JPH0692958B2 - Automatic photothermal spectrophotometer for electrolytic electrodes - Google Patents

Description

Description: INDUSTRIAL APPLICABILITY The present invention relates to in-situ (in sit
u) concerning a spectroscopic measurement device for analyzing the electrode surface,
In particular, it relates to an apparatus for automatically analyzing the electrode surface by photothermal spectroscopy.

As is well known in the prior art, an electrolyte is electrolyzed by immersing two electrodes in a solution containing an electrolyte and applying a sufficient voltage between both electrodes. Such a method of separately producing a target substance by utilizing a cathodic reaction or an anodic reaction associated with electrolysis and quantitatively analyzing it is called an electrolytic analysis method. This electrolytic analysis method includes a constant current electrolysis method and a constant potential electrolysis method. Among them, the constant potential electrolysis method is a working electrode (an electrode in which a target reaction occurs,
Therefore, by using three electrodes, a sample electrode), a reference electrode (reference electrode or reference electrode) composed of a saturated calomel electrode, and a counter electrode, electrolysis is performed while maintaining the potential of the working electrode with respect to the reference electrode with a potentiostat. is there. This potentiostatic electrolysis method can arbitrarily change the strength of the electrode reaction, that is, the oxidation or reduction by changing the set potential of the working electrode with respect to the reference electrode, and is therefore suitable for separation and quantification under coexisting substances.

By the way, in the electrolytic analysis as described above, it is useful in the study of the electrode reaction to obtain information about the condition of the electrode surface in the electrolyte atmosphere at the time when the electrode reaction is actually proceeding. For example, the progress of the electrode reaction can be known by detecting the film thickness of the product on the electrode surface in-situ during the electrode reaction or analyzing the spectrum of the electrode surface in-situ during the electrode reaction. .

Conventionally, as a method for observing the electrode surface in situ and nondestructively during the electrolytic electrode reaction as described above, a transmission method, an internal reflection method, a specular reflection method, an ellipsometry method, or a photoelectric polarization method is known. Has been. However, each method has various drawbacks and is not satisfactory.

That is, among the various methods described above, the transmission method and the internal reflection method have a problem that the applicable electrodes are limited to those having a light-transmitting property, and the thickness of the thin film used in these methods is 50-
It is close to the mean free path of free electrons, around 200Å, and there is also the problem that polarization and other factors may be affected. The specular reflection method is a method of observing the electrochemical process on the electrode surface from the difference between the incident light and the reflected light.There is a relatively common method for in-situ observation of the electrode surface. The stability of the substrate is required to be extremely high, and the electrode to be measured needs to have a strictly polished surface, so it is not accurate in a system where the surface roughness changes significantly with electrode reaction. There is a drawback that the measurement target and conditions are limited, such as the difficulty of measurement. Further, the ellipsometry method has a drawback that the measurement target is strictly limited to a sample which is polished as in the specular reflection method, and has a drawback that the apparatus is complicated and expensive because a highly accurate mechanical system is required. On the other hand, the photoelectric polarization method is a method of measuring the change in the electrode surface by measuring the photoelectromotive force or photocurrent generated by the irradiation of light, but this method is applied only to the sample electrode that produces the photoelectric effect. .

As described above, the conventional method for observing the surface of the electrolytic electrode in-situ has problems that the material and conditions of the observable electrode are limited, and that the device is complicated and expensive. However, it has been difficult to easily and easily observe the surface condition of any sample electrode in situ during the electrode reaction.

OBJECT OF THE INVENTION The present invention has been made in view of the above circumstances, and the electrode surface state at the time of the electrode reaction of the electrolytic electrode under any condition can be performed for any electrode without being restricted by the electrode material and the electrolytic conditions. It is an object of the present invention to provide an apparatus capable of performing measurement in situ, that is, while an electrode reaction is proceeding in an electrolytic solution atmosphere, particularly an apparatus capable of performing spectrum analysis.

It is an object of the present invention to provide a novel apparatus that applies the photothermal spectroscopy (PTS) newly invented by the present inventors to in-situ measurement of electrolytic electrodes.

Conventionally, as a light-based spectroscopic method for various substances, an absorbance measurement method is widely known in which the absorbance, which is the reciprocal of the transmittance, is measured by measuring the transmittance of light. Is not applicable. Recently, a method of measuring the absorbance by utilizing the photoacoustic effect has been receiving attention. In this photoacoustic spectroscopy, the sample is placed in a cell (photoacoustic cell) in which an inert gas is sealed, and the intermittent light is radiated at a constant frequency, and the temperature rise due to the light absorption of the sample causes the pressure expansion of the sealed gas. By utilizing the fact that the light is converted into, the change in gas pressure in the cell corresponding to the intermittent frequency (modulation frequency) of light is detected as a sound wave by the high-sensitivity microphone, and synchronous rectification is performed by the lock-in amplifier in synchronization with the frequency. Therefore, the absorbance of light is detected as the intensity of sound waves, and is widely applicable to opaque solid samples.However, in the case of applying the in-situ measurement of the electrode reaction due to the use of a closed cell, Handling is extremely troublesome and not practical.

On the other hand, the present inventors have developed a photothermal spectroscopic method which should be called a new third spectroscopic method. This photothermal spectroscopy
The temperature rise value of the sample with respect to the wavelength of the irradiation light is directly detected by irradiating the sample with light of different wavelengths and using a high-sensitivity thermosensitive element such as a thermistor placed in direct contact with the sample, The spectrum is measured. According to this photothermal spectroscopy, since the rise in the sample temperature due to the absorption of light is directly detected, the state of the electrode can be known on the spot during the electrode reaction in the electrolytic solution. Therefore, it is an object of the present invention to provide a spectroscopic measurement device capable of automatically performing in-situ measurement of an electrolytic electrode by utilizing photothermal spectroscopy.

Configuration of the Invention In order to achieve the above-mentioned object, the electrolytic electrode automatic photothermal spectroscopic measurement device of the present invention is basically configured as follows.

That is, in the automatic photothermal spectrophotometer for electrolytic electrodes of the first invention, the automatic photothermal spectroscopic apparatus for analyzing the surface state of the electrolytic electrode by photothermal spectroscopy in situ while the electrode reaction by electrolysis is performed: A sample chamber for accommodating the electrolytic solution; a reference electrode and a counter electrode which are immersed in the electrolytic solution in the sample chamber together with a sample electrode to be measured, and the potential of the sample electrode with respect to the reference electrode is maintained at a set potential. And a potential applying unit capable of changing its set potential; a selective irradiation means for irradiating the sample electrode in the sample chamber with light of a selected wavelength; and irradiation for the sample electrode Irradiation light interrupting means for interrupting the irradiation of the light beam; temperature detecting means for directly detecting the temperature rise value of the sample electrode due to the irradiation light; A record display means for recording and displaying the temperature rise value of the sample electrode detected, the current flowing through the sample electrode and the potential of the sample electrode with respect to the reference electrode; the selective irradiation means, the irradiation light interrupting means, and the potential applying section. And a control means for controlling.

