CN208013135U - A kind of electrochemistry-mass spectrometry device - Google Patents
A kind of electrochemistry-mass spectrometry device Download PDFInfo
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- CN208013135U CN208013135U CN201820471407.6U CN201820471407U CN208013135U CN 208013135 U CN208013135 U CN 208013135U CN 201820471407 U CN201820471407 U CN 201820471407U CN 208013135 U CN208013135 U CN 208013135U
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Abstract
The utility model is related to a kind of electrochemistry-mass spectrometry device, solve prior art construction is complicated, manufacture difficulty is high, operation difficulty is big, the stability of electrochemical reaction and poor continuity, be not suitable for progress to complicated electrochemical system in real time, in-situ monitoring with analysis the technical issues of.The utility model provides a kind of electrochemistry-mass spectrometry device, including mass spectrograph and electrochemical reaction appts, electrochemical reaction appts are equipped with power work station, electrochemical electrode combination and electrochemical reaction platform, electrochemical reaction platform is the carrier at least provided with a wedge angle, and a wedge angle of carrier is set as sample angle；Electrochemical electrode combination provides the ionization spray voltage of the voltage and sample solution of electrochemical reaction by power work stand control, makes the testing sample solution at sample angle that electrochemical reaction occur and generates electron spray ionisation, the ion of electron spray enters mass spectrum injection port.The utility model is widely used in electrochemical analysis techniques field.
Description
Technical field
The utility model is related to electrochemical analysis techniques fields, and in particular to a kind of electrochemistry-mass spectrometry device.
Background technology
Electrochemistry and spectral technique are mainly selected in traditional electrochemical reaction mechanism research.However, these methods are limited
In lower detectability and poor chemical analysis specificity.Mass spectrum have high sensitivity, the good, analyze speed of selectivity it is fast,
Can be with real time parsing the features such as, thus by mass spectrum (mass spectrometry, MS) and electrochemistry (electrochemistry,
EC) reaction platform combines composition electrochemistry-mass spectrum (MS-EC) device, for monitoring and analyzing electrochemical reaction process and centre
Product is increasingly becoming forward position and the hot spot of electrochemical reaction mechanism research field.The core component of electrochemistry-mass spectrometric apparatus is electricity
Platform is chemically reacted, effect is both the control unit of electrochemical reaction and mass spectrographic ion source, may be implemented to chemically react
Real-time, in-situ monitoring.Electrochemical reaction platform is usually made of three-electrode system and reaction solution storage pool, wherein three electrode bodies
Owner will include working electrode (working electrode), to electrode (counter electrode) and reference electrode
(reference electrode).And according to the electrochemical properties of analyte, can include using different electrochemical methods
Constant voltage process, constant current anodizing process and cyclic voltammetry realize the electrochemical reaction of analyte.In recent years, it uses with EFI
Mist ion source (ESI) and its derivative ion source are the atmospheric pressure ion source formula electrochemical reaction platform of representative to electrochemical polymerization process
Carrying out real-time, in-situ monitoring becomes the mainstream of electrochemistry-mass-spectrometric technique development.2015, Zare etc. parsed electricity by electron spray
It is combined from-mass spectrum (DESI-MS) and electrochemical reaction appts, successfully captures n,N-Dimethylaniline (DMA) electrochemical polymerization
Dimer (the DMA that process generates+) and other aromatic amines, further specify the Principles of Polymerization of the substance, electricity
Chemical reaction equipment mainly constructs：Be capable of rotation justifies wheel, platinum to electrode, Ag/AgCl reference electrodes and reaction tank.Circle
Wheel surface is covered by platinum and is partially disposed in reaction tank, and effect is working electrode while being also sampler.In electrochemistry
In reaction process, circle wheel by itself rotate being formed on its surface one layer of electrochemical reaction liquid, using air blast by reaction solution from
Circle wheel surface takes mass spectrum entrance to, to realize sample analysis.2016, Qiu etc. used electric spray ion source-mass spectrum (ESI-
MS it) is combined with electrochemistry deinstall, to the electrochemistry electricity of dopamine and uric acid electrochemical oxidation process and bipyridyl ruthenium (II)
Photoluminescence mechanism is studied, and by capturing, analyzing each self-reacting intermediate product, demonstrates the electrochemistry of different kind of material
Reaction mechanism.This electrochemical reaction appts includes mainly that ultra micro electrochemical reaction platform and piezoelectric type pistol form.Wherein, ultra micro
Electrochemical reaction platform tip portion is integrated with three-electrode system, and (glass carbon working electrode, silver is to electrode and Ag/AgCl reference electricity
Pole) and reaction liquid pool, after reaction solution is injected ultra micro electrochemical reaction cell, ion stream is generated by piezoelectric type pistol, is being excited
Ionization spray is generated while electrochemical reaction and enters mass spectrum, completes sample analysis.
