CN109580753B - Electrochemical-combined spectrum measurement method - Google Patents
Electrochemical-combined spectrum measurement method Download PDFInfo
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- CN109580753B CN109580753B CN201811220427.7A CN201811220427A CN109580753B CN 109580753 B CN109580753 B CN 109580753B CN 201811220427 A CN201811220427 A CN 201811220427A CN 109580753 B CN109580753 B CN 109580753B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
Abstract
The invention relates to the field of photochemistry and electrochemistry, in particular to a spectrum measuring method combining electrochemistry, which is used for a spectrum measuring device, wherein the spectrum measuring device comprises a high-voltage direct current power supply, a charging resistor, a charging wire, a spark switch, a capacitor, a power distributor, an attenuator, a transmission line I, an oscilloscope, a transmission line II, a bracket, a sample cavity, an optical tester, a thermometer, a semiconductor refrigerator, a heat conduction table and a potentiostat, and a special sample and a novel high-voltage pulse applying method are adopted, so that after the sample is subjected to high-voltage treatment, the electrochemistry characteristic and the spectrum characteristic of the sample can be studied at the same time, the high-voltage pulse applied to the sample is stable, the light scattering during spectrum measurement is low, and the signal to noise ratio of the spectrum is high; the sample cavity balances the requirements of an electrochemical experiment and a spectrum experiment, the electrode with the light reflection function enables the light diffusion path length to be smaller, the light scattering to be kept lower, the high-voltage pulse generation method is simpler, and the generated high-voltage pulse has no burrs and small jitter.
Description
Technical Field
The invention relates to the field of photochemistry and electrochemistry, in particular to a spectrum measuring method combining electrochemistry, which can apply high voltage to a sample and perform spectrum and electrochemistry measurement.
Background
Electrochemical and spectroscopic combinations can be used for redox-active substances, typically where the sample is located in an electrochemical chamber and irradiated with a laser, where the characteristics of the reaction are studied by recording the light reflected from the sample using an optical tester, where the spectrum collection time in the measurement of some reactions is long and where a different sample is prepared separately for each redox reaction. In some reactions requiring the application of high voltage, particularly in the case of high voltage pulses, the switch needs to be rapidly switched between on and off states, and usually when the discharge switch is turned on, a charging current flows from the high voltage dc power supply to the discharge circuit, and this current needs a certain time to be completely attenuated to zero, which prevents the switch from returning to the off state, and the prior art adopts a special gas or a specially designed switch structure to avoid the above phenomenon, but this complicates the structure of the device, and the operation process is complicated, and an improper experimental operation generates irregular and unstable voltage pulses.
Disclosure of Invention
In order to solve the problems, the invention adopts a special sample cavity and a novel high-voltage pulse application method, and can simultaneously study the electrochemical characteristics and the spectral characteristics of the sample after the sample is subjected to high-voltage treatment.
The technical scheme adopted by the invention is as follows:
the device for spectrum measurement comprises a high-voltage direct current power supply, a charging resistor, a charging wire, a spark switch, a capacitor, a power distributor, an attenuator, a transmission line I, an oscilloscope, a transmission line II, a support, a sample cavity, an optical tester, a thermometer, a semiconductor refrigerator, a heat conduction table and a potentiostat, wherein xyz is a three-dimensional space coordinate system, the high-voltage direct current power supply is provided with an output end anode and an output end cathode, the output voltage range of the high-voltage direct current power supply is 1kV to 2kV, the power distributor is provided with an input end, an output end I and an output end II, the potentiostat is provided with the anode and the cathode, the output end II of the power distributor is sequentially connected with the attenuator, the transmission line I and the oscilloscope through cables, the sample cavity, the support, the semiconductor refrigerator and the heat conduction table are sequentially connected from top to bottom, the support is connected with the thermometer, the optical tester is positioned right above the sample cavity, and the optical tester can emit laser light and perform spectrum analysis on the collected light, and the laser light comprises pumping light and detecting light; the sample cavity comprises a cavity body, a plane mirror, a working electrode, a counter electrode, a gasket, a sample, a transmission window, a cavity cover, a reference electrode, a connector I and a connector II, wherein the plane mirror, the working electrode, the counter electrode, the gasket, the sample and the transmission window are all positioned in the cavity body, the connector I and the connector II of the sample cavity are respectively connected with the anode and the cathode of a constant potentiometer, the constant potentiometer is positioned below the sample cavity in a bracket, and the anode of the output end of a high-voltage direct-current power supply is sequentially connected with a charging resistor, a charging wire, a contact II of a spark switch, a rotating shaft of the spark switch, a capacitor and the cathode of the output end of the high-voltage direct-current power supply through cables; the spark switch comprises a rotary motor, a rotary shaft, a horizontal rod, a trigger electrode I, two contacts I, a trigger electrode II and two contacts II, wherein the rotary shaft is vertically arranged on the rotary motor, the middle of the horizontal rod is connected with the rotary shaft, the length of the horizontal rod is 120 mm, the trigger electrode I and the trigger electrode II are cubes with the side length of 8 mm and are respectively arranged at the two ends of the horizontal rod, and the rotary shaft, the horizontal rod, the trigger electrode I and the trigger electrode II are electrically conducted; the two contacts I are the same metal cylinders with axes along the y direction, the two contacts I are spaced by 10 millimeters and coaxially arranged, the height of the metal cylinders is 10 millimeters, the diameter of the bottom surface is 10 millimeters, the distance between the axes of the contacts I and the axes of the rotating shafts is 64 millimeters, the