Here, the control means controls the irradiation light interrupting means so as to repeat the interrupting of the irradiation light in a state where the wavelength of the irradiation light with respect to the sample electrode is held at a selected constant wavelength, and the sample electrode with respect to the reference electrode The potential applying section is controlled to change the potential according to a predetermined program, and the recording and displaying means increases the temperature of the sample electrode at each irradiation by the current flowing through the sample electrode and the irradiation light interrupting means. The value is recorded and displayed corresponding to the sample electrode potential.

The control means changes the wavelength of the irradiation light each time the irradiation of the sample electrode by the irradiation light interrupting means is performed once or more times a predetermined number of times, so that the wavelength is scanned over the entire measurement wavelength range. The recording / displaying means is configured to record and display the sample electrode temperature rise value at each wavelength corresponding to the wavelength of the irradiation light. In this wavelength scanning measurement, the potential of the sample electrode with respect to the reference electrode is controlled or flowed so that the surface state of the sample electrode (for example, the thickness of the electrode reaction product on the surface) is kept substantially constant. The amount of electricity is controlled to be constant.

Here, as the temperature detecting means, for example, two thermosensitive elements having substantially the same characteristics in the measurement range are used, and one thermosensitive element is in contact with the sample electrode to directly detect the sample electrode temperature. The other heat-sensitive element is placed near the sample electrode to detect the temperature of the electrolyte around the sample electrode, and the detection signals of both heat-sensitive elements are processed by, for example, a DC bridge or an AC bridge to detect the ambient temperature. The automatic photothermal spectroscope is configured to detect the temperature rise only in the sample electrode from which the influence of the change is removed.

Further, the selective irradiation means is composed of, for example, a high-intensity light source and a wavelength selector composed of a plurality of bandpass filters or spectroscopes, and the filter is replaced or the wavelength of the dispersion element is changed by a signal from the irradiation light intermittent control means. By driving the selection driver, the wavelength incident on the sample electrode can be changed.

Alternatively, a plurality of single wavelength laser light sources or variable wavelength laser light sources are used as the selective irradiation means.

On the other hand, as the irradiation interrupting means, an optical interrupter (so-called shutter) that is inserted into or removed from the optical path or an optical interrupter that interrupts the light beam alternately (so-called chopper) is used, and the opening / closing time of the optical interrupter is controlled by a timer. Or processing the output signal of the temperature detecting means to control the opening of the optical circuit breaker at the timing when the differential value of the output signal becomes equal to or less than a certain value, or the optical interrupter (chopper) is set in advance. The optical path is rotated at a set speed to open and close the optical path at a predetermined timing.

Also, the automatic photothermal spectroscopic measuring device of the second invention is an automatic photothermal spectroscopic device for analyzing the surface condition of the electrolytic electrode in situ by photothermal spectroscopy while the electrode reaction by electrolysis is in progress: Thermally separated from the surroundings A sample chamber for accommodating the electrolytic solution; a reference electrode and a counter electrode which are immersed in the electrolytic solution in the sample chamber together with a sample electrode to be measured, and the potential of the sample electrode with respect to the reference electrode is held at a set potential and A potentiostat device comprising an electric potential applying section capable of changing the set electric potential; a selective irradiation means for irradiating the sample electrode in the sample chamber with light of a selected wavelength; Irradiation light interrupting means for interrupting irradiation; sample electrode temperature detecting means for directly detecting a temperature rise value of the sample electrode due to irradiation light; electrolyte solution in the sample chamber A standard carbon black dipped in; a means for switchably guiding at least a part of the irradiation light to the sample electrode to the standard carbon black; and a means for directly detecting the temperature rise value of the standard carbon black. Standard temperature detecting means; means for correcting the temperature rise value of the sample electrode measured by the sample electrode temperature detecting means by the temperature detection signal obtained by the standard temperature detecting means; and the corrected sample Record display means for recording and displaying the temperature rise value of the electrode, the current flowing through the sample electrode, and the potential of the sample electrode with respect to the reference electrode; It is characterized by having and.

In the apparatus according to the second aspect of the invention, the wavelength of the irradiation light with which the sample electrode is irradiated is determined by the selective irradiation means each time the irradiation of the light beam with respect to the sample electrode by the irradiation light interrupting means is completed once or more times. Switching, thereby measuring the temperature rise value of the sample electrode in the entire measurement wavelength region, and simultaneously or separately with the measurement of the sample electrode, the carbon black is sequentially irradiated with irradiation light over the entire measurement wavelength region, and the standard temperature detection means The temperature rise value of the sample electrode is corrected over the entire measurement region by the detection signal obtained from the measurement signal, thereby calibrating the measurement error based on the difference in each wavelength energy of the irradiation light.

Further, in the apparatus of the second invention, for example, the temperature detecting means for the sample electrode is constituted by two heat-sensitive elements having substantially the same characteristics within the measurement range, and the first heat-sensitive element among them is used. The second thermosensitive element is arranged in contact with the sample electrode in order to directly detect the temperature of the sample electrode, and the second thermosensitive element is arranged in the vicinity of the sample electrode in order to detect the temperature of the electrolytic solution around the sample electrode, and the standard temperature detecting means is provided. By a third heat-sensitive element arranged in contact with carbon black and a heat-sensitive element arranged in the vicinity of carbon black, which doubles as the second heat-sensitive element or which is different from the second heat-sensitive element. And detecting the temperature rise value of only the sample electrode from which the influence of the ambient temperature change is removed by processing the output signals of the first heat sensitive element and the second heat sensitive element. 3 heat sensitive element and by processing the output signal of the second heat sensitive element or another heat-sensitive element in the vicinity thereof configured to detect a temperature rise value of the carbon black only removing the influence of changes in ambient temperature.

Examples Hereinafter, an electrolytic electrode automatic photothermal spectroscopic measurement apparatus according to an example of the present invention will be described in detail with reference to the drawings.

FIG. 1 shows an embodiment of the present invention, in which an electrolytic solution is contained in a sample chamber 2 which is thermally separated from the surroundings. A sample electrode 1 to be measured, a reference electrode 31 such as a saturated calomel electrode, and a counter electrode 32 are immersed in the electrolytic solution. The sample electrode 1, the reference electrode 31, and the counter electrode 32 constitute a potentiostat device 30 together with the potential applying section 33. The potential applying unit 33,
The potential of the sample electrode 1 with respect to the reference electrode 31 is held at a set potential, and the set potential is controlled and changed by a signal from a control unit 27C of a data processing / control unit 27 described later. The potential applying unit 33
The value of the electric potential V of the sample electrode 1 with respect to the reference electrode 31 and the value of the current i flowing in the sample electrode 1 which are set to 1 are sent to the signal processing unit 27A of the data processing / control unit 27.