These above-mentioned gerotor types open wide electrochemistry-mass spectrometric apparatus have the advantages that it is respective, but each method there is also
Certain limitation.For example, using runner as working electrode and sampler, the method is not really real-time, in situ to supervise
It surveys, as wheel rotates, detectable substance is detached from original electrochemical reaction system under the action of the centrifugal, cannot be introduced into mass spectrum and is divided
Analysis.Rotation process can also influence the stability and continuity of electrochemical reaction, and the apparatus structure is complicated, wheel quick rotation
It is uncertain more, it is more difficult to promote and apply；Ultra micro electrochemical reaction platform structure is complicated, manufacture difficulty is high, it is difficult to ensure that system every time
The consistency of work, and the moment ion stream generated by piezoelectric type pistol, can not ensure that the reaction solution in its platform has carried out
Whole electrochemical reaction is not suitable for that the electrochemical reaction of complex system is monitored and is analyzed, and adds piezoelectric type pistol
Not ripe product, and can not be obtained by buying, to influence its popularization and application.
Utility model content
The purpose of this utility model be exactly in order to overcome the above-mentioned deficiencies of the prior art, provide it is a kind of it is simple in structure, be convenient for
It manufactures, operate electrochemistry-mass spectrometric platforms that facility, the stability of electrochemical reaction and continuity are high, ion transmission efficiency is high, energy
Enough electrochemical reactions to complex system carry out real-time, in-situ monitoring and analysis electrochemistry-mass spectrometry device.
The utility model solves above-mentioned technical problem, and the scheme of use is：
A kind of electrochemistry-mass spectrometry device, including mass spectrograph and electrochemical reaction appts, mass spectrograph are equipped with injection port,
Electrochemical reaction appts are equipped with power work station and electrochemical electrode combines, and it is flat that electrochemical reaction appts are additionally provided with electrochemical reaction
Platform, electrochemical reaction platform are the carrier at least provided with a wedge angle, and a wedge angle of carrier is set as sample angle；Electrochemical electrode
Combine through power work stand control while being provided the voltage needed for generation electrochemical reaction to testing sample solution and to sample
Voltage difference is provided between angle and injection port, makes the testing sample solution at sample angle that sample to be tested while electro-chemical reaction occur molten
Liquid generates electron spray ionisation；Sample angle is close to each other with injection port, and the ion of electron spray ionisation is made to enter injection port；Electrochemistry electricity
Pole combination is equipped with working electrode and to electrode.
Preferably, power work station is combined to electrochemical electrode provides the input mode of supply voltage as constant voltage input
Method, constant current input method or isosceles triangle pulse voltage input method any of which.
Preferably, electrochemical electrode combination is additionally provided with reference electrode.
Preferably, carrier material is insulator.
Preferably, insulator is quartz, glass.
Preferably, carrier material is conductor.
Preferably, conductor is platinum, glass carbon any of which.
Preferably, it is integrally provided with insulation cover outside carrier and the injection port, insulation cover is by carrier, injection port and electricity
Pole combination sealing covers.
The beneficial effects of the utility model：
(1) a kind of electrochemistry-mass spectrometry device provided by the utility model, it is by electrochemical reaction appts and mass spectrum
Instrument is combined, and reaches real-time, the in-situ monitoring to electrochemical reaction whole process.The use principle of utility model device is：Electricity
It is combined with electrochemical reaction platform horn structure using electrode combination in chemical reaction equipment, it will be raw in electrochemical reaction process
At substance directly by electron spray ionisation, ion enters mass spectrum, realizes to the real-time, former of sample solution electrochemical reaction process
Position detection and analysis.
