CN103263882A - Method and device for preparing water free radical cationic cluster in atmospheric pressure environment - Google Patents
Method and device for preparing water free radical cationic cluster in atmospheric pressure environment Download PDFInfo
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- CN103263882A CN103263882A CN2013101438964A CN201310143896A CN103263882A CN 103263882 A CN103263882 A CN 103263882A CN 2013101438964 A CN2013101438964 A CN 2013101438964A CN 201310143896 A CN201310143896 A CN 201310143896A CN 103263882 A CN103263882 A CN 103263882A
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Abstract
The invention discloses a method and a device for preparing a water free radical cationic cluster in an atmospheric pressure environment. The method is characterized in that high voltage of 3-6KV is applied to the tip of a stainless steel conical discharge needle in the presence of a certain humidity of air as a reagent under the ordinary pressure so that through high-voltage corona discharge, the water free radical cationic cluster (H2O)n<+> is produced. The device comprises an ionization reaction chamber having a framework structure. An ionization channel and an output channel are arranged in the ionization reaction chamber. The stainless steel conical discharge needle is arranged in the ionization channel. Parts of the stainless steel conical discharge needle but the tip and the tail end connected to the high voltage power supply are coated with insulation varnish. An auxiliary gas channel which can introduce a certain humidity of air into the ionization reaction chamber through the ionization channel is arranged in the ionization channel. The method and the device can realize preparation of a large amount of the water free radical cationic clusters under the conditions of a normal temperature and normal pressure.
Description
Technical field
The present invention relates to biologic medical, mass spectral analysis, catalysis, synthetic and correlative technology fields such as radiation chemistry, gas discharge physics, be specifically related to prepare under a kind of atmospheric pressure environment method and the device of water radical cation cluster.
Background technology
Water is Source of life, is the mankind's one of indispensable valuable sources of depending on for existence and development.Water radical cation and cluster are produced through overshoot (solar ultraviolet radiation, X-radiation etc.) or simple ionization (electronics, cosmic ray) by water, are one of main components of air ion on the middle and senior level.Water radical cation cluster (H
2O)
n +.Reactivity is very strong, very easily react with a series of nonpolar organic compound molecules, the hydroxyl radical free radical of its generation is the key factor that causes mankind aging and numerous disease, for example cancer, multiple sclerosis, Parkinson disease, disease of immune system etc.Therefore, the preparation of big water gaging radical cation cluster and research are extremely important for promotion biologic medical, celestial body and atmospheric physics, water ecological environment, catalysis, the synthetic development that reaches ambits such as radiation chemistry, mass spectral analysis.
Yet because free radical is very active, the life-span is very short, and its existence depends on specific reaction environment, and preparation and the research of the radical cation cluster that therefore feeds water have brought great difficulty.At present, preparation water radical cation cluster generally is to carry out in solution, and main method comprises, electron radiation method, hydrogen peroxide method etc.Gas phase water radical cation cluster is utilized ultrasonic molecular beam and electron impact mass spectra method usually or is prepared and characterizes by the VUV photoionization, but these methods generally all are to carry out under vacuum condition, and the needed device volume of using is huge, energy consumption is high, preparation has the harm accessory substance, it is big etc. that environmental condition is relied on.Therefore, research and the application for water radical cation cluster has significant limitation.
From the above, the method for preparing water radical cation cluster at present has many deficiencies, invents a kind of method that can be at normal temperatures and pressures can fast and stable prepares a large amount of water radical cation clusters, has great importance for satisfying real needs.
Summary of the invention
In view of this, technical problem to be solved by this invention is: a kind of method and the device that can stablize the big water gaging radical cation cluster of preparation under the normal temperature and pressure environment is provided.
In order to achieve the above object, the present invention adopts following technical scheme to realize:
The invention provides the method for preparing water radical cation cluster under a kind of atmospheric pressure environment, wherein, adopt a stainless conical spray point, by needle point being imposed 3～6KV high pressure, air with certain humidity under the normal pressure is reagent, produces water radical cation cluster (H by high-voltage corona discharge
2O)
n +.