In the illustrated example, the sample chamber 2 is composed of a double wall including an inner wall 2A made of a heat insulating material and an outer wall 2B made of a heat insulating material, and a space between the inner wall 2A and the outer wall 2B is filled with a liquid. Although the structure is more excellent in heat insulation, a single wall may be used in some cases. A condensing lens 3 for condensing the irradiation light toward the sample electrode is provided on one surface of the outer wall 2B of the sample chamber 2, and the inner wall 2A is provided at a position corresponding to the condensing lens 3. A transparent window 4 is provided. Therefore, the irradiation light from the outside of the sample chamber irradiates the sample electrode 1 through the condenser lens 3 and the transmission window 4. However, if the light source is a laser beam, a condenser lens is not necessary.

A high-sensitivity heat sensitive element 5 for detecting the temperature of the sample electrode 1, for example, a thermistor, is directly attached to the sample electrode 1, and a heat sensitive element 5 for the sample electrode is provided at a position near the sample electrode 1. A reference thermosensitive element 6 composed of a high-sensitivity thermosensitive element such as a thermistor having substantially the same characteristics is arranged. The latter heat-sensitive element 6 is provided to remove the influence of the temperature of the electrolyte solution around the sample 1 on the measurement error and detect the temperature rise of the sample electrode 1 itself. In addition, it is desirable that any of the heat sensitive elements 5 and 6 is arranged at a position where the irradiation light is not directly incident.

Further, in the sample chamber 2, a half mirror 7 is arranged near the irradiation optical path from the condenser lens 3 to the sample electrode 1 as required. The half mirror 7 calibrates the wavelength distribution of the light source 8 to be described later to eliminate a measurement error caused by a variation in intensity depending on the wavelength of the light source 8 (that is, for normalization of output data). This is for guiding a part to the carbon black 9 immersed in the electrolytic solution in the sample chamber 2 as needed, and is rotated by a rotation driving means such as a motor (not shown) in the irradiation optical path (that is, the irradiation light (Position to reflect a part of it to carbon black 9)
And a position separated from the irradiation light path (that is, a position where a part of the irradiation light is not reflected on the carbon black 9). A standard thermosensitive element 10 such as a thermistor having substantially the same characteristics as the thermosensitive elements 5 and 6 described above is attached to the carbon black 9 at a position where it does not directly receive the irradiation light. The half mirror 7 is removed from the irradiation optical path during the normal measurement in which the wavelength distribution of the light source 8 is not calibrated as described above.

The light source 8 is composed of a high-intensity light source such as a xenon light source, and a filter 11 for cutting unnecessary light in the infrared region from the light source 8 and a condenser lens 12 are arranged in that order on the front side thereof. Has been done. Further, in the optical path between the condenser lens 12 and the condenser lens 3 on the side of the sample chamber 2, a shutter 14 as a light blocker forming a part of the first irradiation light interrupting means 13, and a second shutter The chopper 16 as a rotary type optical interrupter which constitutes a part of the irradiation light interrupting means 15 and the spectroscope 17 as a wavelength selector which constitutes a part of the selective irradiation means are provided in that order.

The shutter 14 is connected to a driving means 18 such as a motor for opening and closing the optical path by inserting and removing the shutter into and from the optical path, and the shutter driving means 18 is a drive circuit for driving and controlling the same. Electrically connected to 19. On the other hand, the chopper 16 has a range that forms a predetermined angle with respect to the center of rotation as a light transmitting part by being cut out, and the remaining angle range as a light shielding part, which is rotated at a preset rotation speed to have a required cycle. The optical path is configured to be repeatedly opened and closed. A motor or other chopper drive means 20 is connected to the chopper 16, and the chopper drive means 20 has a drive circuit for driving and controlling the chopper drive means 20.
21 is electrically connected. A synchronization signal generator 22 for outputting a signal synchronized with the opening and closing of the optical path by the chopper 16 is attached to the chopper 16.

In the above-mentioned example, both the first irradiation light interrupting means 13 including the shutter 14 and the second irradiation light interrupting means 15 including the chopper 16 are arranged. However, both are actually provided. It is not necessary to install it, and only one of them may be installed.

The spectroscope 17 is for selecting the wavelength of the irradiation light to be irradiated from the light source 8 to the sample electrode 1, and is a wavelength selection for changing the selection wavelength by rotating the dispersion element 17A such as a diffraction grating. A driver 50 is attached. As the wavelength selector, instead of the spectroscope 17, a plurality of bandpass filters each having a different wavelength band is used, and the light source 8
The wavelength of the irradiation light with respect to the sample electrode 1 may be selected by exchanging the filter through which the light from the. In this case, a plurality of filters may be attached to, for example, a rotating disk, and the wavelength of the irradiation light to the sample electrode 1 may be changed by rotating the rotating disk with a wavelength selection driver such as a motor. .

As the light source, one or more single wavelength laser light sources or variable wavelength laser light sources may be used. In this case, the spectroscope 17 or the wavelength selector consisting of a plurality of bandpass filters is omitted. You can

The sample electrode thermal element 5 and the reference thermal element 6 are
It is connected to an output difference detection circuit 23 that detects the difference between these outputs. The output difference detection circuit 23 is for detecting the temperature rise value of only the sample electrode 1 from which the influence of the temperature of the surrounding electrolytic solution is removed, and in the illustrated example, the heat sensitive elements 5 and 6 are assembled at one end respectively. It is composed of an embedded AC bridge 24 and an oscillator 25 for generating an AC signal of, for example, 10 kHz for driving the AC bridge 24. This AC bridge
The output of 24 is sent to the synchronization detection circuit 26. The synchronization detection circuit 26 is for synchronously rectifying (synchronous detection) the output of the AC bridge 24 in synchronization with the AC signal of the oscillator 25. Therefore, the output level of the synchronization detection circuit 26 corrects the ambient temperature. It corresponds to the temperature rise value of the sample electrode 1. The output of the synchronization detection circuit 26 is sent to the data processing / control unit 27.

Here, when the chopper 16 is used as the irradiation light connecting / disconnecting means, the synchronization detection circuit 26 uses an AC signal for driving the AC bridge 24 and a synchronization signal of the chopper 16 (synchronization signal generator).
The signal generated by 22) and the two types of signals are used for double coherent detection.

Although the output difference detection circuit 23 is composed of the AC bridge 24 in the above example, it may be composed of a DC bridge depending on the circumstances.

Further, as for the standard carbon black 9 arranged as necessary as described above, the temperature rise value of the carbon black itself, which is free from the influence of the temperature of the surrounding electrolytic solution, is also configured to be detected. That is, the standard thermal element 10 attached to the carbon black 9 is also used in the output difference detection circuit 23.
The output difference detection circuit 23 for detecting the output difference between the sample electrode thermal element 5 and the reference thermal element 6 and the output difference between the standard thermal element 10 and the reference thermal element 6. It can be configured with a double bridge that is a combination of the bridges. In some cases, one end of a single bridge is connected to the sample electrode thermal element 5 and the reference thermal element.
You may comprise so that it may switch with 10.

