CN107024469A - A kind of method for differentiating propionic aldehyde and acetone - Google Patents
A kind of method for differentiating propionic aldehyde and acetone Download PDFInfo
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- CN107024469A CN107024469A CN201710208269.2A CN201710208269A CN107024469A CN 107024469 A CN107024469 A CN 107024469A CN 201710208269 A CN201710208269 A CN 201710208269A CN 107024469 A CN107024469 A CN 107024469A
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- acetone
- propionic aldehyde
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
- H01J49/0045—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction
- H01J49/0072—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn characterised by the fragmentation or other specific reaction by ion/ion reaction, e.g. electron transfer dissociation, proton transfer dissociation
Abstract
The invention provides a kind of chemical ionization mass spectrometry detection method for differentiating propionic aldehyde and acetone, comprise the following steps：(1) it is made to produce mononuclear ion metal progress processing using physical-chemical process；(2) mononuclear ion obtained by step (1) is loaded into reaction tube using buffer gas；(3) under test gas sample is sent into the reaction tube described in step (2), reacts generation ionization product in reaction tube with mononuclear ion；(4) by the ionization product described in step (3), device is detected after testing, is distinguishable propionic aldehyde and acetone gas according to testing result.Methods described makes the mononuclear ion that transition metal is produced be reacted as reagent ion and propionic aldehyde and acetone, not only produce the product ion for the different characteristic quality for corresponding to propionic aldehyde and acetone respectively, and reaction efficiency is high, purpose that is effectively ionized and differentiating propionic aldehyde and acetone can reach.
Description
Technical field
The present invention relates to a kind of analysis method for differentiating propionic aldehyde and acetone, specifically, it is related to a kind of resolution propionic aldehyde and third
The chemical ionization mass spectrometry detection method of ketone.
Background technology
Volatile organic matter (Volatile Organic Compounds, VOCs), which is that an important class in air is carbon containing, to be had
Machine thing, not only with toxicity and carcinogenicity, or forms the precursor of photochemical fog and ozone, its high-sensitivity detection is always
It is the problem that people pay special attention to.Particularly isomer propionic aldehyde (CH3CH2) and acetone (CH CHO3COCH3), their conducts
Important oxygen-containing VOCs (Oxygenated VOCs, OVOCs), plays different roles in Atmospheric Chemistry in air, because
This, this resolution to isomer of propionic aldehyde and acetone seems most important in air VOC detections.And chemical ionization mass spectrometry has
The features such as selective high and soft ionization, there is important advantage in mixing analyte detection.Wherein with H3O+For the matter of reagent ion
Sub- transfer reaction mass spectrum (Proton Transfer Reaction Mass Spectrometry, PTR-MS) is because having sensitivity concurrently
Height, the response time it is short and can direct injected the advantages of, be widely used in Atmospheric Trace VOCs detection.But if using PTR-
MS detects propionic aldehyde and acetone, because acetone and propionic aldehyde have identical molecular formula (C3H6), and H O3O+Product ion phase after reaction
Together, it is the product ion C of protonation3H7O+, therefore PTR-MS can not be differentiated.Although by PTR-MS and gas-chromatography skill
Art, which is combined, can reach differentiation aldehyde, the purpose of ketone isomer, but this is needed to sacrifice detection time as cost.Therefore it is directed to
This problem, needs badly and develops the chemical ionization source that new suitable reagent ion is detected as air VOCs, for propionic aldehyde and
The detection and analysis of acetone, so as to make up the defect that PTR-MS cannot distinguish between propionic aldehyde and acetone in VOCs context of detection.