As preferably, be after 40～60% air sends spray point to humidity, the high voltage that spray point is added 3.5kV, the most advanced and sophisticated corona discharge that produces of spray point, airborne steam is ionized to the radical cation of water and protonated ion, be provided with a taper to electrode at described spray point needle point horizontal range 22mm place, and make the temperature of the output channel of above-mentioned ion remain on 140 ℃.
The present invention also provides the device of preparation water radical cation cluster under a kind of atmospheric pressure environment, wherein, it has an ionization reaction cavity of frame structure, inside is provided with an ionization channels, an output channel, a stainless conical spray point and is located in the described ionization channels, described spray point removes needle point and connects the high-tension electricity part and all scribbles insulated paint, and described ionization channels inside also is provided with the air that can introduce to have certain humidity enters the ionization reaction cavity by described ionization channels assist gas passage.
As preferably, a described ionization reaction cavity also built-in sample is introduced passage, a taper to electrode, described output channel is located at described taper on the electrode, described ionization channels and sample are introduced interchannel angle be 60～90 °, ionization channels and taper to interelectrode angle be 60～80 °, passage introduced by sample and taper is 60～80 ° to interelectrode angle.
As preferably, comprise that also one can regulate and control ring heater to the temperature of electrode to taper, described ring heater is located at described taper to outside the output channel in the electrode.
As shown from the above technical solution, the invention has the beneficial effects as follows:
Compared to existing technology, spray point that the present invention is put most advanced and sophisticated with taper to the opening part of electrode on same horizontal line, the prepared ion in discharge back is exported by output channel, among the present invention, one gas interface is arranged in the ionization channels, be characterized in: when air humidity is low, can pass through water blow bubble method supplementing water steam; When air humidity is higher, also can the airborne steam of obstructed any gas direct ionization, the general control of air humidity is advisable 60%.The present invention also provide a kind of can be at normal temperatures and pressures, the water radical cation cluster that the preparation of fast and stable is a large amount of can be carried out the molecular ion reaction with the sample that feeds.In the described mass spectrometric analysis method, assist gas is inert gases such as the nitrogen that has steam, helium, argon gas.Sample is introduced the sample that passage is introduced, and is generally the sample of gaseous sample or atomizing.
Adopt above design, the present invention is directly used in scientific research in a large amount of water radical cation cluster of the preparation of ionization channels discharge stability in output channel output; Also can feed other chemical substance at sample introducing passage and carry out the molecular ion reaction when ionization channels prepare big water gaging free radical, product is exported from output channel.Its design is ingenious, easy to use, has wide range of applications, and can greatly impetus be arranged to biologic medical, celestial body and atmospheric physics, water ecological environment, catalysis, the synthetic development that reaches numerous areas such as radiation chemistry, mass spectral analysis.
Description of drawings
Fig. 1 the present invention prepares structure and the operation principle schematic diagram of the device of water radical cation cluster under atmospheric pressure environment.
The one-level scanning of the mass spectrum figure of the water radical cation cluster that Fig. 2 the present invention prepares under atmospheric pressure environment.
The mass spectrogram that the water radical cation cluster that Fig. 3 the present invention prepares under atmospheric pressure and the reaction of acetone obtain.
The mass spectrogram that the water radical cation cluster that Fig. 4 the present invention prepares under atmospheric pressure and the reaction of ammonia obtain.
The mass spectrogram that the water radical cation cluster that Fig. 5 the present invention prepares under atmospheric pressure and the reaction of methyl alcohol obtain.
The mass spectrogram that the water radical cation cluster that Fig. 6 the present invention prepares under atmospheric pressure and the reaction of ethanol obtain.
The mass spectrogram that the water radical cation cluster that Fig. 7 the present invention prepares under atmospheric pressure and propyl alcohol reaction obtain.
The specific embodiment
In order to make those skilled in the art can further understand feature of the present invention and technology contents, see also following about detailed description of the present invention and accompanying drawing.