two contacts II are the same metal strips in the shape of 1/6 circular arc, the circle centers of the circular arcs are positioned on the axes of the rotating shafts, the curvature radius is 64 millimeters, the two metal strips are spaced by 10 millimeters in the y direction and are vertically arranged, the two contacts I are electrically conducted with each other, the two contacts II are electrically conducted with each other, the rotating motor can enable the horizontal rod to rotate in the horizontal plane through the rotating shafts, and enable the trigger electrode I and the trigger electrode II to pass through the interval between the two contacts I and the interval between the two contacts II in a non-contact manner; the cavity is cylindrical in shape with an axis along the y direction, the plane mirror is cylindrical in shape with the axis along the y direction and is positioned at the bottom of the cavity, the diameter of the plane mirror is 30 mm and is made of polytetrafluoroethylene materials, the upper surface and the side surface of the plane mirror are deposited to prepare a working electrode and a counter electrode, and the working electrode and the counter electrode are both made of gold and have the thickness of 500 micrometers; the side surface of the cavity is provided with two through holes, and the connector I and the connector II can be respectively in close contact with the working electrode and the counter electrode on the side surface of the plane mirror through the two through holes; the packing ring is made by epoxy material and is located the upper surface of plane mirror, and the external diameter of packing ring is 30 millimeters, internal diameter is 26 millimeters, thickness typical value is 5 to 30 microns, and the transmission window is located the top of packing ring, and the diameter of transmission window is 30 millimeters, and the sample is arranged in the internal diameter of packing ring, and the chamber lid is installed in the cavity top, and the chamber lid can be printing opacity and can seal the cavity, and the chamber lid can compress tightly between transmission window, packing ring and the plane mirror, and chamber lid and transmission window all have the via hole of y direction, and the reference electrode can insert in the sample through the via hole, the reference electrode cable connection electric capacity in proper order, spark switch's rotation axis, spark switch's contact I, power distributor's input, power distributor's output I, transmission line II and joint II.
Principle of applying high voltage pulse to sample:
the spark switch is provided with two spark gaps which are respectively used for charging and discharging, and can eliminate irregular and unstable pulses generated by charge discharging in the pulse generating circuit. The rotary motor of the spark switch drives the trigger electrode I and the trigger electrode II to rotate in the horizontal plane through the rotary shaft and the horizontal rod, so that the trigger electrode I and the trigger electrode II alternately pass through the contact I and the contact II in time, and at the same moment, the trigger electrode I and the trigger electrode II cannot pass through the contact I and the contact II at the same time, and likewise, the trigger electrode I and the trigger electrode II cannot pass through the contact II and the contact I at the same time. When the trigger electrode I or the trigger electrode II passes through the contact II, a spark is generated in a gap between the trigger electrode I or the trigger electrode II and the contact II, so that the trigger electrode I or the trigger electrode II is conducted with the contact II, and the capacitor is charged by a high-voltage direct-current power supply; when the trigger electrode I or the trigger electrode II passes through the contact I, a spark is generated in a gap between the trigger electrode I or the trigger electrode II and the contact I, so that the trigger electrode I or the trigger electrode II is conducted with the contact I, and the capacitor discharges a sample in the sample cavity.
Principle of electrochemical measurement of a sample:
the positive electrode and the negative electrode of the potentiostat are respectively connected with the working electrode and the counter electrode through the connector I and the connector II so as to apply electrochemical potentials to the sample, and the sample can have different chemical forms under different electrochemical potentials.
Principle of spectral experimental measurement of samples:
the optical tester emits two light pulses, namely pump light and probe light, the pump light and the probe light have different powers, frequencies and durations, the delay time of the probe light relative to the pump light can be adjusted, the pump light emitted by the optical tester sequentially passes through the cavity cover and the transmission window from top to bottom and irradiates the sample, so that the sample reacts, the probe light emitted by the optical tester sequentially passes through the cavity cover and the transmission window and irradiates the sample to generate a certain degree of scattering, part of the probe light irradiated to the upper surfaces of the working electrode and the counter electrode is reflected to form reflected light, the reflected light is irradiated to the sample again from bottom to top, part of the reflected light passes through the sample to form secondary transmission light, and the secondary transmission light sequentially passes through the transmission window and the cavity cover and then enters the optical tester.
The laser emitted by the optical tester is incident to the sample at an angle of 0.5 degrees with the upper surface of the transmission window, and has the advantages of spatially separating the light reflected by the upper surface of the transmission window from the light after the action of the sample, thereby avoiding the interference of pump light in the spectrogram acquired by the optical tester.
The invention adopts the working electrode and the counter electrode which are made of gold on the upper surface of the plane mirror as the working electrode, instead of adopting a metal grid mesh as the working electrode as in certain spectrum measuring devices in the prior art, and has the advantages of avoiding the scattering problem of light, increasing the signal to noise ratio of the optical signal collected by the optical tester, and doubling the intensity of the signal collected by the optical tester because the light passes through the sample twice.
The structural design of the sample cavity can be suitable for samples with different thicknesses by selecting gaskets with different thicknesses, and has good air tightness. The voltage difference V in the following method steps varies depending on the specific sample under investigation 1 Ranging from 0 to 300mV, voltage difference V 2 Ranging from 300mV to 800mV.