In order to realize that chemical ionization mass spectrometry detects the resolution to propionic aldehyde and acetone, people also developed other reagent ions,
Such as NO+(de Gouw et al., Atmos.Meas.Teach.2016,9, the 2909-2925 pages；Store up flame south et al., institution of higher education
Chemical journal .2012,33, the 263-267 pages) and O2 +(Et al., Int.J.Mass Spectrom.1997,165/
166, the 25-37 pages) ion.When they are with propionic aldehyde and acetone reaction, respective reaction channel is different.Specifically, NO+With propionic aldehyde
Generation hydride-transfer reaction, the reaction of methyl anionotropy then occurs with acetone and adds and reacts；O2 +Occurs electricity with propionic aldehyde
Charge transfer reaction and hydride-transfer reaction, methyl anionotropy then only occurs with acetone and reacts.Therefore, NO+And O2 +With
After propionic aldehyde and acetone reaction, there is notable difference between product ion, and parent molecule amount can be reflected, available for propionic aldehyde and third
The resolution of ketone.However, above ion also has certain defect, such as NO in VOC context of detection+Do not reacted with formaldehyde, it is right
The small molecule such as methanol OVOC activity is smaller, and O2 +Easily cause the fracture of alkanes VOC molecules.
In order to find suitable reagent ion, in addition to above major element ion, it has also been found that monokaryon transition metal
The many organic molecules of ion pair show reactivity (Operti et al., the Mass quite enriched
Spectrom.Rev.2006,25, the 483-513 pages), can not only activated olefins, alkynes, aromatic hydrocarbon and the weaker alkane of activity
Hydrocarbon, with ethers, ketone, aldehydes, nitrogen-containing compound, sulfur-containing compound and many micro-molecular gas (H2、N2、O2) etc. compound
Also there is higher reactivity in course of reaction, the potential reagent ion for distinguishing propionic aldehyde and acetone molecules can be used as.However,
Although monokaryon transition metal ions has so abundant reactivity, from the chemical-electrical for being not used for differentiating propionic aldehyde acetone molecules
From analysis.In addition, some monokaryon early transition metals Sc, Ti and V metal ions M+(Tolbert et al.,
J.Am.Chem.Soc.1984,106, the 8117-8122 pages) with acetone reaction after product ion be MO+, it is impossible to formation represents third
The parent ion of ketone molecular weight, and with the rare research of reactivity of propionic aldehyde, therefore be unfavorable for the resolution of acetone and propionic aldehyde.
Have been reported that for different molecular weight gas linear paraffin carry out chemi-ionization when, using monokaryon late transition metal from
The sub reagent ion as chemi-ionization linear paraffin, by being chemically reacted at a certain pressure with linear paraffin, no
Can occur the fragmentation of alkane, formation can directly reflect the product ion of alkane molecule amount.But it is due to acetone and propionic aldehyde and straight
The property and structure of alkane are entirely different, and more importantly how to distinguish molecular weight identical acetone and propionic aldehyde, at present
Not yet have been reported that and made a distinction using the chemi-ionization of transition metal ions (preferably late transition metal ion).
Based on this, the present inventor after substantial amounts of experimental study by having found, transition metal ions, especially late transition metal
Ion, when with propionic aldehyde and acetone reaction, shows visibly different reactivity, inventor to reaction condition by entering accordingly
Chemi-ionization method, is successfully applied to the separation and detection of the gas molecule of isomer, effectively by row adjustment and screening
Realize the resolution of acetone and propionic aldehyde.
The content of the invention
In order to improve the above-mentioned problems in the prior art, the present invention is intended to provide a kind of change for differentiating propionic aldehyde and acetone
MALDI-MS detection method is learned, the reagent ion of propionic aldehyde and acetone is differentiated as chemi-ionization using monokaryon transition metal ions,
Reach purpose that is effectively ionized and differentiating propionic aldehyde and acetone.
To achieve the above object, specifically adopt the following technical scheme that：
A kind of chemical ionization mass spectrometry detection method for differentiating propionic aldehyde and acetone, methods described comprises the following steps：
(1) it is made to produce mononuclear ion metal progress processing using physical-chemical process；
(2) the mononuclear ion obtained by step (1) is loaded into reaction tube using buffer gas；
(3) under test gas sample is sent into the reaction tube described in step (2), makes it with mononuclear ion in reaction tube
Reaction generation ionization product；
(4) by the ionization product described in step (3), device is detected after testing, according to the testing result of differential responses activity
Differentiate propionic aldehyde and acetone gas.
The application have chosen the suitable mononuclear cation of chemism for reagent ion, with propionic aldehyde or acetone
Reaction is learned, while efficient ionization propionic aldehyde and acetone, the production for the different characteristic for corresponding to propionic aldehyde and acetone respectively is directly formed
Thing ion.