(2) a kind of electrochemistry-mass spectrometry apparatus structure provided by the utility model is simply convenient for making, and is using process
In, first sample solution is added drop-wise at the sample angle of electrochemical reaction platform, sample solution drop did not had electrode bottom end, applied electricity
Pressure Δ V makes electrochemical reaction, it is ensured that the stability and continuity of electrochemical reaction；It is passed through voltage I to working electrode
For V1；It is V to voltage II is passed through to electrode1-ΔV；The voltage of injection port is V2, Δ HV=│ V1-V2│, wherein Δ HV are sample angles
Voltage difference between injection port makes the testing sample solution at carrier tip generate electron spray ionisation, under the two synergistic effect
Cleverly the product in electrochemical reaction whole process is brought into mass spectrum by electron spray ionisation in real time, carries out inspection real-time, in situ
Survey analysis；Such mode can not only ensure that electrochemical reaction occurred for working electrode surface on electrochemical reaction platform, but also can protect
It demonstrate,proves while generating electron spray ionisation, the free radical etc. that some are unstable and chemism is high can will be generated in electrochemical reaction process
Substance, instantaneous orientation are sent to mass spectrometric injection port, complete the analysis detection of sample solution into mass spectrum, and in whole process from
Sub- transmission efficiency is high, can carry out real-time, in-situ monitoring and analysis to the electrochemical reaction of complex system.
(3) electrochemical reaction appts are additionally provided with electrochemical reaction platform, and electrochemical reaction platform is at least provided with a point
One wedge angle of the carrier at angle, carrier is set as sample angle；Electrochemical electrode combination provides electrochemical reaction by power work station
The voltage of required voltage and electron spray makes the testing sample solution at sample angle generate electrochemical reaction while electron spray occurs
Ionization；Sample angle and mass spectrum injection port are close to each other, and electron spray is made to enter mass spectrum injection port.Due to sample angle with it is mass spectrometric into
There are voltage difference and sample angle and mass spectrum injection port close to each other between sample mouth, the ion that electron spray ionisation generates is made to pass through sample introduction
Mouth enters mass spectrum, realizes the real-time of electrochemical reaction process, in situ detection analysis.
(4) a kind of electrochemistry-mass spectrometry device provided by the utility model operates facility during entire use, surely
Qualitative height does not need excessive complicated debugging process, the moment ion stream that need not be generated by piezoelectric type pistol, it is ensured that
Stable and reliable ion stream is generated every time.
Description of the drawings
Fig. 1 is the structural schematic diagram (being not added with insulation cover) of the front view of the utility model embodiment 1；
Fig. 2 is the structural schematic diagram (being not added with insulation cover) of the vertical view of the utility model embodiment 1；
Fig. 3 is the structural schematic diagram of the carrier of Fig. 2；
Fig. 4 is the structural schematic diagram (adding insulation cover) of the front view of the utility model embodiment 1；
Fig. 5 is the structural schematic diagram (adding insulation cover) of the stereogram of the utility model embodiment 1；
Fig. 6 is the structural schematic diagram (being not added with insulation cover) of the vertical view of the utility model embodiment 2；
Fig. 7 is the structural schematic diagram of the carrier of Fig. 6；
Fig. 8 is the structural schematic diagram (adding insulation cover) of the vertical view of the utility model embodiment 2.
It is marked in figure：1. power work station, 2. carriers, the combination of 3. electrochemical electrodes, 4. mass spectrographs, 5. sample angle drop sides
Edge line, 6. sample angles, 7. injection ports, 8. working electrodes, 9. pairs of electrodes, 10. reference electrodes, 11. insulation covers, A1. samples angle
Vertex, A2. injection ports center, the bottom end of A3. working electrodes, A4. is to the bottom end of electrode, the bottom end of A5. reference electrodes, and L is straight
Line, the distance of the vertex A1 to injection port center A2 at S1. samples angle, the vertex A1 of the bottom end A3 of S2. working electrodes to sample angle
Distance, S3. is to the distance of the bottom end A4 to straight line L of electrode, the distance of the bottom end A5 to straight line L of S4. reference electrodes 10.
Specific implementation mode
The utility model is described in further detail in the following with reference to the drawings and specific embodiments, to help the utility model is understood
Content.Method used in the utility model is conventional production method unless otherwise required；Used raw material and
Equipment is unless otherwise required conventional commercial product.