The spectrum measurement method combining electrochemistry comprises the following steps:
step 1, adding a sample into a sample cavity, mounting a cavity cover to the cavity and compacting between a transmission window, a gasket and a plane mirror;
step 2, starting a high-voltage direct-current power supply, outputting voltage to a spark switch through a charging resistor and a charging wire, starting a rotary motor, wherein the rotating speed range of the rotary motor is 1000-5000 revolutions per minute, and the spark switch periodically enables the capacitor to be conducted with the high-voltage direct-current power supply or the capacitor to be conducted with a sample cavity, and the two processes of charging the capacitor by the high-voltage direct-current power supply and discharging the capacitor to the sample cavity are alternately performed for 5 minutes;
step 3, turning off the high-voltage direct-current power supply and turning off the rotary motor;
step 4, starting the optical tester, enabling laser emitted by the optical tester to enter at an angle of 0.5 degrees with the normal direction of the upper surface of the transmission window and to be emitted to the sample, wherein the energy range of each pumping light pulse is 4mJ to 8mJ, the duration time is 1 picosecond, the energy range of each detection light pulse is 0.5mJ to 1mJ, the duration time is 800 femtoseconds, and the time delay of the detection light pulse relative to the pumping light pulse is 2 to 5 picoseconds;
step 5, adjusting the potentiostat to enable the voltage difference between the working electrode and the counter electrode to be V 1 Voltage difference V 1 Ranging from 0 to 300mV to apply an electrochemical potential to the sample such that a first chemical morphology occurs in the sample, the optical tester collecting the reflected light for 2 minutes;
step 6, adjusting the potentiostat to enable the voltage difference between the working electrode and the counter electrode to be V 2 Voltage difference V 2 Ranging from 300mV to 800mV to apply an electrochemical potential to the sample such that a second chemical morphology occurs in the sample, the optical tester collecting the reflected light for 2 minutes;
and 7, repeating the steps 5 and 6, wherein the repeated steps are performed for ten times continuously, and processing and averaging the reflected light information collected by the optical tester to obtain a differential spectrum of the first chemical form and the second chemical form of the sample.
The beneficial effects of the invention are as follows:
the sample cavity balances the requirements of an electrochemical experiment and a spectrum experiment, the electrode with the light reflection function enables the light diffusion path length to be smaller, keeps lower light scattering, increases the signal to noise ratio of a spectrum, and in addition, the high-voltage pulse generation method is simpler, and the generated high-voltage pulse has no burrs and small jitter.
Drawings
The following is further described in connection with the figures of the present invention:
FIG. 1 is a schematic illustration of the present invention;
FIG. 2 is an enlarged schematic diagram of a spark switch;
FIG. 3 is a top view of FIG. 2;
FIG. 4 is an enlarged schematic view of a sample chamber;
fig. 5 is a cross-sectional view A-A of fig. 4.
In the figure, 1.high voltage DC power supply, 2.charging resistor, 3.charging wire, 4.spark switch, 4-1.rotary motor, 4-2.rotary shaft, 4-3.horizontal rod, 4-4.trigger electrode I, 4-5.contact I, 4-6.trigger electrode II, 4-7.contact II, 5.capacitor, 6.power divider, 7.attenuator, 8.transmission line I, 9.oscilloscope, 10.transmission line II, 11.bracket, 12.sample cavity, 12-1.cavity, 12-2.plane mirror, 12-3.working electrode, 12-4.counter electrode, 12-5.gasket, 12-6.sample, 12-7.transmission window, 12-8.cavity cover, 12-9.reference electrode, 12-10.connector I, 12-11.connector II, 13.optical tester, 14.thermometer, 15.semiconductor refrigerator, 16.heat conducting stage, 17.potentiostat.
Detailed Description
Fig. 1 is a schematic diagram of the invention, xyz is a three-dimensional space coordinate system, fig. 2 is an enlarged schematic diagram of a spark switch, fig. 3 is a top view of fig. 2, the three-dimensional space coordinate system comprises a high-voltage direct current power supply (1), a charging resistor (2), a charging wire (3), a spark switch (4), a capacitor (5), a power distributor (6), an attenuator (7), a transmission line I (8), an oscilloscope (9), a transmission line II (10), a bracket (11), a sample cavity (12), an optical tester (13), a thermometer (14), a semiconductor refrigerator (15), a heat conduction table (16) and a potentiostat (17), the high-voltage direct current power supply (1) is provided with an output end positive electrode and an output end negative electrode, the output voltage range of the high-voltage direct current power supply (1) is 1kV to 2kV, the power distributor (6) is provided with an input end, an output end I and an output end II, the potentiostat (17) is provided with a positive electrode and a negative electrode, the output end II of the power distributor (6) is sequentially connected with the attenuator (7), the transmission line I (8) and the oscilloscope (9), the sample cavity (12), the sample cavity (11), the semiconductor refrigerator (16) and the potentiostat (12) are sequentially connected with the sample cavity (12), the semiconductor refrigerator (16) and the thermometer (13) from top to the