In the above-mentioned example, the heat sensitive element for detecting the ambient temperature of the sample electrode 1 is commonly used as a means for detecting the ambient temperature of the standard carbon black 9, but in some cases, another heat sensitive element may be used as the carbon black 9. You may install in the vicinity of.

The data processing / control unit 27 controls the potential V of the sample electrode 1 with respect to the reference electrode 31 in the potentiostat device 30.
A signal processing section 27A for processing the current i flowing in the sample electrode 1 and the output of the synchronization detection circuit 26, a recording display section 27B for recording and displaying the data obtained by the signal processing section 27A, and a preset value. It is configured to have the potential applying unit 33, the shutter drive circuit 19, the chopper drive circuit 21, and the control unit 27C for controlling the wavelength selection driver 50 according to a program or a signal from the signal processing unit 27A. .

Regarding the control of the shutter drive circuit 19, for example, the control unit 27C, a circuit for processing and determining a signal corresponding to the temperature rise value of the sample electrode itself output from the synchronization detection circuit 26, and the opening time of the shutter 14. And a timer to set the shutter temperature, and outputs a shutter release command signal based on the result of processing judgment of the temperature rise value signal, and also outputs a shutter cutoff command signal when the opening time set in the timer has elapsed. Just go. As described above, the circuit for processing and determining the sample electrode temperature rise value signal is specifically configured by a circuit that differentiates the temperature rise value and a circuit that determines and compares the differentiated value with a reference level. If the differential value of is a negative value (that is, the temperature rise value is decreasing), the shutter open command signal is output when the absolute value of the differential value falls below a certain level. good.

Alternatively, regarding the control of the shutter drive circuit, the control unit 27C is configured to include a timer that sets the shutoff time of the shutter 14 and a timer that sets the open time of the shutter 14, and the shutter is released when the set shutoff time elapses. It may be configured to output the opening command signal and output the shutter cutoff command signal when the set opening time elapses.

On the other hand, regarding the control of the chopper drive circuit 21, the control unit 27
C is a configuration including a chopper rotation speed control means for controlling the rotation speed of the chopper 16 to a preset speed,
The irradiation time of the irradiation light by the chopper 16 and the interruption time may be determined by controlling the rotation speed.

Further, regarding the control of the wavelength selection driver 23, for example, the control unit 27C is configured to include a counting unit that counts the interruption of the irradiation light by the shutter 14 or the chopper 16, and the number of irradiations at a certain wavelength is preset. A command signal for changing the irradiation wavelength may be output when the number of times is reached. Specifically, the shutter 14 opening command signal or shutoff command signal, or the chopper 16 synchronization signal generator
The signal synchronized with the operation of the chopper 16 from 22 is counted, and when the count value reaches a preset value, a wavelength change command signal is output, and the wavelength selection driver is operated by the command signal and counting is performed. Just reset the means.

Further, as described above, the shutter 14 is used as the irradiation light intermittent means, and the shutter is determined by processing the temperature rise value by differentiation.
When opening 14, the wavelength change command signal may be output together with the chopper open command signal depending on the processing determination result.

In some cases, the wavelength may be fixed and the potential of the sample electrode 1 may be changed to perform the measurement. In that case, the wavelength change command signal may not be output.

On the other hand, the control of the set potential of the sample electrode 1 with respect to the reference electrode 31 in the potential applying section 33 varies depending on the specific mode of measurement, but for example, the set potential V is continuously and cyclically applied at a constant change rate, Alternatively, the control unit 27C may be configured to change in accordance with a preset program, such as a pulse-like change between a certain constant potential and a different constant potential.

FIG. 2 shows a specific example of the AC bridge 24 used in the output difference detection circuit 23 for detecting the output difference between the sample electrode thermal element 5 and the reference thermal element 6. In FIG. 2, the operational amplifier 28 operates as an operational amplifier of an AC bridge, and the operational amplifier 29 is an oscillation frequency of the oscillator 25, for example, 10 kHz.
Acts as a Z bandpass filter.

FIG. 3 shows the potential applying section of the potentiostat device 30.
33 shows specific examples. In FIG. 3, 40 is a voltage application circuit, 4
1, 42 and 43 are amplifiers, respectively, and 44 is a variable resistor for adjusting current measurement sensitivity. The voltage application circuit 40 is controlled by a signal from the control unit 27C of the data processing / control unit 27, and the voltage output terminal 45 and the current output terminal 46 are connected to the signal processing unit 27A of the data processing / control unit 27, respectively. It is connected.

Next, a description will be given of the overall operation or measuring method of the apparatus when the sample electrode is measured by the above-described automatic spectrophotothermal measuring apparatus.

The thermosensitive element 5 is attached to the sample electrode 1 to be measured in advance, and the sample electrode 1, the reference electrode 31, and the counter electrode 32 are provided with a potential applying portion.
33 to connect the electrodes 1 in the electrolyte in the sample chamber 2,
Soak 31 and 32. In addition, the wavelength of the light to be first irradiated is set by the wavelength selector such as the spectroscope 17 or the bandpass filter. Then, the potential V of the sample electrode 1 with respect to the reference electrode is controlled according to a preset program according to the purpose of measurement, and the electrode reaction proceeds. The electric current i and the electric potential V that have flowed to the sample electrode 1 in the electrode reaction are recorded and displayed on the recording / display unit 27B.

If the optical path is opened by the shutter 14 or the chopper 16 in this state, the light of the wavelength is irradiated to the sample electrode 1, and the energy absorbed by the sample electrode 1 out of the energy of the irradiation light becomes heat, and the sample electrode 1 Temperature rises. The temperature of the sample electrode 1 is detected by the thermosensitive element 5. On the other hand, the ambient temperature of the sample electrode 1 also rises, and the ambient temperature is detected by the thermosensitive element 6. The temperature difference between the two is detected by the output difference detection circuit 23, and the temperature corresponding to the temperature obtained by subtracting the ambient temperature from the temperature of the sample electrode 1, that is, the signal corresponding to the temperature rise value of only the sample electrode 1 corrected for the ambient temperature is synchronously detected. The signal is output from the circuit 26 and sent to the data processing / control unit 27.

When the irradiation time of the sample electrode 1 reaches the opening time of the shutter 14 preset by the timer or the light transmission time determined by the rotation speed of the chopper 16, the optical path of the irradiation light to the sample electrode 1 is changed. Alternatively, it is shut off by the shielding part of the chopper 16. The temperature of the sample electrode 1 rapidly drops due to the blocking of the optical path, while the temperature of the surrounding electrolytic solution hardly drops. However, since the ambient temperature is corrected as described above, the data processing / control unit 27 Means that the temperature rise value due to the irradiation light of the sample electrode 1 itself from which the influence of the ambient temperature is removed is given.