Embodiment 1
As shown in FIG. 1 to 3, a kind of electrochemistry-mass spectrometry device, including mass spectrograph 4 and electrochemical reaction appts, matter
Spectrometer 4 is equipped with injection port 7, and electrochemical reaction appts are equipped with power work station 1 and electrochemical electrode combination 3, electrochemical reaction dress
It sets and is additionally provided with electrochemical reaction platform, the sheet glass carrier 2 that electrochemical reaction platform is square, the sheet glass specification
Length × width × height is 18mm × 18mm × 0.15mm, and a wedge angle of the sheet glass of square is set as sample angle 6, sample angle 6
Edge be equipped with sample angle drop edge line 5.
Electrochemical electrode combination 3 is three electrode combinations, is equipped with working electrode 8, to electrode 9 and reference electrode 10, wherein：
Platinum circle is working electrode 8, and platinum disk is to electrode 9, and Ag/AgCl is reference electrode 10；The bottom of electrochemical electrode combination 3
End：The bottom end A3 of working electrode, the bottom end A4 of electrode and the bottom end A5 of reference electrode are located in sample angle 6 and are carried with sheet glass
The upper surface of body 2 contacts；The bottom end of electrochemical electrode combination 3 is not in contact with each other and bottom end is distributed.
Electrochemical electrode combination 3 is controlled anti-to electrochemistry is provided between sample angle 6 and injection port 7 by power work station 1
Voltage and electron spray voltage are answered, the testing sample solution at sample angle 6 is made to generate electrochemical reaction and generates electron spray ionisation；Sample
Product angle 6 and injection port 7 are close to each other, and the distance S1 of the vertex A1 to injection port center A2 at sample angle is 3.5mm, makes generation EFI
Ion after mist can be detected into injection port 7.
The bottom end A3 of working electrode, the vertex A1 at sample angle and injection port center A2 on same straight line L, working electrode
The distance of bottom end A3 to the vertex A1 at sample angle is less than the distance of the vertex A1 of the bottom end A4 to electrode to sample angle, working electrode
Bottom end A3 to sample angle vertex A1 distance be less than reference electrode bottom end A5 to sample angle vertex A1 distance；Work
The distance S2 of the bottom end A3 of electrode to the vertex A1 at sample angle is 2.5mm, to the distance S3 and ginseng of the bottom end A4 to straight line L of electrode
Distance S4 than the bottom end A5 of electrode 10 to straight line L is equal, and respectively 3mm is most preferably that the electron spray generated at this time sprays outward
The vertex A1 and injection port center A2 in the direction and sample angle penetrated on the same line, keep the complete substance of ionization accurate
Completely into injection port 7, the real-time of sample solution electrochemical reaction process, in situ detection analysis are completed into mass spectrograph 4.
As shown in Figure 4, Figure 5, it is integrally provided with insulation cover 11 outside sheet glass carrier 2 and injection port 7, insulation cover 11 will
Sheet glass carrier 2 and the sealing of injection port 7 cover, and electrochemical electrode combination 3 is each passed through insulation cover 11, on the one hand, insulation is outer
Cover 11 using high-voltage electricity during sample detection it is possible to prevente effectively from cause Danger Electric shock risk；On the other hand, insulation cover 11 can be with
Ambient enviroment is influenced caused by testing result during reducing sample detection, final to ensure that detection process is stablized, detection data
As a result reliable.
Power work station 1, mainly by high voltage power supply, relay switching circuit, resistor voltage divider circuit, signal coupling coil etc.
Composition.Power work station 1 is that electrochemical electrode combination 3 provides electrochemical reaction voltage；Working electrode in electrochemical electrode combination 3
8 connect one circuit of composition with to electrode 9 by reaction solution, and electrochemical electrode combination 3 is controlled by power work station 1 to sample
Voltage is provided between angle 6 and injection port 7, make the testing sample solution at sample angle 6 that electrochemical reaction occur while generating EFI
Mist ionizes；Working electrode 8 and there are voltage differences to ensure that electrochemical reaction occurs on working electrode 8 between electrode 9；Reference
Electrode 10 is used for the potential change of monitoring electrode 8.The voltage signal input mode that supply unit provides is that constant voltage is defeated
Enter or constant current inputs or isosceles triangle pulse voltage input any of which.