top down, the sample (13) is sequentially connected with the sample (13), the optical tester (13) can emit laser light and perform spectrum analysis on the collected light, wherein the laser light comprises pump light and probe light; the positive electrode of the output end of the high-voltage direct-current power supply (1) is sequentially connected with a charging resistor (2), a charging wire (3), a contact II (4-7) of a spark switch (4), a rotating shaft (4-2) of the spark switch (4), a capacitor (5) and the negative electrode of the output end of the high-voltage direct-current power supply (1) through cables; the spark switch (4) comprises a rotary motor (4-1), a rotary shaft (4-2), a horizontal rod (4-3), a trigger electrode I (4-4), two contacts I (4-5), a trigger electrode II (4-6) and two contacts II (4-7), wherein the rotary shaft (4-2) is vertically arranged on the rotary motor (4-1), the middle of the horizontal rod (4-3) is connected with the rotary shaft (4-2), the length of the horizontal rod (4-3) is 120 mm, the trigger electrode I (4-4) and the trigger electrode II (4-6) are square bodies with the side length of 8 mm and are respectively arranged at two ends of the horizontal rod (4-3), and the rotary shaft (4-2), the horizontal rod (4-3), the trigger electrode I (4-4) and the trigger electrode II (4-6) are electrically conducted; the two contacts I (4-5) are identical metal cylinders with axes along the y direction, the two contacts I (4-5) are arranged at intervals of 10 millimeters and are coaxially, the height of the metal cylinders is 10 millimeters, the diameter of the bottom surface is 10 millimeters, the distance between the axes of the contacts I (4-5) and the axes of the rotating shafts (4-2) is 64 millimeters, the two contacts II (4-7) are identical metal strips in the shape of 1/6 circular arcs, the centers of the circular arcs are positioned on the axes of the rotating shafts (4-2) and have the curvature radius of 64 millimeters, the two metal strips are arranged at intervals of 10 millimeters in the y direction and are arranged up and down, the two contacts I (4-5) are electrically communicated with each other, the two contacts II (4-7) are electrically communicated with each other, the rotating motor (4-1) can enable the horizontal rod (4-3) to rotate in the horizontal plane through the rotating shafts (4-2), and enable the trigger electrode I (4-6) to pass through the interval between the two contacts I (4-5) and the interval between the two contacts (4-7).
FIG. 4 is an enlarged schematic view of a sample chamber, and FIG. 5 is a cross-sectional view of A-A of FIG. 4, wherein the sample chamber (12) comprises a chamber body (12-1), a plane mirror (12-2), a working electrode (12-3), a counter electrode (12-4), a gasket (12-5), a sample (12-6), a transmission window (12-7), a chamber cover (12-8), a reference electrode (12-9), a joint I (12-10) and a joint II (12-11), and the plane mirror (12-2), the working electrode (12-3), the counter electrode (12-4), the gasket (12-5), the sample (12-6) and the transmission window (12-7) are all positioned in the chamber body (12-1); the reference electrode (12-9) is sequentially connected with the capacitor (5), the rotating shaft (4-2) of the spark switch (4), the contact I (4-5) of the spark switch (4), the input end of the power distributor (6), the output end I of the power distributor (6), the transmission line II (10) and the connector II (12-11) in a cable manner, the connector I (12-10) and the connector II (12-11) of the sample cavity (12) are respectively connected with the anode and the cathode of the constant potentiometer (17), and the constant potentiometer (17) is positioned below the sample cavity (12) in the bracket (11); the cavity (12-1) is cylindrical in shape with an axis along the y direction, the plane mirror (12-2) is cylindrical in shape with the axis along the y direction and is positioned at the bottom of the cavity (12-1), the diameter of the plane mirror (12-2) is 30 mm and is made of polytetrafluoroethylene materials, the upper surface and the side surface of the plane mirror (12-2) are deposited to prepare a working electrode (12-3) and a counter electrode (12-4), and the working electrode (12-3) and the counter electrode (12-4) are both made of gold and have a thickness of 500 micrometers; the side surface of the cavity (12-1) is provided with two through holes, and the joint I (12-10) and the joint II (12-11) can be respectively in close contact with the working electrode (12-3) and the counter electrode (12-4) on the side surface of the plane mirror (12-2) through the two through holes; the gasket (12-5) is made of epoxy resin material and is positioned on the upper surface of the plane mirror (12-2), the outer diameter of the gasket (12-5) is 30 mm, the inner diameter is 26 mm, the typical thickness value is 5-30 microns, the transmission window (12-7) is positioned above the gasket (12-5), the diameter of the transmission window (12-7) is 30 mm, the sample (12-6) is placed in the inner diameter of the gasket (12-5), the cavity cover (12-8) is mounted above the cavity (12-1), the cavity cover (12-8) can transmit light and can seal the cavity (12-1), the cavity cover (12-8) can compress the transmission window (12-7), the gasket (12-5) and the plane mirror (12-2), the cavity cover (12-8) and the transmission window (12-7) are provided with y-direction through holes, and the reference electrode (12-9) can be inserted into the sample (12-6) through the through holes.