After the irradiation light to the sample electrode 1 is blocked as described above, the optical path is opened again and the irradiation light is irradiated to the sample electrode 1. Here, after the light path is blocked, the timing at which irradiation is started again is controlled by setting the timer as described above in the case of the shutter 14 or by controlling the differential value of the temperature rise value to be below a certain value. Also, if the chopper 16 is used, it is determined by its rotational speed. In any case, the timing at which the irradiation is started again after the light path is blocked is set or controlled so that the temperature of the sample electrode 1 is sufficiently lowered to become substantially the same as the ambient temperature. Then, the second measurement at the same wavelength is performed in the same manner as described above, and the subsequent repeated measurement is similarly performed. Of course, in some cases, the measurement at a certain wavelength may be performed only once, and when the measurement at one wavelength is completed once, the wavelength may be changed and the measurement at the next wavelength may be performed as described later.

FIG. 4 shows the waveform of the temperature change of the sample electrode 1 measured as described above with respect to time. In FIG. 4, a broken line A shows a temperature change of the sample electrode 1 when the ambient temperature is not corrected, a broken line B shows a change of the ambient temperature, and a line C is a temperature of the sample electrode 1 corrected with respect to the ambient temperature. A change, that is, an output waveform of the synchronization detection circuit 26 is shown. The output waveform C of this synchronization detection circuit 26 and the maximum temperature rise value (ΔT in FIG. 4) during each irradiation period are recorded on the recording display section 27B as the temperature rise value of the sample electrode 1 at the measurement potential or the measurement wavelength at that time. Recorded and displayed.

In the actual measurement, the shutter 14 and chopper 16
Any of the above may be used, but normally the shutter 14 can be used when the response speed of the heat sensitive element is slow, and the chopper 16 can be used when the response speed is sufficiently fast.

On the other hand, when it is desired to scan the spectrum of the surface product of the sample electrode 1 by scanning the wavelength, the measurement of the sample electrode temperature rise value at the same wavelength is completed once or twice or more as described above. At this time, a wavelength changing command signal is output from the control unit 27C equipped with a counting unit that counts the number of irradiations at the wavelength or a circuit that differentiates the temperature rise value, and the wavelength selecting driver 50 is operated. Select the wavelength.
Then, the measurement at the newly selected wavelength is performed in the same manner as described above. If measurements are sequentially performed at different wavelengths, the measurement in all measurement wavelength regions is finally completed. That is, in order to observe the state of the electrode surface in situ where the reaction is proceeding between the electrodes, the potential V of the sample electrode 1 from the start to the end of the wavelength scanning measurement in the entire wavelength region of the irradiation light. Is controlled to be constant or the amount of electricity flowing between the electrodes is controlled to be constant.

It is desirable that the measured values at each wavelength in the above wavelength scanning measurement be corrected by the measured values of the thermosensitive element 10 of the standard carbon black 9. That is, since the light source 8 has a wavelength characteristic and the intensity differs depending on the wavelength, in order to obtain an absolute light absorption characteristic of the sample electrode 1, a correction for removing the influence of the wavelength characteristic of the light source 8 is performed. Is desirable. In the above-mentioned device, the half mirror 7 is inserted in the optical path, the irradiation light is guided to the carbon black 9, and the temperature rise value is measured by the heat sensitive element 10 for each wavelength in the entire measurement wavelength region. The specific measurement method in this case is the same as the measurement for the sample electrode 1. The sample electrode 1 was obtained by dividing the temperature rise value of the sample electrode 1 by the temperature rise value of the carbon black 9 thus obtained at each wavelength.
The temperature rise value of is corrected and the influence of the wavelength characteristic of the light source 8 is removed. When the half mirror 7 is provided as described above, it is possible to measure the temperature rise value of the carbon black 9 at the same time as the temperature rise value of the sample electrode 1. The temperature rise value of the electrode 1 can be divided by the temperature rise value of the carbon black 9 on the spot, and the correction for removing the influence of the wavelength characteristics can be performed on the spot. It is also possible to correct the measured value of the sample electrode 1 by performing the measurement separately from the measurement of No. 1 and storing the measured value and reading out and dividing the measured value of the carbon black 9 when measuring the sample electrode 1. In the latter case, a normal mirror can be used instead of the half mirror 7.

As described above, the temperature rise value of the sample electrode 1 is corrected by the temperature rise value of the carbon black 9 over the entire wavelength range, whereby the temperature rise value spectrum of the sample electrode 1 can be obtained. Here, the temperature rise value of the sample electrode 1 corresponds to the degree of light absorbed by the sample electrode, that is, the absorbance, so that the spectrum of the temperature rise value corresponds to the absorbance spectrum. Electrode analysis can be performed.

In the above description, the configurations of the embodiments and the respective embodiments described in claims 2 to 18 with respect to the first invention defined in claim 1 and claims 19 With respect to the second invention defined in paragraph (1), the relationship with each of the embodiments described in claims 20 to 22 will be briefly described.

First, the embodiment of the first invention will be described.
The control unit 27C as the control means in the embodiment is configured as a configuration including a counting means for counting the interruption of the irradiation light by the shutter 14 or the chopper 16 as the irradiation light interrupting means, and the number of times of irradiation at a certain wavelength is set in advance. Is configured to output a command signal to change the irradiation wavelength when the temperature reaches, but in some cases, the wavelength change command signal is not output to keep the wavelength constant while measuring the potential by changing the potential of the sample electrode 1. It is also possible, which corresponds to the embodiment of claim 2. That is, in this case, the control unit 27C as the control means, the shutter 14 as the irradiation light interrupting means so as to repeat the interrupting of the irradiation light while maintaining the wavelength of the irradiation light with respect to the sample electrode 1 at the selected constant wavelength. The record display unit 27B, which is configured to control the chopper 16 and to control the potential applying unit 33 so as to change the potential of the sample electrode 1 with respect to the reference electrode 31 according to a predetermined program, and as the record display unit, The current flowing through the sample electrode 1 and the temperature rise value of the sample electrode 1 at each irradiation by the shutter 14 or the chopper 16 are recorded and displayed corresponding to the sample electrode potential.

On the other hand, the control unit 27C as the control means in the embodiment,
As described above, the wavelength change command is issued when the number of irradiations at a certain wavelength reaches a preset number, as a configuration provided with a counting means for counting the number of interruptions of the irradiation light by the shutter 14 or the chopper 16 as the irradiation light interrupting means. The example in which the signal is output corresponds to the embodiment defined in claim 3. That is, in this case, the control unit 27C as the control means controls the sample electrode 1 by the shutter 14 or the chopper 16 as the irradiation light intermittent means.
Each time the irradiation of a predetermined number of times or more is completed, the spectroscope 17 as the selective irradiation means is controlled so that the wavelength of the irradiation light is changed and the wavelength is scanned over the entire measurement wavelength region, and the recording / display means The record display section 27B as
The sample electrode temperature rise value at each wavelength corresponding to the wavelength of the irradiation light is recorded and displayed.

On the other hand, the control unit 27C as the control means also controls the potential and the current with respect to the sample electrode at the time of wavelength measurement. In the case of the above-mentioned embodiment, the control unit 27C controls the potential of the sample electrode 1 through the potential applying unit 33. To do. That is, as shown in the embodiment of claim 4, the control unit 27C as the control means controls the sample electrode with respect to the reference electrode to keep the surface state of the sample electrode 1 substantially constant during the wavelength scanning measurement. It is configured to control the electric potential.

