupole mass analyzer 4 after being sufficiently focused.
Further, as shown in fig. 1 and 2, the ion detector 5 includes a faraday cup 51 and an electron multiplier 52, the faraday cup 51 is located at the outlet side of the quadrupole rod mass analyzer 4, a third communicating structure 53 is provided on the side wall surface of the faraday cup 51 close to the quadrupole rod mass analyzer 4, a fourth communicating structure 54 is provided on the upper wall surface of the faraday cup 51, and the electron multiplier 52 is located above the fourth communicating structure 54. When the ion detector is used, ions are firstly screened according to the mass-to-charge ratio by the quadrupole rod mass analyzer 4, only the ions meeting the stable condition can enter the ion detector 5 through the quadrupole rod mass analyzer 4, then the ions enter the Faraday cup 51, and the electron multiplier 52 detects the ions in the Faraday cup 51 through the fourth communicating structure 54, so that the concentration of the ions can be known.
In an alternative embodiment of the present invention, the third communicating structure 53 and the fourth communicating structure 54 are through holes, for example. It should be understood that the third and fourth via structures may be any other suitable communication structure.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A photoionization-quadrupole mass spectrometry system is characterized by comprising a photoionization photon source, an ionization chamber, an ion focusing assembly, a quadrupole mass analyzer and an ion detector which are sequentially arranged from left to right;
the ionization chamber is used for storing gas molecules to be detected;
the photoionization photon source is used for emitting photons to the ionization chamber so that the photons ionize gas molecules in the ionization chamber to obtain ions;
one end of the ion focusing assembly is communicated with the ionization chamber, and the ion focusing assembly is used for focusing ions;
the inlet of the quadrupole mass analyzer is communicated with the other end of the ion focusing assembly, and the quadrupole mass analyzer is used for screening ions;
the ion detector is communicated with an outlet of the quadrupole mass analyzer and is used for detecting the ion concentration.
2. The photoionization-quadrupole mass spectrometry system of claim 1, wherein the photoionization photon source comprises a light source cavity and at least one discharge assembly, one end of which is located within the light source cavity.
3. The photoionization-quadrupole mass spectrometry system of claim 2, wherein the photoionization photon source comprises two discharge assemblies, one of which is located in an upper portion of the source cavity and the other of which is located in a lower portion of the source cavity.
4. The photoionization-quadrupole mass spectrometry system of claim 2 or 3, wherein the discharge assembly comprises an anode plate and a cathode plate arranged in parallel side by side, one end of each of the anode plate and the cathode plate being located within the light source cavity.
5. The photoionization-quadrupole mass spectrometry system of any one of claims 1-3, wherein a sidewall surface of the light source cavity adjacent to the ionization chamber is a light-transmissive plate.
6. A photoionization-quadrupole mass spectrometry system according to any one of claims 1 to 3, wherein a first communication structure is provided on a sidewall of the ionization chamber adjacent to the photoionization photon source, a second communication structure is provided on a sidewall of the ionization chamber adjacent to the ion focusing assembly, and a gas inlet structure is provided on a sidewall of the ionization chamber.
7. The photoionization-quadrupole mass spectrometry system of any one of claims 1-3, wherein the ion focusing assembly comprises at least one focusing lens having a through-hole disposed therein.
8. The photoionization-quadrupole mass spectrometry system of claim 7, wherein the ion focusing assembly comprises two or more focusing lenses disposed in parallel with one another.
9. The photoionization-quadrupole mass spectrometry system of claim 8, wherein an aperture of the through-hole on the focusing lens proximate to the quadrupole mass analyzer is smaller than an aperture of the through-hole on the focusing lens proximate to the ionization chamber.
10. The photoionization-quadrupole mass spectrometry system of any one of claims 1-3, wherein the ion detector comprises a faraday cup and an electron multiplier, the faraday cup is located at an outlet side of the quadrupole mass analyzer, a third communicating structure is arranged on a side wall surface of the faraday cup close to the quadrupole mass analyzer, a fourth communicating structure is arranged on an upper wall surface of the faraday cup, and the electron multiplier is located above the fourth communicating structure.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117288829A (en) * 2023-09-27 2023-12-26 武汉科益研创科技有限公司 Gas generation detecting system

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