A kind of application method of above-mentioned electrochemistry-mass spectrometry device, specific steps are followed successively by：
First testing sample solution is injected in the 6 sample angle drop edge line 5 of sample angle of electrochemical reaction platform, electrochemistry
Working electrode 8 in electrode combination 3 is immersed in testing sample solution the bottom end of electrode 9 and reference electrode 10 respectively, and and glass
Glass piece carrier 2 contacts；Electrochemical electrode combination 3, which controls to provide to testing sample solution simultaneously by power work station 1, occurs electricity
It chemically reacts required voltage and provides voltage difference between sample angle 6 and injection port 7, test sample is waited at sample angle 6 to excite
Product solution occurs testing sample solution while electro-chemical reaction and generates electron spray ionisation：1) during use, when 4 sample introduction of mass spectrograph
Voltage V at mouth 72In the case of for 0 volt or low-voltage, voltage I (V are passed through to working electrode 81) it is 4510 volts；To electrode 9
It is passed through voltage II (V1Δ V) it is 4500 volts；Δ HV=│ V1-V2│, wherein Δ HV are the voltage between sample angle 6 and injection port 7
Difference is 4510 volts, i.e. sample solution generates the voltage of electron spray ionisation；Δ V is that electrochemical reaction occurs for excitation testing sample solution
Voltage be 10 volts；2) during use, the voltage HV at 4 injection port 7 of mass spectrograph2In the case of for 4500 volts of high voltage, to
Working electrode 8 is passed through voltage I (V1) it is 10 volts；It is passed through voltage II (V to electrode 91Δ V) it is 0 volt；Δ HV=│ V1-V2│,
Middle Δ HV is that the voltage difference between sample angle 6 and injection port 7 is 4490 volts, i.e. sample solution generates the voltage of electron spray ionisation；
Δ V is that the voltage of excitation testing sample solution generation electrochemical reaction is 10 volts.
Electrochemical reaction is occurred by the surface of the working electrode 8 of sample solution submergence on electrochemical reaction platform, simultaneously
The electron spray ionisation of reaction solution is generated, electron spray sprays from the vertex A1 at sample angle 6, and the substance of ionization instantaneously enters sample introduction
Mouth 7 is completed the analysis to sample solution and is detected.
A kind of electrochemistry-mass spectrometry device provided by the utility model, the sample to be tested during use on sample angle 6
Solution is electrochemically reacted under voltage effect, while sample solution forms electron spray ionisation at A1；Due to sample angle
The distance S1 of vertex A1 to injection port center A2 is 3.5mm, is controlled to sample by power work station 1 in electrochemical electrode combination 3
When offer voltage difference is 4510 volts between product angle 6 and injection port 7, the testing sample solution at sample angle 6 can be made to generate EFI
After mist, the substance of ionization completes the analysis detection of sample solution into mass spectrograph 4 completely into injection port 7.It can be cleverly
Ionspray after electrochemical reaction is sent into the injection port 7 of mass spectrograph 4, it is anti-to complete sample solution electrochemistry into mass spectrograph 4
Answer the real-time of process, in situ detection analysis；When needing to reduce the concentration of detection substance in detection process, increase sample can be adjusted
Voltage difference between the distance S1 or reduction sample angle 6 and injection port 7 of the vertex A1 at product angle to injection port center A2, to reduce
Into the amount of the ionised species of sample port 7；When needing to improve the concentration of detection substance in detection process, reduction can be adjusted
Voltage difference between the distance S1 or increase sample angle 6 and injection port 7 of the vertex A1 at sample angle to injection port center A2, to increase
The amount into the ionised species of sample port 7 is added to meet detection demand.
Voltage difference delta HV in above example between sample angle 6 and injection port 7 is theoretical value, due to actually using process
In have certain energy loss etc. voltage difference between sample angle 6 and injection port 7 caused to reduce but close to Δ HV, can also expire
Sufficient detection demand.
A kind of electrochemistry-mass spectrometry device provided by the utility model can will generate in electrochemical reaction process
The substances such as unstable and high chemism free radical, instantaneous orientation are sent to injection port 7, and sample solution is completed into mass spectrograph 4
Analysis detection, and whole process intermediate ion transmission efficiency is high, the electrochemical reaction of complex system can be carried out in real time, it is in situ
Monitoring and analysis.