However, as shown in the embodiment defined in claim 5, the control means sets the amount of electricity flowing between the electrodes to be constant in order to keep the surface state of the sample electrode 1 substantially constant during wavelength scanning measurement. You may comprise so that it may be controlled to.

Further, the high-intensity light source 8 and the spectroscope 17 as the wavelength selector in the above-described embodiment are provided with the light of the wavelength selected for the sample electrode 1 as defined in the embodiment of claim 6. Corresponds to a selective irradiation means for irradiating.

Here, the wavelength selector is not limited to the spectroscope shown in the embodiment, and is constituted by a plurality of bandpass filters having a predetermined bandwidth, and the light from the light source passes by the signal from the irradiation light interrupting means. The filters to be replaced may be sequentially replaced, and this embodiment has the following features.
Corresponds to the term.

On the other hand, in the embodiment, the wavelength selector is composed of a spectroscope 17 including a dispersive element 17A that disperses light from a light source,
The wavelength selection driver 50 of the dispersive element 17A is driven by a signal from the shutter 14 or the chopper 16 as the irradiation light connecting / disconnecting means, and this configuration corresponds to the embodiment described in claim 8. .

Further, the above-mentioned wavelength selecting means is not limited to the high-intensity light source 8 and the spectroscope 17 as in the embodiment, but as shown in the embodiment of claim 9, one or a plurality of single It may be composed of a wavelength laser light source, or may be composed of a variable wavelength laser light source as shown in the embodiment of claim 10.

On the other hand, in the above-described embodiment, both the shutter (light blocker) 14 and the chopper (light interrupter) 16 are used as the irradiation light interrupting means for interrupting the irradiation of the irradiation light beam to the sample electrode 1. As described above, only one of them can be used. Further, it is the claims 11 to 13 that define the embodiment especially when the shutter (optical breaker) 14 is used, and when the chopper (optical interrupter) 16 is used. The embodiments are defined in claims 14 to 16.

Further, in the above-mentioned embodiment, as the temperature detecting means, two heat-sensitive elements 5, which have substantially the same characteristics within the measurement temperature range,
6, one of the heat-sensitive elements 5 is arranged in contact with the sample electrode 1 to directly detect the temperature of the sample electrode, and the other heat-sensitive element 6 is used to detect the temperature of the electrolyte solution around the sample electrode 1. Placed near the sample electrode,
By detecting the output difference of the detection signal of 6 by the output difference detection circuit 23, the temperature rise of only the sample electrode from which the influence of the temperature change of the surrounding electrolyte solution is removed is configured to be detected. Corresponds to the embodiment defined in claim 17.

Further, here, a DC bridge or an AC bridge is used as the output difference detection circuit 23, and such a configuration corresponds to the embodiment defined in claim 18.

Next, the embodiment of the second invention will be described.
The embodiment itself of the second invention is the same as the embodiment of the first invention, and in this embodiment, the shutter 14 or the chopper 16 as the irradiation light intermittent means irradiates the sample electrode 1 a predetermined number of times or more. Every time I finish,
The wavelength of the irradiation light is changed by the spectroscope 17 as the selective irradiation means to control the spectroscope 17 as the selective irradiation means so as to scan the wavelength over the entire measurement wavelength region, and simultaneously with or separately from the measurement of the sample electrode 1. The carbon black 9 is sequentially irradiated with irradiation light over the entire measurement wavelength region, and the temperature rise value of the sample electrode 1 is corrected over the entire measurement region by the detection signal obtained from the thermosensitive element 10 as the standard temperature detection means. By this, the measurement error based on the difference in the wavelength energy of the irradiation light is calibrated, and such a configuration corresponds to the embodiment described in claim 20.

Further, in the embodiment, the first heat sensitive element 5 of the two heat sensitive elements 5 and 6 having substantially the same characteristics within the measurement range is arranged in contact with the sample electrode 1 so as to directly detect the sample electrode temperature. At the same time, the second heat sensitive element 6 is arranged in the vicinity of the sample electrode in order to detect the temperature of the electrolytic solution around the sample electrode 1,
On the other hand, the third heat sensitive element 10 is arranged in contact with the carbon black, and another heat sensitive element is arranged near the carbon black if necessary. Such a construction is claimed in claim 21. It corresponds to the embodiment described in the paragraph.

Further, in the embodiment, the above-mentioned heat-sensitive element is incorporated in a DC bridge or an AC bridge, and such a configuration corresponds to the embodiment described in claim 22.

The following is an example of actual measurement of various sample electrodes using the apparatus of the present invention.

Fig. 5 shows the results of investigating the reaction of Cu electrodeposition on the Au electrode and the formation reaction of the surface oxide film. The Au electrode was used as the sample electrode and the saturated calomel electrode was used as the reference electrode. Using Na ₂ SO ₂ as the electrolyte, the potential of the sample electrode was cyclically changed with the irradiation light wavelength kept constant, and the V-i curve (cyclic portometry) and V-ΔT (temperature rise of the sample electrode) (Value) shows the result of measuring the curve. The irradiation light was interrupted at 8 Hz using a chopper, and the irradiation light was an Argo ion laser light having a light intensity of 0.8 W and a wavelength of 541.5 nm.

As shown in FIG. 5, as the potential V becomes negative and Cu is electrodeposited, ΔT tends to increase. This indicates that the light absorption on the electrode surface is increased by Cu electrodeposition. Furthermore, as the potential V is changed in the positive direction and Cu elutes,
It can be seen that ΔT decreases and Cu elutes completely from the surface to the solution side and the surface returns to the original Au, and ΔT returns to the initial point. Such a behavior of ΔT shows good reproducibility with respect to repeated potential sweeps as in the case of the V-i curve. Therefore, it can be seen from the V-ΔT curve that copper is electrodeposited or dissolved on the surface of gold. Can be observed depending on whether light is absorbed or reflected easily, that is, as a change in ΔT.

FIG. 6 is a plot of the relative change in ΔT accompanying Cu electrodeposition-Cu elution with respect to the amount of electricity flowing, using the same electrodes and electrolytes as in the measurement of FIG. 5 and the same irradiation conditions. is there. Here, the potential of the sample electrode was kept constant at a Cu deposition potential of −0.5 V in the first half period, and was kept constant at a Cu elution potential of +0.5 V in the second half period. From FIG. 6, ΔT increases almost linearly with the amount of electricity in the region where the deposited layer is thin, and then reaches saturation. This occurs in relation to the amount of the electrodeposited, and indicates that the light is completely absorbed and saturated at a certain thickness.
Therefore, it becomes possible to analyze the surface electrodeposition state.

FIG. 7 is a graph showing the formation reaction of the anodic oxide film on the Au electrode, as shown in FIG. 5 when the Au electrode was used as the sample electrode, the saturated calomel electrode was used as the reference electrode, and 1 molar HClO ₄ was used as the electrolyte. Similar measurement results are shown. The irradiation conditions are the same as in FIG.

