WO2013077166A1 - ラマン分光測定用反応容器及びこれを用いたラマン分光測定方法 - Google Patents
ラマン分光測定用反応容器及びこれを用いたラマン分光測定方法 Download PDFInfo
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- WO2013077166A1 WO2013077166A1 PCT/JP2012/078386 JP2012078386W WO2013077166A1 WO 2013077166 A1 WO2013077166 A1 WO 2013077166A1 JP 2012078386 W JP2012078386 W JP 2012078386W WO 2013077166 A1 WO2013077166 A1 WO 2013077166A1
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- reaction vessel
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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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N2021/0325—Cells for testing reactions, e.g. containing reagents
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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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N2021/651—Cuvettes therefore
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
-
- 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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/09—Cuvette constructions adapted to resist hostile environments or corrosive or abrasive materials
Definitions
- the present invention relates to a reaction vessel for Raman spectroscopy measurement and a Raman spectroscopy measurement method using the same, and particularly to Raman spectroscopy measurement under an electrochemical reaction.
- the chemical reaction involving the solid surface is related to various industrially important applications such as batteries, catalysts, coatings, particle formation, corrosion, and sensors.
- Laser Raman spectroscopy is a technique for estimating the chemical structure of a molecule by measuring the vibrational state of the molecule.
- Laser Raman spectroscopy has an advantage that measurement can be performed even in an aqueous solution or the like, unlike infrared spectroscopy that provides similar information. Therefore, according to laser Raman spectroscopy, a chemical reaction process on a solid surface surrounded by a solution can be traced at a molecular level (see, for example, Non-Patent Document 1).
- the present invention has been made in view of the above problems, and provides a reaction vessel for Raman spectroscopy measurement suitable for an electrochemical reaction on a solid surface in an electrolytic solution and a Raman spectroscopy measurement method using the same.
- a reaction vessel for Raman spectroscopy measurement suitable for an electrochemical reaction on a solid surface in an electrolytic solution and a Raman spectroscopy measurement method using the same.
- a reaction vessel for Raman spectroscopic measurement for solving the above-described problem has a transparent window part, and a casing part in which a hollow part for accommodating an electrolyte is formed; It is composed of a conductive material that is electrochemically inert in the electrolyte solution, and a part of the conductive material is disposed in the hollow part to face the window part to hold the sample, and the other part is connected to an external power source. And a working electrode portion extending to the outside of the housing portion for connection.
- the reaction container for Raman spectroscopy measurement suitable for the electrochemical reaction in the solid surface in electrolyte solution can be provided.
- the working electrode part may be a member extending in parallel to the window part.
- the conductive material may be at least one selected from the group consisting of conductive carbon materials, conductive ceramics, gold, and gold-plated conductive materials.
- the said reaction container is good also as being used for micro Raman spectroscopy measurement.
- a Raman spectroscopic measurement method includes a casing portion having a transparent window portion and a hollow portion for accommodating an electrolyte solution, and the electrolyte solution. It is composed of an electrically conductive material that is electrochemically inactive, part of which is disposed in the hollow part so as to face the window part, and the other part is extended outside the casing part.
- a reaction vessel including an electrode part, holding a sample in the part arranged to face the window part of the working electrode part, and to the outside of the casing part of the working electrode part Connecting the other part extended to an external power source, storing the electrolyte in the hollow portion, and performing Raman spectroscopic measurement during the electrochemical reaction of the sample in the electrolyte It is characterized by including.
- ADVANTAGE OF THE INVENTION According to this invention, the Raman spectroscopy measuring method suitable for the electrochemical reaction in the solid surface in electrolyte solution can be provided.
- the working electrode part may be a member extending in parallel to the window part.
- the conductive material may be at least one selected from the group consisting of conductive carbon materials, conductive ceramics, gold, and gold-plated conductive materials.
- the Raman spectroscopic measurement may be microscopic Raman spectroscopic measurement.
- the microscopic Raman spectroscopic measurement may be performed by arranging the reaction container between a lens for irradiating excitation light and a microscope stage arranged to face the lens.
- a reaction vessel for Raman spectroscopy measurement suitable for an electrochemical reaction on a solid surface in an electrolytic solution and a Raman spectroscopy measurement method using the same can be provided.
- FIG. 3 is an explanatory diagram showing a cross section of the reaction vessel for Raman spectroscopic measurement cut along line III-III shown in FIG.