The device for spectrum measurement comprises a high-voltage direct current power supply (1), a charging resistor (2), a charging wire (3), a spark switch (4), a capacitor (5), a power distributor (6), an attenuator (7), a transmission line I (8), an oscilloscope (9), a transmission line II (10), a support (11), a sample cavity (12), an optical tester (13), a thermometer (14), a semiconductor refrigerator (15), a heat conduction table (16) and a potentiostat (17), xyz is a three-dimensional space coordinate system, the high-voltage direct current power supply (1) is provided with an output end anode and an output end cathode, the output voltage range of the high-voltage direct current power supply (1) is 1kV to 2kV, the power distributor (6) is provided with an input end, an output end I and an output end II, the potentiostat (17) is provided with an anode and a cathode, the output end II of the power distributor (6) is sequentially connected with the attenuator (7), the transmission line I (8) and the oscilloscope (9) through cables, the sample cavity (12), the support (11), the semiconductor refrigerator (15) and the heat conduction table (16) are sequentially connected with the heat conduction table (16) through the cable, the support (11) is sequentially connected with the thermometer (14) and can be positioned on the optical tester (13) from top to bottom, and the optical tester (13) can analyze the spectrum, the laser comprises pump light and detection light; the sample cavity (12) comprises a cavity (12-1), a plane mirror (12-2), a working electrode (12-3), a counter electrode (12-4), a gasket (12-5), a sample (12-6), a transmission window (12-7), a cavity cover (12-8), a reference electrode (12-9), a connector I (12-10) and a connector II (12-11), wherein the plane mirror (12-2), the working electrode (12-3), the counter electrode (12-4), the gasket (12-5), the sample (12-6) and the transmission window (12-7) are all positioned in the cavity (12-1), the connector I (12-10) and the connector II (12-11) of the sample cavity (12) are respectively connected with the anode and the cathode of a potentiostat (17), the potentiostat (17) is positioned below the sample cavity (12) in a bracket (11), the output end of a high-voltage direct current power supply (1) is connected with a charging resistor (2), a charging wire (3), the contact II (4-7) of the anode switch (4), and a rotating shaft of the switch (4-2) of the spark switch (4) in sequence, the capacitor (5) and the negative electrode of the output end of the high-voltage direct-current power supply (1); the spark switch (4) comprises a rotary motor (4-1), a rotary shaft (4-2), a horizontal rod (4-3), a trigger electrode I (4-4), two contacts I (4-5), a trigger electrode II (4-6) and two contacts II (4-7), wherein the rotary shaft (4-2) is vertically arranged on the rotary motor (4-1), the middle of the horizontal rod (4-3) is connected with the rotary shaft (4-2), the length of the horizontal rod (4-3) is 120 mm, the trigger electrode I (4-4) and the trigger electrode II (4-6) are square bodies with the side length of 8 mm and are respectively arranged at two ends of the horizontal rod (4-3), and the rotary shaft (4-2), the horizontal rod (4-3), the trigger electrode I (4-4) and the trigger electrode II (4-6) are electrically conducted; the two contacts I (4-5) are identical metal cylinders with axes along the y direction, the two contacts I (4-5) are spaced by 10 millimeters and coaxially arranged, the height of the metal cylinders is 10 millimeters, the diameter of the bottom surface is 10 millimeters, the distance between the axes of the contacts I (4-5) and the axes of the rotating shafts (4-2) is 64 millimeters, the two contacts II (4-7) are identical metal strips in the shape of 1/6 circular arcs, the centers of the circular arcs are positioned on the axes of the rotating shafts (4-2) and have the curvature radius of 64 millimeters, the two metal strips are spaced by 10 millimeters in the y direction and are arranged up and down, the two contacts I (4-5) are electrically communicated with each other, the two contacts II (4-7) are electrically communicated with each other, the rotating motor (4-1) can enable the horizontal rod (4-3) to rotate in the horizontal plane through the rotating shafts (4-2), and enable the trigger electrode I (4-6) to pass through the spacing between the two contacts I (4-5) and the spacing between the two contacts (4-7); the cavity (12-1) is cylindrical in shape with an axis along the y direction, the plane mirror (12-2) is cylindrical in shape with the axis along the y direction and is positioned at the bottom of the cavity (12-1), the diameter of the plane mirror (12-2) is 30 mm and is made of polytetrafluoroethylene materials, the upper surface and the side surface of the plane mirror (12-2) are deposited to prepare a working electrode (12-3) and a counter electrode (12-4), and the working electrode (12-3) and the counter electrode (12-4) are both made of gold and have a thickness of 500 micrometers; the side surface of the cavity (12-1) is provided with two through holes, and the joint I (12-10) and the joint II (12-11) can be respectively in close contact with the working electrode (12-3) and the counter electrode (12-4) on the side surface of the plane mirror (12-2) through the two through holes; the gasket (12-5) is made of epoxy resin material and is positioned on the upper surface of the plane mirror (12-2), the outer diameter of the gasket (12-5) is 30 mm, the inner diameter is 26 mm, the typical thickness value is 5-30 microns, the transmission window (12-7) is positioned above the gasket (12-5), the diameter of the transmission window (12-7) is 30 mm, the sample (12-6) is placed in the inner diameter of the gasket (12-5), the cavity cover (12-8) is arranged above the cavity (12-1), the cavity cover (12-8) can transmit light and can seal the cavity (12-1), the cavity cover (12-8) can compress the transmission window (12-7), the gasket (12-5) and the plane mirror (12-2), the cavity cover (12-8) and the transmission window (12-7) are provided with y-direction through holes, the reference electrode (12-9) can be inserted into the sample (12-6) through the through holes, and the reference electrode (12-9) is connected with the power distributor (4) and the power distributor (4) of the power distributor (4-6), the power distributor (4) and the power distributor (4-6) of the power distributor (4) of the power switch (4) in turn connected with the capacitor (4-5) and the power distributor (4) A transmission line II (10) and a joint II (12-11).