It the above is only the embodiments of the present invention, when the range that cannot limit the utility model implementation with this, example
It is for example, quartzy if the material of carrier 2 can be insulator；The distance S1 of the vertex A1 at sample angle to injection port center A2 can roots
According to the type of the solvent used and the size of spray voltage, the best position of detection result is adjusted out, at present sample when detection
The distance S1 of the vertex A1 at angle to injection port center A2 is less than or equal to 20mm；As long as the bottom end of electrochemical electrode combination 3 is located at sample
In product angle 6, the bottom end mutual alignment relation regardless of electrochemical electrode combination 3 may be implemented；Three electrode combination of electrochemistry
In the structure and materials of three electrodes can need arbitrary change according to reaction；Carrier 2 is the carrier at least provided with a wedge angle
2, such as triangle, pentagon or can be with angular irregular shape；Working electrode in electrochemical electrode combination 3
8, the bottom end of electrode 9 and reference electrode 10 is immersed in sample solution respectively, and is not contacted with carrier 2；Electrochemical electrode group
It is two electrode combinations to close 3：Only working electrode and to electrode, no reference electrode 10；Working electrode 8 and electrode material to electrode 9
Material can be any electrode material, such as copper, conductive carbon base class material, conducting polymer etc.；Between sample angle 6 and injection port 7
Voltage difference HV is 3000~5000 volts, the voltage Δ V that is electrochemically reacted of excitation sample be 0~20 volt etc. can be with.
Embodiment 2
As shown in Figure 6, Figure 7, a kind of electrochemistry-mass spectrometry device, including mass spectrograph 4 and electrochemical reaction appts, matter
Spectrometer 4 is equipped with injection port 7, and electrochemical reaction appts are equipped with power work station 1 and electrochemical electrode combination 3, electrochemical reaction dress
Set and be additionally provided with electrochemical reaction platform, electrochemical reaction platform be pentagonal platinum piece carrier 2, the one of pentagonal platinum piece
A wedge angle is set as sample angle 6, and the edge at sample angle 6 is equipped with sample angle drop edge line 5.Electrochemical electrode combination 3 is equipped with work
Electrode 8 and to electrode 9, wherein electrochemical electrode combination 3 is two electrode combinations, and platinum piece carrier 2 is to electrode 9, and platinum circle is
Working electrode 8.Electrochemical electrode combination 3 is controlled by power work station 1 is passed through voltage to the sample solution on sample angle 6, makes
Electrochemical reaction occurs for the testing sample solution at sample angle 6, while generating electron spray ionisation；Sample angle 6 is mutual with injection port 7
Close, the distance S1 of the vertex A1 to injection port center A2 at sample angle is 3.5mm, enables the ionised species after generation electron spray
Enough it is detected into injection port 7.
As shown in figure 8, be integrally provided with insulation cover 11 outside platinum piece carrier 2 and injection port 7, insulation cover 11 is by platinum
Piece carrier 2 and the sealing of injection port 7 cover, and electrochemical electrode combination 3 passes through insulation cover 11, on the one hand, insulation cover 11 can be with
Sample detection is effectively avoided to cause Danger Electric shock risk using high-voltage electricity in the process；On the other hand, insulation cover 11 can reduce sample
Ambient enviroment is influenced caused by testing result in detection process, and final to ensure that detection process is stablized, detection data result is reliable.
Power work station 1, mainly by high voltage power supply, relay switching circuit, resistor voltage divider circuit, signal coupling coil etc.
Composition.Power work station 1 is that electrochemical electrode combination 3 provides power supply；Working electrode 8 and to electrode 9 in electrochemical electrode combination 3
A circuit is formed by sample solution, electrochemical electrode combination 3 is controlled by power work station 1 to sample angle 6 and injection port 7
Between voltage difference is provided, so that testing sample solution at sample angle 6 is generated electron spray；Working electrode 8 and the electricity between electrode 9
Pressure difference can ensure that electrochemical reaction occurs on working electrode 8.The input mode of power supply can be constant voltage input or constant
Electric current inputs or isosceles triangle pulse voltage inputs any of which.