According to the present invention, in step (1), the metal is transition metal, preferably post transition metal elements, described
Mononuclear ion is monokaryon late transition metal ion.
, according to the invention it is preferred to monokaryon transition metal ions be monokaryon late transition metal ion.The late transition metal
One kind for example, in osmium, cobalt, ruthenium, silver, nickel, gold, palladium, copper, rhodium, iron, iridium or platinum.Its produce monokaryon late transition metal from
Son, for example, osmium, cobalt, ruthenium, silver, nickel, gold, palladium, copper, rhodium, iron, the mononuclear ion of iridium or platinum.
The application preferably uses late transition metal ion as reacting metal ion, in the process of ionization propionic aldehyde and acetone
In, different reactivities are shown to propionic aldehyde and acetone, occurs hydride-transfer reaction with propionic aldehyde, then occurs first with acetone
Base anionotropy reacts, and the product ion of the two has obvious difference, the resolution available for propionic aldehyde and acetone.
According to the present invention, in step (1), the physical-chemical process is included in laser splash, magnetron sputtering or arc discharge
One kind, preferably laser splash, such as its laser frequency can be 1~2000Hz, preferably 10-200Hz.
According to the present invention, in step (2), the buffer gas is not lazy with propionic aldehyde or acetone and its ionization product reaction
Property gas, for example, one or more in helium, argon gas or nitrogen, its pressure be not less than 1atm, for example, 5atm；Its purity
For more than 98%, for example, 99.999% helium.
Using the inert gas not reacted with propionic aldehyde or acetone as buffer gas, it can be prevented with propionic aldehyde and acetone or
Had an effect with the ionization product of propionic aldehyde and acetone, it is to avoid impurity, which enters detector, influences final detection result.
According to the present invention, in step (3), before gaseous sample is sent into reaction tube, under test gas sample is first adjusted
Instantaneous pressure；The instantaneous pressure is about 0.01~1Pa, preferably 0.1~1Pa.
According to the present invention, in step (3), the under test gas sample is propionic aldehyde, acetone or the mixture of the two, but is surveyed
Before examination and do not know its be specially which kind of gas.
According to the present invention, in step (4), the detector is flight time mass spectrum, quadrupole rod mass spectrum or Fourier transformation
Ion cyclotron Resonance Mass Spectrometry, preferably flight time mass spectrum.
According to the present invention, in step (4), the testing result of propionic aldehyde is that mass-to-charge ratio occur be 57, one or both of 115
Peak, the testing result of acetone is the peak that mass-to-charge ratio is 43, one or both of 101 occur.
When occur in testing result mass-to-charge ratio for 57 or 115 when, or both simultaneously when occurring, you can sentenced according to testing result
Disconnected detection sample is propionic aldehyde gas；When occur in testing result mass-to-charge ratio for 43 or 101 when, or both simultaneously when occurring, you can
Judge detection sample for acetone gas according to testing result.Therefore, the present invention can incite somebody to action both areas according to different testing results
Separate.
The present invention also provides a kind of detection method of propionic aldehyde gas, it is characterised in that use as above step (1)-(4), when
When there is the peak that mass-to-charge ratio is 57, one or both of 115 in testing result, you can be judged as propionic aldehyde gas.
The present invention also provides a kind of detection method of acetone gas, it is characterised in that use as above step (1)-(4), when
When there is the peak that mass-to-charge ratio is 43, one or both of 101 in testing result, you can be judged as acetone gas.
Heretofore described post transition metal elements mean the metallic element in the periodic table of elements in 8-11 races.
Beneficial effects of the present invention：
The advantage of present invention is that it is reagent to choose the specific suitable monokaryon transition metal cation of chemism
Ion, chemically reacts with propionic aldehyde or acetone, while effectively ionized propionic aldehyde and acetone, produces and corresponds to propionic aldehyde and third respectively
The product ion of the different characteristic of ketone, can reach purpose that is effectively ionized and differentiating propionic aldehyde and acetone.The present invention in practice, no
It can only be used to the chemi-ionization of isomer propionic aldehyde and acetone, it may also be used for the chemical ionization mass spectrometry of propionic aldehyde and acetone in air
Detection and analysis.