Principle of applying high voltage pulse to sample (12-6):
the spark switch (4) is provided with two spark gaps for charging and discharging respectively, and can eliminate irregular and unstable pulses generated by charge and discharge in the pulse generating circuit. A rotary motor (4-1) of a spark switch (4) drives a trigger electrode I (4-4) and a trigger electrode II (4-6) to rotate in a horizontal plane through a rotary shaft (4-2) and a horizontal rod (4-3), so that the trigger electrode I (4-4) and the trigger electrode II (4-6) alternately pass through a contact I (4-5) and a contact II (4-7) in time, and at the same moment, the trigger electrode I (4-4) and the trigger electrode II (4-6) cannot pass through the contact I (4-5) and the contact II (4-7) at the same time, and likewise, the trigger electrode I (4-4) and the trigger electrode II (4-6) cannot pass through the contact II (4-7) and the contact I (4-5) at the same time. When the trigger electrode I (4-4) or the trigger electrode II (4-6) passes through the contact II (4-7), a spark is generated in a gap between the trigger electrode I (4-4) or the trigger electrode II (4-6) and the contact II (4-7), so that the trigger electrode I (4-4) or the trigger electrode II (4-6) is conducted with the contact II (4-7), and the capacitor (5) is charged by the high-voltage direct current power supply (1); when the trigger electrode I (4-4) or the trigger electrode II (4-6) passes through the contact I (4-5), a spark is generated in a gap between the trigger electrode I (4-4) or the trigger electrode II (4-6) and the contact I (4-5), so that the trigger electrode I (4-4) or the trigger electrode II (4-6) is conducted with the contact I (4-5), and the capacitor (5) discharges a sample (12-6) in the sample cavity (12).
Principle of electrochemical measurement of sample (12-6):
the positive electrode and the negative electrode of the potentiostat (17) are respectively connected with the working electrode (12-3) and the counter electrode (12-4) through the connector I (12-10) and the connector II (12-11) so as to apply electrochemical potentials to the sample (12-6), and the sample (12-6) can have different chemical forms under different electrochemical potentials.
Principle of spectral experimental measurement on sample (12-6):
the optical tester (13) emits two light pulses, namely pump light and probe light, the pump light and the probe light have different powers, frequencies and durations, the delay time of the probe light relative to the pump light can be adjusted, the pump light emitted by the optical tester (13) sequentially passes through the cavity cover (12-8) and the transmission window (12-7) from top to bottom and then is emitted to the sample (12-6), so that the sample (12-6) reacts, the probe light emitted by the optical tester (13) sequentially passes through the cavity cover (12-8) and the transmission window (12-7) and then is emitted to the sample (12-6) and generates a certain degree of scattering, part of the probe light emitted to the upper surfaces of the working electrode (12-3) and the counter electrode (12-4) is reflected to form reflected light, and the reflected light is emitted to the sample again from bottom to top
(12-6), wherein a part of the reflected light passes through the sample (12-6) to form secondary transmission light, the secondary transmission light sequentially passes through the transmission window (12-7) and the cavity cover (12-8) and then enters the optical tester (13), and the relevant characteristics of the sample (12-6) can be obtained by analyzing the characteristics of the secondary transmission light acquired by the optical tester (13).
The laser emitted by the optical tester (13) is incident to the sample (12-6) at an angle of 0.5 degrees with the upper surface of the transmission window (12-7), and has the advantages that the light reflected by the upper surface of the transmission window (12-7) is separated from the light after the action of the sample (12-6) in space, so that the interference of pump light in a spectrogram acquired by the optical tester (13) is avoided.
The working electrode (12-3) and the counter electrode (12-4) which are made of gold on the upper surface of the plane mirror (12-2) are used as working electrodes, instead of using a metal grid as the working electrodes as in certain spectrum measuring devices in the prior art, the advantage is that the scattering problem of light can be avoided, the signal to noise ratio of the light signal collected by the optical tester (13) is increased, in addition, the intensity of the signal collected by the optical tester (13) is doubled because the light passes through the sample twice, which is very important under the condition that the sample amount is small, when the spectrum experiment is carried out by the device, only fewer samples are needed, and the time for reaching an electrochemical equilibrium state can be reduced by adopting thinner samples, which is very important for certain rapid redox cycle processes.
The structural design of the sample cavity (12) can be suitable for samples with different thicknesses by selecting gaskets (12-5) with different thicknesses, and has good air tightness.
The voltage difference V in the following method steps varies depending on the specific sample under investigation 1 Ranging from 0 to 300mV, voltage difference V 2 Ranging from 300mV to 800mV, one example is: for iron phthalocyanine molecular film sample on gold substrate surface in oxygen saturated electrolyte, voltage difference V 1 50mV of voltage difference V 2 350mV.