A kind of application method of above-mentioned electrochemistry-mass spectrometry device, specific steps are followed successively by：
First sample solution drop is injected in the 6 sample angle drop edge line 5 of sample angle of electrochemical reaction platform, electrochemistry
The bottom end of working electrode 8 is immersed in sample solution in electrode combination 3, and is not contacted with platinum piece carrier 2；Electrochemical electrode group
Conjunction 3 controls the sample solution on sample angle 6 by power work station 1 and is passed through voltage, to excite sample solution that electrochemistry occurs
Reaction, while generating the electron spray of sample solution：1) during use, the voltage V at 4 injection port 7 of mass spectrograph2For 0 volt or
In the case of low-voltage, voltage I (V are passed through to working electrode 81) it is 5020 volts；It is passed through voltage II (V to platinum piece carrier 21-Δ
V) it is 5000 volts；Δ HV=│ V1-V2│, wherein Δ HV are that the voltage difference between sample angle 6 and injection port 7 is 5020 volts, i.e. sample
Product solution generates the voltage of electron spray ionisation；Δ V is that the voltage of excitation testing sample solution generation electrochemical reaction is 20 volts；2)
During use, the voltage V at 4 injection port 7 of mass spectrograph2In the case of for 5000 volts of high voltage, voltage is passed through to working electrode 8
I(V1) it is 20 volts；It is passed through voltage II (V to platinum piece carrier 21Δ V) it is 0 volt；Δ HV=│ V1-V2│, wherein Δ HV are samples
Voltage difference between angle 6 and injection port 7 is 4980 volts, i.e. sample solution generates the voltage of electron spray ionisation；Δ V is that excitation is to be measured
The voltage that electrochemical reaction occurs for sample solution is 20 volts.
Electrochemical reaction is occurred by the surface of the working electrode 8 of sample solution submergence on electrochemical reaction platform, simultaneously
Electron spray ionisation is generated, electron spray sprays from the vertex A1 at sample angle 6, and the substance of ionization instantaneously enters injection port 7, completes
Analysis detection to sample solution.
A kind of electrochemistry-mass spectrometry device provided by the utility model, the sample solution during use on sample angle 6
It is electrochemically reacted after being excited by voltage, while sample solution can generate electron spray ionisation in the vertex A1 at sample angle；Due to
The distance S1 of the vertex A1 at sample angle to injection port center A2 is 3.5mm, passes through power work station 1 in electrochemical electrode combination 3
It controls and provides voltage difference delta HV between sample angle 6 and injection port 7 when being 4980 volts, the sample to be tested at sample angle 6 can be made
After solution generates electron spray, ion instantaneously enters injection port 7, and the analysis detection of sample solution is completed into mass spectrograph 4.It can be skilful
Wonderful will be sent into the injection port 7 of mass spectrograph 4 after the substance generated in electrochemical reaction process ionization, be completed into mass spectrograph 4
The real-time of sample solution electrochemical reaction process, in situ detection analysis；When the concentration for needing reduction detection substance in detection process
When, the distance S1 for the vertex A1 to injection port center A2 for increasing sample angle can be adjusted or reduce sample angle 6 and injection port 7 it
Between voltage difference, to reduce the amount of the ionised species into sample port 7；The dense of substance is detected when needing to improve in detection process
When spending, the distance S1 for the vertex A1 to injection port center A2 for reducing sample angle can be adjusted or increase sample angle 6 and injection port 7
Between voltage difference, meet detection demand to increase the amount into the ionised species of sample port 7.
Voltage difference delta HV in above example between sample angle 6 and injection port 7 is theoretical value, due to actually using process
In have certain energy loss etc. voltage difference between sample angle 6 and injection port 7 caused to reduce but close to Δ HV, can also expire
Sufficient detection demand.
A kind of electrochemistry-mass spectrometry device provided by the utility model can will generate in electrochemical reaction process
The substances such as unstable and high chemism free radical, instantaneous orientation are sent to injection port 7, and sample solution is completed into mass spectrograph 4
Analysis detection, and whole process intermediate ion transmission efficiency is high, the electrochemical reaction of complex system can be carried out in real time, it is in situ
Monitoring and analysis.
It the above is only specific embodiment of the utility model, when the model for the implementation that cannot limit the utility model with this
It encloses, such as the material of carrier 2 can be any conductor, such as copper；The distance S1 of the vertex A1 at sample angle to injection port center A2 can
According to the type of the solvent used and the size of spray voltage, the best position of detection result is adjusted out, at present sample when detection
The distance S1 of the vertex A1 at product angle to injection port center A2 is less than or equal to 20mm；Two electrodes in two electrode combination of electrochemistry
Structure and material can need arbitrary change according to reaction；Voltage difference HV between sample angle 6 and injection port 7 is 3000~5000
Volt, the voltage Δ V that excitation sample is electrochemically reacted are 0~20 volt；Carrier 2 is the carrier 2 at least provided with a wedge angle, such as
Triangle, hexagon or with angular irregular shape etc.；Working electrode 8 and can be any to the electrode material of electrode 9
Electrode material, such as copper, conductive carbon base class material, conducting polymer etc. can be all should still belong to the utility model claims
The scope that book is covered.