The technical solution used in the present invention is, can stablize method and the device of the big water gaging radical cation cluster of preparation under a kind of atmospheric pressure environment, adopt a stainless conical draw point, by to needle point high-pressure (3～6KV), air (about 60%) with certain humidity under the normal pressure is reagent, produces water radical cation cluster (H by high-voltage corona discharge
2O)
n +.Its device mainly comprises an ionization reaction cavity, the built-in ionization channels of described ionization reaction cavity, establish an assist gas passage in the described ionization channels, put a spray point in the described assist gas passage, described spray point end is connected to a high voltage source interface, the space angle of described ionization channels in reaction cavity can be regulated, the built-in sample of described ionization reaction cavity is introduced passage, described sample is introduced the space angle of passage in reaction cavity and can be regulated, the built-in taper of described ionization reaction cavity is to electrode, described taper is to establishing an output channel in the electrode, described output channel external one has ring heater, described ring heater can be controlled temperature, described output channel can be coupled with the ion transfer tube of mass spectrometer, and described reaction cavity disposes a horizontal range and regulates card, and described horizontal range is regulated card and can be regulated the horizontal range of electrode ionization reaction cavity and taper.Its main feature is: spray point most advanced and sophisticated with taper to the opening part of electrode on same horizontal line, the prepared ion in discharge back is exported by output channel.On the spray point in its ionization channels a high voltage interface is arranged, the angle between ionization channels and horizontal plane can be regulated, and ionization channels and taper can be regulated interelectrode distance, and output channel can link to each other with spectrometer interface.Output channel can with the reaction cavity interface.
Specifically see also Fig. 1 and shown in Figure 7, describe apparatus structure and the operation principle that the present invention prepares big water gaging radical cation cluster at normal temperatures and pressures in detail below in conjunction with accompanying drawing.
Fig. 1 is basic comprising and the operation principle of water radical cation cluster preparation facilities under the atmospheric pressure of the present invention.Whole system comprises: 1. ionization channels, and 2. sample is introduced passage, and 3. taper is to electrode, 4. output channel, 5. assist gas passage, 6. spray point, 7. gas circuit pipe, 8. sample pipe, 9. reaction cavity, 10. annular electro heater, 11. horizontal horizontal ranges are regulated card.Length and angle that ionization channels 1 inserts reaction cavity can be regulated, sample is introduced length and the angle of passage 2 insertion reaction cavities and can be regulated, taper is fixed on the inside of reaction cavity to electrode, output channel 4 is connected to cavity and also can be connected with the mass spectrum mouth outward, assist gas passage 5 can be coupled with gas pipeline for insulating materials, spray point 6 removes needle point and connects the high-tension electricity part and all scribbles insulated paint, gas circuit pipe 7 is insulating materials, sample pipe 8 is the acid-alkali-corrosive-resisting material, and reaction cavity 9 is the insulating materials cavity.Ionization channels 1 and taper are 60 °＜α＜80 ° to the angle of 3 at electrode, the angle that ionization channels 1 and sample are introduced 2 in passage is 60 °＜β＜90 °, it is 60 °＜γ＜80 ° to the angle of 3 at electrode that sample is introduced passage 2 and taper, ionization channels spray point tip and taper are about 22mm to the optimum optimization distance of eletrode tip, annular electro heater 10 can carry out adjusting and the control of temperature to output channel, temperature optimization value for the water radical cation cluster that produces maximum abundance is about 140 ℃, and the optimal value of voltage is 3.5kV.
Feed after humidity is 40～60% gas from the assist gas passage, the high voltage that spray point is added 3.5kV, the most advanced and sophisticated corona discharge that produces of spray point, airborne steam is ionized to the radical cation of water and protonated ion, optimize the voltage (V=3.5kV) of spray point by experiment, spray point and taper can obtain the bigger radical cation cluster of abundance to the horizontal range (d=22mm) of electrode and the temperature (T=140 ℃) of ion output channel.At this moment, also can introduce at sample and feed atomized sample in the passage, sample molecule and the reaction of water radical cation cluster generation molecular ion obtain product in reaction cavity, export from output channel.