- FIG. 4 is an explanatory diagram showing a cross section of the reaction vessel for Raman spectroscopic measurement cut along line IV-IV shown in FIG. 2. It is explanatory drawing which shows an example of a mode that microscopic Raman spectroscopy measurement is performed using the reaction container for Raman spectroscopy measurement shown in FIG.
- FIG. 1 is an explanatory view showing an example of a reaction vessel for Raman spectroscopy measurement (hereinafter referred to as “the present reaction vessel 1”) according to the present embodiment in a perspective view.
- FIG. 2 is an explanatory view showing the reaction container 1 shown in FIG. 1 in a plan view.
- FIG. 3 is an explanatory view showing a cross section of the reaction vessel 1 taken along the line III-III shown in FIG.
- FIG. 4 is an explanatory view showing a cross section of the present reaction vessel 1 taken along line IV-IV shown in FIG.
- FIG. 5 is an explanatory diagram showing an example of a state in which microscopic Raman spectroscopic measurement is performed using the reaction vessel 1.
- the present reaction vessel 1 has a transparent window portion 11, a casing portion 10 in which a hollow portion 12 for accommodating the electrolyte solution E is formed, and the electrolyte solution E
- a part thereof (hereinafter referred to as “sample stage portion 21”) is formed in the window portion 11 in the hollow portion 12 and is made of an electrically conductive material that is electrochemically inactive.
- a working electrode portion 20 that is disposed to face the other portion (hereinafter referred to as “extension portion 22”) and extends to the outside of the housing portion 10 in order to be connected to an external power source. ing.
- This reaction container 1 is used for Raman spectroscopic measurement of an electrochemical reaction on the solid surface in the electrolyte E (specifically, the surface 21a facing the window portion 11 of the sample base portion 21 of the working electrode portion 20).
- the electrochemical reaction is not particularly limited as long as it is an electrochemical reaction that occurs on the solid surface in the electrolytic solution E, but may be, for example, an oxidation-reduction reaction.
- this reaction container 1 can be used also for the Raman spectroscopic measurement in an electrochemical polymerization process, a crystal precipitation process, an electrical reaction process, an electrochemical synthesis process, a sensor reaction process, and a biochemical reaction process, for example.
- the electrochemical reaction may be, for example, a heterogeneous catalytic reaction. That is, in this case, the sample S containing a heterogeneous catalyst is used. More specifically, the sample S including the heterogeneous catalyst is held on the sample stage 21 of the working electrode portion 20 of the reaction vessel 1.
- the Raman spectroscopic measurement of the heterogeneous catalytic reaction for example, the oxidation-reduction reaction catalyzed by the heterogeneous catalyst
- the Raman spectroscopic measurement of the heterogeneous catalytic reaction for example, the oxidation-reduction reaction catalyzed by the heterogeneous catalyst
- the heterogeneous catalyst is not particularly limited, and examples thereof include an immobilized catalyst such as a carbon catalyst, a metal catalyst, and a metal compound catalyst, and an immobilized biomolecule (such as an immobilized antigen, an immobilized antibody, an immobilized nucleic acid, and an immobilized enzyme).
- an immobilized catalyst such as a carbon catalyst, a metal catalyst, and a metal compound catalyst
- an immobilized biomolecule such as an immobilized antigen, an immobilized antibody, an immobilized nucleic acid, and an immobilized enzyme.
- the carbon catalyst include a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal (preferably a transition metal), and exhibit a redox reaction catalytic activity (for example, an oxygen reduction reaction catalytic activity).
- a carbon catalyst may be used.
- the electrolytic solution E is not particularly limited as long as it can perform the electrochemical reaction of the sample S therein. That is, the pH of the electrolytic solution E is not particularly limited, and the acidic electrolytic solution E may be used, or the alkaline electrolytic solution E may be used. Further, as the electrolytic solution E, a corrosive electrolytic solution may be used.
- the pH may be 0 to 5, for example.
- the acidic electrolytic solution E may be selected from the group consisting of mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, super strong acids, organic acids, organic electrolytes, buffer solutions (buffers), and ionic liquids, for example. Good.
- the housing unit 10 is a box-shaped hollow body that accommodates at least the electrolytic solution E and the sample stage unit 21 of the working electrode unit 20 therein.
- the casing 10 is formed as a rectangular parallelepiped having a hollow inside.