Similarly, FIG. 8 is a plot of the relative change in ΔT associated with Au oxide film formation and Au oxide film elution with respect to the amount of electricity flowing. The electrodes, the electrolytic solution, and the irradiation conditions were the same as in the case of FIG. 7, and the potential of the sample electrode was kept constant at +1.2 V until the middle, and then changed to +0.5 V. Gold is a stable metal that is very hard to oxidize because it has only one or two oxide layers. However, from the results of FIG. 8, according to the method of the present invention, a region where ΔT changes linearly and a saturation region are also observed, and the sensitivity is sufficient to detect even one or two layers of oxide film with good resolution. I understand.

FIG. 9 shows a photothermal spectroscopic spectrum obtained by wavelength scanning measurement when a DHV ⁺ Br ⁻ film was electrodeposited on a platinum electrode. In this measurement, a pulse potential varying between −0.2 V and −0.55 V was applied to the sample electrode to keep the thickness of the electrodeposition film constant, and the wavelength was scanned in that state to measure ΔT.
In this way, it is also possible to obtain a photothermal spectrum by wavelength scanning and examine the products on the electrode surface.

Similar to the case of FIG. 9, FIG. 10 shows the relation between ΔT and the charge flowing per unit area measured by a Coulomb meter when a DHV ⁺ Br ⁻ film was electrodeposited on a platinum electrode. In this case, the sample electrode potential was kept constant at -0.5 V, and ΔT was measured over time with irradiation light of 500 nm. ΔT increases almost linearly up to about 3 × 10 ^-3 coulomb / cm ² . Since the amount of charge is almost proportional to the film thickness, it is possible to know the film thickness by measuring ΔT.

EFFECTS OF THE INVENTION According to the automatic spectroscopic measurement apparatus for electrolytic electrodes of the present invention, the electrolytic electrode in which the electrode reaction is progressing in the electrolytic solution can be measured in situ, and therefore the progress of the electrode reaction and the like can be measured. Since it can be known in the field, it can contribute to the research of electrode reactions and the like. In particular, it is possible to obtain a spectrum of the electrode surface product that is solid in the electrolytic solution and to know the film thickness of the product. It is possible to achieve a remarkable effect. Further, since the apparatus of the present invention is capable of automatically performing in-situ measurement of the electrolytic electrode and measuring by the temperature rise, it is not necessary to strictly polish the sample electrode, and further, it is a target. The sample electrode has a feature that cannot be obtained by the conventional in-situ measurement method of the electrolytic electrode, such as the optical thickness is not limited.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing an embodiment of an electrolytic electrode automatic photothermal spectroscopic measurement device of the present invention, and FIG. 2 is an alternating current as an output difference detection circuit used in the device of FIG. FIG. 4 is a connection diagram showing an example of a bridge, FIG. 3 is a connection diagram showing a specific example of the potential applying section of the potentiostat device used in the device of FIG. 1, and FIG. FIG. 5 is a waveform diagram schematically showing an example of the temperature change of the sample electrode (output waveform of the period detection circuit 26) when the measurement is performed, and FIG. 5 is a cyclic V-i curve in the Cu electrodeposition experiment on the Au electrode. And V-Δ
FIG. 6 is a diagram showing a T curve, FIG. 6 is a diagram showing a relationship between ΔT and an electric quantity in the Cu electrodeposition experiment on the Au electrode, and FIG. 7 is a cyclic V-i curve in the anodic oxidation experiment of the Au electrode and FIG. 8 is a view showing a V-ΔT curve, FIG. 8 is a view showing a relationship between ΔT and an electric quantity in the anodic oxidation experiment of the Au electrode, and FIG. 9 is a photothermal spectroscopic spectrum in the electrodeposition experiment of the DHV ⁺ Br ⁻ film. Similarly, FIG. 10 and FIG. 10 are views showing the relationship between ΔT and electric charge in the electrodeposition experiment of DHV ⁺ Br ⁻ film. 1 ... Sample electrode, 2 ... Sample chamber, 5 ... Sample electrode thermal element, 6 ... Reference thermal element, 8 ... Light source, 9 ... Carbon black, 10 ... Standard thermal element, 13 ... … First irradiation light interrupter, 14 …… Shutter (light blocker), 15 ……
Second irradiation light interrupting means, 16 ... Chopper (optical interrupter), 17 ... Spectrometer as wavelength selector, 17A ... Dispersion element, 18 ... Shutter driving means, 20 ... Chopper driving means, 23 ...... Output difference detection circuit, 24 …… AC bridge,
26 ... Synchronous detection circuit, 27 ... Data processing / control section, 30 ...
… Potentiostat device, 31 …… reference electrode, 32 …… counter electrode, 33 …… potential application section.

Claims (22)