A kind of electrochemistry-mass spectrometry device of the utility model offer, it is simple in structure, convenient, electric convenient for making, operating
The stability and continuity of chemical reaction are high, the high electrochemistry-mass spectrometric platforms of ion transmission efficiency, need not excessive complicated tune
Examination process, the moment ion stream that need not be generated by piezoelectric type pistol, it is ensured that generate stable and reliable ion every time
Stream can carry out real-time, in-situ monitoring and analysis to the electrochemical reaction of complex system.
In the description of the present invention, it should be understood that term "upper", "lower", "inner", "outside", "bottom", "center"
The orientation or positional relationship of equal instructions is to be based on the orientation or positional relationship shown in the drawings, and is merely for convenience of describing this practicality newly
Type and simplified description, specific orientation must be had, with specific orientation by not indicating or implying the indicated device or element
Construction and operation, therefore should not be understood as limiting the present invention.
Only as described above, only specific embodiment of the utility model, when the utility model cannot be limited with this
The range of implementation, all equivalent changes and modifications done according to present utility model application the scope of the claims, should all belong to the utility model
Covering scope.
Claims (8)
1. a kind of electrochemistry-mass spectrometry device, including mass spectrograph and electrochemical reaction appts, the mass spectrograph is equipped with sample introduction
Mouthful, the electrochemical reaction appts are equipped with power work station and electrochemical electrode combines, which is characterized in that the electrochemical reaction
Device is additionally provided with electrochemical reaction platform, and the electrochemical reaction platform is the carrier at least provided with a wedge angle, the carrier
A wedge angle be set as sample angle；The electrochemical electrode combination is molten to sample to be tested simultaneously by the power work stand control
Liquid provides the voltage occurred needed for electrochemical reaction and provides voltage difference between the sample angle and the injection port, makes described
The testing sample solution at sample angle occurs testing sample solution while electro-chemical reaction and generates electron spray ionisation；Institute
It states sample angle and the injection port is close to each other, the ion of the electron spray ionisation is made to enter the injection port；The electrochemistry
Electrode combination is equipped with working electrode and to electrode.
2. a kind of electrochemistry-mass spectrometry device according to claim 1, which is characterized in that the power work station is given
The input mode that the electrochemical electrode combination provides supply voltage is constant voltage input method, constant current input method or isosceles
Triangular pulse voltage method any of which.
3. a kind of electrochemistry-mass spectrometry device according to claim 1, which is characterized in that the electrochemical electrode group
Conjunction is additionally provided with reference electrode.
4. a kind of electrochemistry-mass spectrometry device according to claim 1, which is characterized in that the carrier material is exhausted
Edge body.
5. a kind of electrochemistry-mass spectrometry device according to claim 4, which is characterized in that the insulator be quartz,
Glass.
6. a kind of electrochemistry-mass spectrometry device according to claim 1, which is characterized in that the carrier material is to lead
Body.
7. a kind of electrochemistry-mass spectrometry device according to claim 6, which is characterized in that the conductor is platinum, glass
Carbon any of which.
8. a kind of electrochemistry-mass spectrometry device according to claim 1, which is characterized in that the carrier and it is described into
Insulation cover is integrally provided with outside sample mouth, the insulation cover seals the carrier, the injection port and the electrode combination
It covers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201820471407.6U CN208013135U (en) | 2018-04-03 | 2018-04-03 | A kind of electrochemistry-mass spectrometry device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201820471407.6U CN208013135U (en) | 2018-04-03 | 2018-04-03 | A kind of electrochemistry-mass spectrometry device |
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| Publication Number | Publication Date |
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| CN208013135U true CN208013135U (en) | 2018-10-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108680619A (en) * | 2018-04-03 | 2018-10-19 | 哈尔滨工业大学（威海） | A kind of electrochemistry-mass spectrometry device and its application method |
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2018
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108680619A (en) * | 2018-04-03 | 2018-10-19 | 哈尔滨工业大学（威海） | A kind of electrochemistry-mass spectrometry device and its application method |
| CN108680619B (en) * | 2018-04-03 | 2023-12-26 | 哈尔滨工业大学（威海） | Electrochemical-mass spectrum combined device and application method thereof |
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