Brief description of the drawings
Fig. 1 is the mass spectrogram that the two kinds of gas detections of embodiment 1-12 propionic aldehyde and acetone are obtained.
Embodiment
The methods and applications of the present invention are done below in conjunction with specific embodiment and further described in detail.It is following to implement
Example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.It is all to be based on this
In the range of the technology that invention the above is realized is encompassed by it is contemplated that protecting.
Unless otherwise indicated, raw material, instrument and the reagent used in following examples is commercial goods, or can be led to
Cross known method preparation.
Embodiment 1
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Osmium monokaryon cation is produced on late transition metal target osmium；
(2) carrier band of the osmium ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted osmium ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 2
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Rhodium monokaryon cation is produced on late transition metal target rhodium；
(2) carrier band of the rhodium ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted rhodium ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 3
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Golden monokaryon cation is produced on late transition metal target gold；
(2) carrier band of the gold ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted gold ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 4
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Palladium monokaryon cation is produced on late transition metal target palladium；
(2) carrier band of the palladium ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted palladium ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 5
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Ruthenium monokaryon cation is produced on late transition metal target ruthenium；
(2) carrier band of the ruthenium ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted ruthenium ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 6
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Silver-colored monokaryon cation is produced on late transition metal target silver；
(2) carrier band of the silver ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted silver ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 7
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Iridium monokaryon cation is produced on late transition metal target iridium；
(2) carrier band of the iridium ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted iridium ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 8
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Platinum monokaryon cation is produced on late transition metal target platinum；
(2) carrier band of the platinum ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted platinum ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 9
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Cobalt monokaryon cation is produced on late transition metal target cobalt；
(2) carrier band of the cobalt ions produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted cobalt ions fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 10
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Nickel monokaryon cation is produced on late transition metal target nickel；
(2) carrier band of the nickel ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.1~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted nickel ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 11
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Copper monokaryon cation is produced on late transition metal target copper；
(2) carrier band of the copper ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted copper ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
Embodiment 12
The present embodiment is in the reflection time-of-flight mass device equipped with pulsed laser deposition and quick flowing reactive pipe
Middle completion, comprise the following steps that：
(1) Nd is used3+：Two frequency doubled light 532nm pulse lasers (10Hz) of YAG laser, focus on translation and rotation
Iron monokaryon cation is produced on late transition metal target iron；
(2) carrier band of the iron ion produced in high-purity (99.999%) helium He (5atm) by first pulse valve control
Under, it is 2mm into internal diameter, outlet diameter is 1mm, and length is after length is 25mm tubule cooling by a diameter of 2mm
In 60mm quick flowing reactive pipe；
(3) propionic aldehyde and acetone gas are passed into quick flowing reactive pipe respectively using second pulse valve, and propionic aldehyde
Or the instantaneous pressure of acetone gas is about 0.01~1Pa, the moment total pressure (T=298K) in quick flow duct is about
1500Pa；
(4) after being reacted in quick flowing reactive pipe, product ion and unreacted iron ion fly out from reaction tube, warp
Conical nozzle (a diameter of 2mm) is crossed to be detected by reflection type flight time mass spectrometer.
Gained testing result is substantially as shown in Figure 1.
As shown in Figure 1, in embodiment 1~12, with propionic aldehyde hydride-transfer reaction occurs for metal ion, is directly formed
C3H5O+Ion, and with secondary reaction product ion C3H5O(C3H6O)+Formation, with acetone occur methyl anionotropy it is anti-
Should, directly form C2H3O+, while also with secondary reaction product ion C3H5O(C3H6O)+Formation, the lotus of the two product ion
Matter, can be by mass spectrometric resolution than difference, and reaction efficiency is very high, close to theory collision rate, can reach effectively ionized and differentiates
The purpose of propionic aldehyde and acetone, and for the chemical ionization mass spectrometry detection and analysis of propionic aldehyde and acetone in air.