- casing part 10 will not be restricted especially if it is an insulating material,
- the casing 10 is preferably made of a corrosion-resistant material.
- the resin for example, one or more selected from the group consisting of vinyl chloride resin, phenol resin, polyolefin resin (for example, polyethylene and / or polypropylene), acrylic resin, fluororesin, and silicon resin are preferably used. be able to.
- the window portion 11 constitutes a part of the outer wall of the housing portion 10 through which excitation light (laser) is transmitted in Raman spectroscopic measurement.
- the window portion 11 is a plate-like member made of a transparent material.
- the material constituting the window portion 11 is not particularly limited as long as it is a transparent material that transmits excitation light.
- the material is selected from the group consisting of glass (preferably quartz glass), transparent synthetic resin, and transparent ceramics. It is good also as being 1 or more types.
- the thickness of the window portion 11 is not particularly limited as long as Raman spectroscopy measurement is possible.
- the hollow portion 12 is a space formed inside the housing portion 10 in order to accommodate the electrolytic solution E.
- the hollow portion 12 is preferably a sealed space at least during Raman spectroscopic measurement.
- the working electrode part 20 has a sample stage part 21 arranged in the hollow part 12 of the casing part 10 and an extending part 22 extending outside the casing part 10.
- the shape of the working electrode part 20 is not particularly limited as long as the Raman spectroscopic measurement of an electrochemical reaction using the working electrode part 20 as a working electrode is possible, but the working electrode part 20 is, for example, the window part 11. It may be a member (for example, a plate-like member as shown in FIGS. 1 to 5) extending in parallel with the member.
- the sample stage part 21 and the extending part 22 are formed as a part of the member extending in parallel to the window part 11 and the other part, the height of the reaction container 1 (in particular, the casing part). 10 height) can be effectively reduced.
- the thickness of the working electrode portion 20 is not particularly limited.
- the conductive material constituting the working electrode portion 20 is a material that has conductivity and is electrochemically inactive in the electrolytic solution E.
- the conductive material is electrochemically inactive, for example, that the conductive material does not dissolve when a potential is applied to the conductive material, and is in contact with the conductive material. This includes not showing electrolysis of the solvent (electrolyte) over a wide potential range. That is, this conductive material is, for example, an electrically conductive material that is electrochemically inactive in the range of ⁇ 0.2 V to 1.2 V (vs. NHE) regardless of the pH of the electrolyte E. Material.
- the conductive material is not particularly limited as long as it is electrochemically inactive in the electrolytic solution E.
- the conductive material is selected from the group consisting of conductive carbon materials, conductive ceramics, gold, and gold-plated conductive materials. It is good also as being 1 or more types.
- the conductive carbon material is not particularly limited as long as it is a conductive carbon material.
- the conductive carbon material is one or more selected from the group consisting of glassy carbon, isotropic carbon, and graphite material (for example, HOPG). It may be there.
- the conductive ceramic is not particularly limited as long as it is a ceramic material having conductivity.
- the conductive ceramic may be one or more selected from the group consisting of titanium oxide, tin oxide, and indium tin oxide (ITO). .
- the sample stage part 21 is a part of the working electrode part 20, and is a part arranged facing the window part 11 in the hollow part 12 of the housing part 10.
- the sample S is held on the surface 21 a facing the window portion 11 of the sample table 21.
- the surface 21a is formed as a flat surface.
- the distance between the window part 11 and the sample stage part 21 is not particularly limited as long as Raman spectroscopic measurement is possible.
- the extending part 22 is a part of the working electrode part 20 different from the sample stage part 21, and is provided so as to protrude from the outer surface 10 a of the housing part 10. That is, the extending portion 22 is formed by extending a part of the working electrode portion 20 from the inside of the hollow portion 21 to the outside of the housing portion 10 through the housing portion 10.
- the extending portion 22 is configured so that a part of the member is partly parallel to the window portion 11. It is formed by extending up to 10.
- the extending portion 22 is formed by exposing one end portion of a plate-like member constituting the working electrode portion 20 to the outside of the housing portion 10.
- the extension 22 is electrically connected to an external power source. That is, in the example shown in FIG. 5, the extending portion 22 is connected to an external power source (not shown) via the wiring W.
- an extended portion 22 formed by extending a part of the working electrode portion 20 to the outside of the housing portion 10 is provided. It is not necessary to arrange the wiring W for efficient connection in the electrolytic solution E.