Describe application of the present invention in detail below in conjunction with instantiation, preparation facilities prepares a large amount of water radical cation clusters to utilize this to install at normal temperatures and pressures, carry out the molecular ion reaction with the sample molecule (acetone, ammonia, methyl alcohol, ethanol, propyl alcohol) of different chemical characteristic, obtain different product.In this exemplary application, the output channel of the preparation facilities of water radical cation cluster under the atmospheric pressure is linked to each other with mass spectrometer, can obtain the spectrogram information of product, thereby product be carried out qualitative and quantitative.
Spray point is added high voltage, adjust the discharge needle point to the distance of taper to electrode, from mass spectrogram, can observe, a large amount of water radical cation cluster m/z36 and m/z54 are arranged, as shown in Figure 2.Illustrate that then water radical cation cluster preparation facilities can prepare a large amount of water radical cation clusters under the atmospheric pressure environment, and the output channel by device.In the research of water radical cation cluster is used, can directly collect use in output channel.
Acetone is a kind of good solvent, extractant, also is a kind of important organic synthesis raw material, obtains widely using at chemical industry with in industrial synthesizing.Acetone is more stable at normal temperatures, be difficult for oxidized, and as acetone and water radical cation cluster (H
2O)
2 +After the m/z36 combination, it is active that character can become, and easy and other material prepares corresponding chemical reaction.As Fig. 3, be acetone and water radical cation cluster reaction of formation product m/z76.This has significance in industry in the synthetic and catalytic reaction.
Ammonia is a kind of important raw material of industry, use widely at chemical field, the affine energy of the proton of ammonia is higher, after being ionized, can only give the affine sample molecule that can be higher of proton with electric charge or proton transfer, therefore, with the carrier of ammonia as electric charge and energy transmission, has the certain selectivity ionization.As Fig. 4, be ammonia and water radical cation cluster reaction primary product m/z35.
Methyl alcohol is the simplest saturated alcohols, also is important chemical industry basic material and clean fuel liquid, and it is widely used in the industry such as organic synthesis, medicine, agricultural chemicals, coating, dyestuff, automobile and national defence.The proton of methyl alcohol is affine can be lower, therefore, easily with electric charge or proton transfer give sample molecule, with methyl alcohol as electric charge and carrier of energy, can the most sample molecule of ionization.As Fig. 5, for the product of methyl alcohol and water radical cation cluster is m/z50.
Water radical cation cluster chemical property is very active, can react with polarity, low pole even nonpolar sample molecule, changes the activity of sample molecule, is a kind of good ion selective reagent in mass spectral analysis therefore; Because the very high chemism of water radical cation cluster also is a kind of good chemical catalyst, and potential using value is arranged in chemical synthesis; Simultaneously, water radical cation and cluster are the important products of atmospheric discharge layer, and the hydroxyl radical free radical of its generation also is the important research object of radiotherapy and water ecological environment process.As Fig. 6 and Fig. 7, be respectively the spectrogram that the reaction of water radical cation cluster m/z36 and ethanol, propyl alcohol obtains.
Output channel of the present invention can be connected with spectrometer interface.
Step 1: the assist gas passage that will have steam is connected gas, and flow velocity is 300psi;
Step 2: impose 3～6kV high pressure at spray point;
Step 3: introduce passage from sample and feed sample, flow velocity is 20～50 μ L/min;
Step 4: start the mass spectrograph scanning system, obtain the spectrogram behind water radical cation cluster and the example reaction.
Horizontal range is regulated to be preferably on the card and is provided with scale, can regulate as required.Taper has a ring heater outward to the output channel in the electrode, according to the stability size that generates ion, can regulate and control the temperature of electrode taper.Be provided with a sample inlet tube in the ionisation chamber, feed sample and can react or be ionized the preparation secondary ion with the water radical cation cluster of preparation.Ionization channels and sample are introduced passage and taper can be carried out free adjustment (5～30mm) to interelectrode distance.