The spectrum measurement method combining electrochemistry comprises the following steps:
step 1, adding a sample (12-6) into a sample cavity (12), mounting a cavity cover (12-8) to the cavity (12-1) and compacting between a transmission window (12-7), a gasket (12-5) and a plane mirror (12-2);
step 2, starting a high-voltage direct current power supply (1), outputting voltage to a spark switch (4) through a charging resistor (2) and a charging wire (3), starting a rotary motor (4-1), enabling the rotating speed range of the rotary motor (4-1) to be 1000-5000 revolutions per minute, enabling a capacitor (5) to be conducted with the high-voltage direct current power supply (1) or enabling the capacitor (5) to be conducted with a sample cavity (12) periodically by the spark switch (4), and alternately conducting two processes of charging the capacitor (5) and discharging the capacitor (5) to the sample cavity (12) by the high-voltage direct current power supply (1) for 5 minutes;
step 3, turning off the high-voltage direct-current power supply (1) and turning off the rotary motor (4-1);
step 4, opening the optical tester (13), enabling laser emitted by the optical tester (13) to enter at an angle of 0.5 degrees with the normal direction of the upper surface of the transmission window (12-7) and to be emitted to the sample (12-6), wherein the energy range of each pumping light pulse is 4mJ to 8mJ, the duration time is 1 picosecond, the energy range of each detecting light pulse is 0.5mJ to 1mJ, the duration time is 800 femtoseconds, and the time delay of the detecting light pulse relative to the pumping light pulse is 2 to 5 picoseconds;
step 5, adjusting the potentiostat (17) so that the voltage difference between the working electrode (12-3) and the counter electrode (12-4) is V 1 Voltage difference V 1 Ranging from 0 to 300mV, to apply an electrochemical potential to the sample (12-6) such that a first chemical morphology occurs in the sample (12-6), the reflected light being collected by the optical tester (13) for 2 minutes;
step 6, adjusting the potentiostat (17) so that the voltage difference between the working electrode (12-3) and the counter electrode (12-4) is V 2 Voltage difference V 2 Ranging from 300mV to 800mV to apply an electrochemical potential to the sample (12-6) such that a second chemical morphology appears in the sample (12-6), the reflected light being collected by the optical tester (13) for 2 minutes;
and 7, repeating the steps 5 and 6, wherein the repeated steps are performed for ten times continuously, and the reflected light information collected by the optical tester (13) is processed and averaged to obtain the differential spectrum of the first chemical form and the second chemical form of the sample (12-6).
The method of the invention adopts a special sample and a novel high-voltage pulse application method, can simultaneously study the electrochemical characteristics and the spectral characteristics of the sample after carrying out high-voltage treatment on the sample, has stable high-voltage pulse applied to the sample, low light scattering during spectral measurement and high signal to noise ratio of the spectrum.
Claims (1)
1. The utility model provides a spectrum measurement method combining electrochemistry, a device for spectrum measurement includes high voltage direct current power supply (1), charging resistor (2), charging wire (3), spark switch (4), electric capacity (5), power distributor (6), attenuator (7), transmission line I (8), oscilloscope (9), transmission line II (10), support (11), sample chamber (12), optical tester (13), thermometer (14), semiconductor refrigerator (15), heat conduction platform (16) and potentiostat (17), xyz is three-dimensional space coordinate system, high voltage direct current power supply (1) has output positive pole and output negative pole, high voltage direct current power supply (1) output voltage range is 1kV to 2kV, power distributor (6) has input, output I and output II, potentiostat (17) have positive pole and negative pole, output II of power distributor (6) cable connection attenuator (7) in proper order, transmission line I (8) and (9), sample chamber (12), support (11), semiconductor (15) and thermometer (16) are connected to the top-down in proper order to the sample chamber (12), the heat conduction platform (16) is connected with the top-down, the sample chamber (13) is located in proper order on the top-down side of the oscilloscope (13), the optical tester (13) can emit laser light and perform spectrum analysis on the collected light, wherein the laser light comprises pump light and probe light; the sample cavity (12) comprises a cavity (12-1), a plane mirror (12-2), a working electrode (12-3), a counter electrode (12-4), a gasket (12-5), a sample (12-6), a transmission window (12-7), a cavity cover (12-8), a reference electrode (12-9), a connector I (12-10) and a connector II (12-11), wherein the plane mirror (12-2), the working electrode (12-3), the counter electrode (12-4), the gasket (12-5), the sample (12-6) and the transmission window (12-7) are all positioned in the cavity (12-1), the connector I (12-10) and the connector II (12-11) of the sample cavity (12) are respectively connected with the anode and the cathode of a potentiostat (17), the potentiostat (17) is positioned below the sample cavity (12) in a bracket (11), the output end of a high-voltage direct current power supply (1) is connected with a charging resistor (2), a charging wire (3), the contact II (4-7) of the anode switch (4), and a rotating shaft of the switch (4-2) of the spark switch (4) in sequence, the capacitor (5) and the negative electrode of the output end of the high-voltage direct-current power supply (1); the spark switch (4) comprises a rotary motor (4-1), a rotary shaft (4-2), a horizontal rod (4-3), a trigger electrode I (4-4), two contacts I (4-5), a trigger electrode II (4-6) and two contacts II (4-7), wherein the rotary shaft (4-2) is vertically arranged on the rotary motor (4-1), the middle of the horizontal rod (4-3) is connected with the rotary shaft (4-2), the length of the horizontal rod (4-3) is 120 mm, the trigger electrode I (4-4) and the trigger electrode II (4-6) are square bodies with the side length of 8 mm and are respectively arranged at two ends of the horizontal rod (4-3), and the rotary shaft (4-2), the horizontal rod (4-3), the trigger electrode I (4-4) and the