[Claims] 1. An automatic photothermal spectroscopic apparatus for in-situ analysis of the surface state of an electrolytic electrode by photothermal spectroscopy while an electrode reaction by electrolysis is in progress: A sample containing an electrolytic solution, which is thermally separated from the surroundings. Chamber; a reference electrode and a counter electrode that are immersed in an electrolytic solution in the sample chamber together with a sample electrode as an electrolytic electrode to be measured, and the potential of the sample electrode with respect to the reference electrode is held at a set potential and the set potential is changed. A potentiostat device composed of a potential applying section adapted to be capable of controlling; a selective irradiation means for irradiating the sample electrode in the sample chamber with light of a selected wavelength; and for intermittently irradiating the sample electrode with the irradiation light beam. Irradiation light interrupting means; temperature detecting means for directly detecting a temperature rise value of the sample electrode due to the irradiation light; temperature of the sample electrode detected by the temperature detecting means A recording and displaying means for recording and displaying an ascending value, a current flowing through the sample electrode, and the potential of the sample electrode with respect to a reference electrode; and a control means for controlling the selective irradiation means, the irradiation light interrupting means, and the potential applying section. An automatic photothermal spectroscopic measurement device for electrolytic electrodes, characterized by being configured as follows. 2. The control means controls the irradiation light interrupting means so as to repeat the interrupting of the irradiation light while keeping the wavelength of the irradiation light with respect to the sample electrode at a selected constant wavelength, and the sample with respect to the reference electrode. Control the potential applying section to change the potential of the electrode according to a predetermined program,
Further, the recording and displaying means records and displays the current flowing through the sample electrode and the temperature rise value of the sample electrode at each irradiation by the irradiation light interrupting means in correspondence with the sample electrode potential. An automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 1. 3. The control means changes the wavelength of the irradiation light every time when the irradiation light interrupting means completes the irradiation of the sample electrode one or more times, and scans the wavelength over the entire measurement wavelength range. 2. The selective irradiation means is controlled, and the recording / display means records and displays the sample electrode temperature rise value at each wavelength corresponding to the irradiation light wavelength. An automatic photothermal spectroscopic measurement device for the electrolytic electrode described. 4. The control means according to claim 3, wherein the control means controls the potential of the sample electrode with respect to the reference electrode in order to keep the surface state of the sample electrode substantially constant during wavelength scanning measurement. An automatic photothermal spectroscopic measurement device for the electrolytic electrode described. 5. The control means according to claim 3, wherein the quantity of electricity flowing between the electrodes is controlled to be constant in order to keep the surface state of the sample electrode substantially constant during wavelength scanning measurement. An automatic photothermal spectroscopic measurement device for an electrolytic electrode according to the item. 6. The electrolysis according to claim 1, wherein the selective irradiation means comprises a high-intensity light source and a wavelength selector for selecting light of a required wavelength from the light from the light source. Automatic photothermal spectrophotometer for electrodes. 7. The wavelength selector is composed of a plurality of bandpass filters having a predetermined bandwidth, and the filters from which the light from the light source should pass are sequentially replaced by signals from the irradiation light interrupting means. The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 6. 8. The wavelength selector is composed of a spectroscope having a dispersive element that disperses light from a light source, and drives a wavelength selecting driver of the dispersive element by a signal from the irradiation light interrupting means. 7. An automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 6. 9. The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 1, wherein the selective irradiation means comprises one or a plurality of single wavelength laser light sources. 10. The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 1, wherein the selective irradiation means is composed of a variable wavelength laser light source. 11. The irradiation light interrupting means comprises an optical breaker and a driving means for inserting the optical breaker into and out of the optical path, and the control means comprises an optical path by the optical breaker. The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 1, wherein the automatic photothermal spectroscopic measurement device has a timer for setting an opening time and a closing time of the. 12. The irradiation light interrupting means comprises an optical breaker and a driving means for inserting the optical breaker into and out of the optical path, and the control means outputs the output of the temperature detecting means. 2. The structure according to claim 1, wherein the timing of opening the optical path by the optical circuit breaker is controlled according to the result of processing determination of a signal, and the opening time of the optical circuit breaker is controlled by a time preset in a timer. Photothermal Spectrometer for Electrolysis Electrodes. 13. The control means is configured to differentiate the output signal of the temperature detecting means and to cause the optical breaker to open the optical path when the differential value becomes smaller than a predetermined value. 13. An automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 12. 14. The irradiation light interrupting means comprises an optical interrupter in which a light transmitting portion and a light interrupting portion are alternately formed, and a driving means for continuously driving the optical interrupter, and the optical interrupter is preliminarily provided. The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 1, wherein the irradiation light is alternately and intermittently driven by driving at a set speed. 15. The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 14, wherein the optical interrupter is composed of a rotary chopper. 16. The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 14, wherein the signal from the temperature detecting means is synchronously detected in synchronization with opening and closing of the optical interrupter. 17. The temperature detecting means comprises two heat-sensitive elements having substantially the same characteristics within a measuring range,
One heat-sensitive element is placed in contact with the sample electrode to directly detect the sample electrode temperature, and the other heat-sensitive element is placed near the sample electrode to detect the temperature of the electrolyte around the sample electrode. The temperature rise of only the sample electrode from which the influence of the temperature change of the surrounding electrolyte solution is removed by detecting the output difference of the detection signal of the element by the output difference detection circuit. Automatic photothermal spectrophotometer. 18. The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 17, wherein said output difference detection circuit is constituted by a DC bridge or an AC bridge incorporating said two thermosensitive elements. 19. An automatic photothermal spectroscopic apparatus for in-situ analysis of the surface state of an electrolytic electrode by photothermal spectroscopy during the progress of an electrode reaction by electrolysis: a sample containing an electrolytic solution, which is thermally separated from the surroundings. A chamber; a reference electrode and a counter electrode that are immersed in an electrolyte solution in the sample chamber together with a sample electrode to be measured, and the potential of the sample electrode with respect to the reference electrode can be maintained at a set potential and the set potential can be changed. A potentiostat device comprising: a potential applying part; a selective irradiation means for irradiating the sample electrode in the sample chamber with light of a selected wavelength; and an intermittent irradiation light for intermittent irradiation of the irradiation light beam to the sample electrode. Means; a temperature detecting means for the sample electrode for directly detecting the temperature rise value of the sample electrode due to the irradiation light; and a standard carbon bra immersed in the electrolytic solution in the sample chamber. Means for guiding at least part of the irradiation light to the sample electrode to the standard carbon black in a switchable manner; standard temperature detecting means for directly detecting the temperature rise value of the standard carbon black; A means for correcting the temperature rise value of the sample electrode measured by the temperature detection means for sample electrode by the temperature detection signal obtained by the temperature detection means for standard; and the temperature rise value of the corrected sample electrode, A recording and displaying means for recording and displaying the current flowing through the sample electrode and the potential of the sample electrode with respect to the reference electrode; and a control means for controlling the selective irradiation means, the irradiation light interrupting means, and the potential applying section. An automatic photothermal spectroscopic measurement device for electrolytic electrodes. 20. Each time the irradiation light interrupting means completes irradiation of the sample electrode one or more times a predetermined number of times,
The selective irradiation means is controlled so that the wavelength of the irradiation light is changed by the selective irradiation means to scan the wavelength over the entire measurement wavelength range, and the carbon black is sequentially measured over the entire measurement wavelength range simultaneously with or separately from the measurement of the sample electrode. Irradiation light is irradiated, and the temperature rise value of the sample electrode is corrected over the entire measurement area by the detection signal obtained from the standard temperature detection means, thereby calibrating the measurement error based on the difference in the wavelength energy of the irradiation light. 20. An automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 19, characterized in that. 21. The sample electrode temperature detecting means is composed of two heat-sensitive elements having substantially the same characteristics within a measurement range, and the first heat-sensitive element among them directly detects the sample electrode temperature. Therefore, the second heat sensitive element is arranged in contact with the sample electrode, and the second heat sensitive element is arranged in the vicinity of the sample electrode to detect the temperature of the electrolyte around the sample electrode, and the standard temperature detecting means is in contact with the carbon black. And a second heat-sensitive element which is arranged in the vicinity of carbon black and which is common to or different from the second heat-sensitive element, the first heat-sensitive element and the second heat-sensitive element. By processing the output signal of the heat sensitive element, the temperature rise value of only the sample electrode from which the influence of the ambient temperature change is removed is detected, and the third heat sensitive element and the second heat sensitive element in the vicinity thereof are also detected. 20. The automatic electrolytic electrode according to claim 19, wherein the temperature rise value of only carbon black from which the influence of ambient temperature change is removed is processed by processing the output signal of another heat-sensitive element. Photothermal spectrophotometer. 22. The first and second heat sensitive elements are incorporated into a DC bridge or an AC brush, and the third heat sensitive element and the second heat sensitive element near the heat sensitive element or another heat sensitive element is connected to the DC bridge or The automatic photothermal spectroscopic measurement device for an electrolytic electrode according to claim 21, which is incorporated in an AC bridge.