Apparatus structure of the present invention is simple, and low cost of manufacture can satisfy existing research to water radical cation and cluster and application demand.
But the above only is preferable possible embodiments of the present invention, is not in order to limiting to claim of the present invention, thus the equivalent structure that all utilizations specification of the present invention and accompanying drawing content are done change, all in like manner within the scope of the present invention.
Claims (5)
1. the method for preparing water radical cation cluster under the atmospheric pressure environment, it is characterized in that, adopt a stainless conical spray point, by needle point being imposed 3～6KV high pressure, air with certain humidity under the normal pressure is reagent, produces water radical cation cluster (H by high-voltage corona discharge
2O)
n +.
2. the method for preparing water radical cation cluster under the atmospheric pressure environment as claimed in claim 1, it is characterized in that, be after 40～60% air sends spray point to humidity, the high voltage that spray point is added 3.5kV, the most advanced and sophisticated corona discharge that produces of spray point, airborne steam is ionized to the radical cation of water and protonated ion, is provided with a taper to electrode at described spray point needle point horizontal range 22mm place, and makes the temperature of the output channel of above-mentioned ion remain on 140 ℃.
3. the device of preparation water radical cation cluster under the atmospheric pressure environment, it is characterized in that, it has an ionization reaction cavity of frame structure, inside is provided with an ionization channels, an output channel, a stainless conical spray point and is located in the described ionization channels, described spray point all scribbles insulated paint except needle point and end connect the high-tension electricity part, described ionization channels inside also is provided with the air that can introduce to have certain humidity enters the ionization reaction cavity by described ionization channels assist gas passage.
4. the device for preparing water radical cation cluster under the atmospheric pressure environment as claimed in claim 3, it is characterized in that, a described ionization reaction cavity also built-in sample is introduced passage, a taper to electrode, described output channel is located at described taper on the electrode, described ionization channels and sample are introduced interchannel angle be 60～90 °, ionization channels and taper to interelectrode angle be 60～80 °, passage introduced by sample and taper is 60～80 ° to interelectrode angle.
5. the device for preparing water radical cation cluster under the atmospheric pressure environment as claimed in claim 4, it is characterized in that, comprise that also one can regulate and control ring heater to the temperature of electrode to taper, described ring heater is located at described taper to outside the output channel in the electrode.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110018221A (en) * | 2019-03-02 | 2019-07-16 | 金华职业技术学院 | A kind of test device of the metal cluster of chemical modification |
| CN110482505A (en) * | 2019-09-12 | 2019-11-22 | 东华理工大学 | A method of azanol is prepared using nitrogen |
| CN112661108A (en) * | 2020-12-08 | 2021-04-16 | 东华理工大学 | Hydrogen preparation method based on hydrodimer free radical cation |
-
2013
- 2013-04-14 CN CN2013101438964A patent/CN103263882A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 贾滨: ""表面解吸常压化学电离的机理及其在食品和医药样品分析中的应用研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110018221A (en) * | 2019-03-02 | 2019-07-16 | 金华职业技术学院 | A kind of test device of the metal cluster of chemical modification |
| CN110482505A (en) * | 2019-09-12 | 2019-11-22 | 东华理工大学 | A method of azanol is prepared using nitrogen |
| CN110482505B (en) * | 2019-09-12 | 2022-08-26 | 东华理工大学 | Method for preparing hydroxylamine by using nitrogen |
| CN112661108A (en) * | 2020-12-08 | 2021-04-16 | 东华理工大学 | Hydrogen preparation method based on hydrodimer free radical cation |
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Inventor after: Ouyang Yongzhong Inventor after: Hong Feng Inventor after: Jia Bin Inventor after: Chen Huanwen Inventor before: Hong Feng Inventor before: Jia Bin Inventor before: Ouyang Yongzhong |
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Application publication date: 20130828 |