trigger electrode II (4-6) are electrically conducted; the two contacts I (4-5) are identical metal cylinders with axes along the y direction, the two contacts I (4-5) are spaced by 10 millimeters and coaxially arranged, the height of the metal cylinders is 10 millimeters, the diameter of the bottom surface is 10 millimeters, the distance between the axes of the contacts I (4-5) and the axes of the rotating shafts (4-2) is 64 millimeters, the two contacts II (4-7) are identical metal strips in the shape of 1/6 circular arcs, the centers of the circular arcs are positioned on the axes of the rotating shafts (4-2) and have the curvature radius of 64 millimeters, the two metal strips are spaced by 10 millimeters in the y direction and are arranged up and down, the two contacts I (4-5) are electrically communicated with each other, the two contacts II (4-7) are electrically communicated with each other, the rotating motor (4-1) can enable the horizontal rod (4-3) to rotate in the horizontal plane through the rotating shafts (4-2), and enable the trigger electrode I (4-6) to pass through the spacing between the two contacts I (4-5) and the spacing between the two contacts (4-7); the cavity (12-1) is cylindrical in shape with an axis along the y direction, the plane mirror (12-2) is cylindrical in shape with the axis along the y direction and is positioned at the bottom of the cavity (12-1), the diameter of the plane mirror (12-2) is 30 mm and is made of polytetrafluoroethylene materials, the upper surface and the side surface of the plane mirror (12-2) are deposited to prepare a working electrode (12-3) and a counter electrode (12-4), and the working electrode (12-3) and the counter electrode (12-4) are both made of gold and have a thickness of 500 micrometers; the side surface of the cavity (12-1) is provided with two through holes, and the joint I (12-10) and the joint II (12-11) can be respectively in close contact with the working electrode (12-3) and the counter electrode (12-4) on the side surface of the plane mirror (12-2) through the two through holes; the gasket (12-5) is made of epoxy resin material and is positioned on the upper surface of the plane mirror (12-2), the outer diameter of the gasket (12-5) is 30 mm, the inner diameter is 26 mm, the typical thickness value is 5-30 microns, the transmission window (12-7) is positioned above the gasket (12-5), the diameter of the transmission window (12-7) is 30 mm, the sample (12-6) is placed in the inner diameter of the gasket (12-5), the cavity cover (12-8) is arranged above the cavity (12-1), the cavity cover (12-8) can transmit light and can seal the cavity (12-1), the cavity cover (12-8) can compress the transmission window (12-7), the gasket (12-5) and the plane mirror (12-2), the cavity cover (12-8) and the transmission window (12-7) are provided with y-direction through holes, the reference electrode (12-9) can be inserted into the sample (12-6) through the through holes, and the reference electrode (12-9) is connected with the power distributor (4) and the power distributor (4) of the power distributor (4-6), the power distributor (4) and the power distributor (4-6) of the power distributor (4) of the power switch (4) in turn connected with the capacitor (4-5) and the power distributor (4) A transmission line II (10) and a joint II (12-11),
the method is characterized in that: the spectrum measurement method combining electrochemistry comprises the following steps:
step 1, adding a sample (12-6) into a sample cavity (12), mounting a cavity cover (12-8) to the cavity (12-1) and compacting between a transmission window (12-7), a gasket (12-5) and a plane mirror (12-2);
step 2, starting a high-voltage direct current power supply (1), outputting voltage to a spark switch (4) through a charging resistor (2) and a charging wire (3), starting a rotary motor (4-1), enabling the rotating speed range of the rotary motor (4-1) to be 1000-5000 revolutions per minute, enabling a capacitor (5) to be conducted with the high-voltage direct current power supply (1) or enabling the capacitor (5) to be conducted with a sample cavity (12) periodically by the spark switch (4), and alternately conducting two processes of charging the capacitor (5) and discharging the capacitor (5) to the sample cavity (12) by the high-voltage direct current power supply (1) for 5 minutes;
step 3, turning off the high-voltage direct-current power supply (1) and turning off the rotary motor (4-1);
step 4, opening the optical tester (13), enabling laser emitted by the optical tester (13) to enter at an angle of 0.5 degrees with the normal direction of the upper surface of the transmission window (12-7) and to be emitted to the sample (12-6), wherein the energy range of each pumping light pulse is 4mJ to 8mJ, the duration time is 1 picosecond, the energy range of each detecting light pulse is 0.5mJ to 1mJ, the duration time is 800 femtoseconds, and the time delay of the detecting light pulse relative to the pumping light pulse is 2 to 5 picoseconds;
step 5, adjusting the potentiostat (17) so that the voltage difference between the working electrode (12-3) and the counter electrode (12-4) is V 1 Voltage difference V 1 Ranging from 0 to 300mV, to apply an electrochemical potential to the sample (12-6) such that a first chemical morphology occurs in the sample (12-6), the reflected light being collected by the optical tester (13) for 2 minutes;
step 6, adjusting the potentiostat (17) so that the voltage difference between the working electrode (12-3) and the counter electrode (12-4) is V 2 Voltage difference V 2 Ranging from 300mV to 800mV to apply an electrochemical potential to the sample (12-6) such that a second chemical morphology appears in the sample (12-6), the reflected light being collected by the optical tester (13) for 2 minutes;
and 7, repeating the steps 5 and 6, wherein the repeated steps are performed for ten times continuously, and the reflected light information collected by the optical tester (13) is processed and averaged to obtain the differential spectrum of the first chemical form and the second chemical form of the sample (12-6).
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| WO1999013318A1 (en) * | 1997-09-05 | 1999-03-18 | Brown University Research Foundation | Optical method for the characterization of the electrical properties of semiconductors and insulating films |
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