More than, embodiments of the present invention are illustrated.But, the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of chemical ionization mass spectrometry detection method for differentiating propionic aldehyde and acetone, it is characterised in that comprise the following steps：
(1) it is made to produce mononuclear ion metal progress processing using physical-chemical process；
(2) the mononuclear ion obtained by step (1) is loaded into reaction tube using buffer gas；
(3) under test gas sample is sent into the reaction tube described in step (2), it is reacted with mononuclear ion in reaction tube
Generation ionization product；
(4) by the ionization product described in step (3), device is detected after testing, according to the testing result of differential responses activity
Differentiate propionic aldehyde and acetone gas.
2. the chemical ionization mass spectrometry detection method of propionic aldehyde and acetone is differentiated as claimed in claim 1, it is characterised in that step (1)
In, the metal is transition metal, and the mononuclear ion is monokaryon transition metal ions.
Preferably, the transition metal is post transition metal elements, and the monokaryon transition metal ions is monokaryon late transition metal
Ion.The late transition metal is, for example, one kind in osmium, cobalt, ruthenium, silver, nickel, gold, palladium, copper, rhodium, iron, iridium or platinum.It is produced
Monokaryon late transition metal ion, for example, the mononuclear of osmium, cobalt, ruthenium, silver, nickel, gold, palladium, copper, rhodium, iron, iridium or platinum from
Son.
3. the chemical ionization mass spectrometry detection method of propionic aldehyde and acetone is differentiated as claimed in claim 1 or 2, it is characterised in that step
(1) in, the physical-chemical process includes one kind in laser splash, magnetron sputtering or arc discharge, preferably laser splash, example
If its laser frequency can be 1~2000Hz, preferably 10-200Hz.
4. the chemical ionization mass spectrometry detection method of propionic aldehyde and acetone is differentiated as described in claim any one of 1-3, it is characterised in that
In step (2), the buffer gas for not with propionic aldehyde or acetone and its ionization product reaction inert gas, for example, helium,
One or more in argon gas or nitrogen, its pressure is not less than 1atm, for example, 5atm；Its purity is more than 98%, is, for example,
99.999% helium.
5. the chemical ionization mass spectrometry detection method of propionic aldehyde and acetone is differentiated as described in claim any one of 1-4, it is characterised in that
In step (3), before gaseous sample is sent into reaction tube, the instantaneous pressure of under test gas sample is first adjusted；The moment pressure
Power is about 0.01~1Pa.
Preferably, in step (3), the under test gas sample be propionic aldehyde, acetone or the mixture of the two, but test before simultaneously
Do not know which kind of gas it is specially.
6. the chemical ionization mass spectrometry detection method of propionic aldehyde and acetone is differentiated as described in claim any one of 1-5, it is characterised in that
In step (4), the detector be flight time mass spectrum, quadrupole rod mass spectrum or Fourier transform ion cyclotron resonance mass spectroscopy, it is excellent
Elect flight time mass spectrum as.
7. the chemical ionization mass spectrometry detection method of propionic aldehyde and acetone is differentiated as described in claim any one of 1-6, it is characterised in that
In step (4), the testing result of propionic aldehyde is the peak that mass-to-charge ratio is 57, one or both of 115, the testing result of acetone occur
To there is the peak that mass-to-charge ratio is 43, one or both of 101.
8. the chemical ionization mass spectrometry detection method of propionic aldehyde and acetone is differentiated as described in claim any one of 1-7, it is characterised in that
In step (4), when occur in testing result mass-to-charge ratio for 57 or 115 when, or both simultaneously when occurring, you can according to testing result
Judge detection sample for propionic aldehyde gas；When occur in testing result mass-to-charge ratio for 43 or 101 when, or both simultaneously when occurring, i.e.,
Detection sample can be judged for acetone gas according to testing result.
9. a kind of detection method of propionic aldehyde gas, it is characterised in that using as above any one of claim 1-6 steps (1)-
(4), when the peak that mass-to-charge ratio is 57, one or both of 115 occurs in testing result, you can be judged as propionic aldehyde gas.
10. a kind of detection method of acetone gas, it is characterised in that using as above any one of claim 1-6 steps
(1)-(4), when the peak that mass-to-charge ratio is 43, one or both of 101 occurs in testing result, you can be judged as acetone gas.
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