- reaction container 1 it is possible to effectively reduce the presence of members that can affect the electrochemical reaction in the electrolytic solution E in the reaction vessel 1. Moreover, the structure of this reaction container 1 can also be simplified.
- this reaction container 1 is preferably used for microscopic Raman spectroscopic measurement. That is, as shown in FIG. 5, the reaction vessel 1 is arranged between a lens L for irradiating excitation light and a microscope stage M arranged opposite to the lens L in a microscopic Raman spectroscopic measurement system. Can be placed in a small space. Therefore, by using this reaction container 1, for example, a commercially available microscopic Raman spectroscopic measurement system can be used as it is without modifying the microscopic Raman spectroscopic measurement system.
- the reaction vessel 1 may further include a counter electrode 30 and a reference electrode 40 as shown in FIGS.
- a counter electrode 30 for example, a platinum (Pt) electrode can be used.
- a reference electrode 40 for example, a silver / silver chloride (Ag / AgCl) electrode can be used.
- one end portion 32 of the counter electrode 30 and one end portion 42 of the reference electrode 40 are disposed in the hollow portion 12 so as to be immersed in the electrolytic solution E.
- the other end portion 31 of 30 and the other end portion 41 of the reference electrode 40 are extended outside the housing portion 10 in order to be connected to an external power source.
- the end 31 of the counter electrode 30 and the end 41 of the reference electrode 40 are oriented differently from the outer surface 10a of the casing 10 from which the extended portion 22 of the working electrode 20 protrudes (example shown in FIGS. 1 to 5). It is good also as protruding from the other outer surface 10b formed in (orthogonal direction). That is, in the example shown in FIGS. 1 to 5, the extending portion 22 of the working electrode portion 20 protrudes from one outer surface 10a of the housing portion 10, and the end portion 31 of the counter electrode 30 and the end portion 41 of the reference electrode 40 are , And protrudes from the other outer surface 10b of the casing portion 10 orthogonal to the outer surface 10a.
- the housing 10 has a shelf 13 that supports the working electrode 20 from the side opposite to the window 11, and a distance between the working electrode 20 and the window 11. It further has a bottom portion 14 that is separated from the window portion 11 by a large distance and faces the window portion 11.
- the working electrode portion 20 is disposed close to the window portion 11, and between the window portion 11 and the bottom portion 14, between the window portion 11 and the working electrode portion 20.
- a larger amount of the electrolytic solution E can be accommodated.
- one end 32 of the counter electrode 30 and one end 42 of the reference electrode 40 are disposed between the window portion 11 and the bottom portion 14.
- the Raman spectroscopic measurement method according to the present embodiment is a method for performing the Raman spectroscopic measurement using the reaction vessel 1 described above. That is, this method has a transparent window portion 11 and a casing portion 10 in which a hollow portion 12 for accommodating the electrolytic solution E is formed, and an electrically conductive material that is electrochemically inert in the electrolytic solution E. Part (sample base part 21) is arranged to face the window part 11 in the hollow part 12, and the other part (extension part 22) is outside the casing part 10.
- a reaction vessel (main reaction vessel 1) having a working electrode portion 20 extended to a position, holding the sample S on the sample base portion 21, and connecting the extension portion 22 to an external power source Doing, storing the electrolytic solution E in the hollow portion 12, and performing Raman spectroscopic measurement of the electrochemical reaction of the sample S in the electrolytic solution E.
- the reaction vessel 1 is disposed between a lens L for irradiating excitation light and a microscope stage M disposed opposite to the lens L, and microscopic Raman spectroscopic measurement is performed. Do.
- the reaction container 1 is placed on the microscope stage M so that the window 11 faces the lens L (the sample S faces the lens L through the window 11). Install in.
- a microscopic Raman spectroscopic system including the lens L and the microscope stage M a commercially available system may be used.
- the method for holding the sample S on the sample stage 21 is not particularly limited as long as the sample S can be fixed to the surface 21 a of the sample stage 21. That is, for example, using a binder (for example, Nafion (registered trademark)), a method of applying a slurry containing the sample S to the surface 21a of the sample table 21 or the sample S on the surface 21a of the sample table 21
- the sample S can be fixed to the surface 21a by using a method of directly forming a film.
- the method for connecting the extended portion 22 to an external power source is not particularly limited as long as the extended portion 22 and the external power source can be electrically connected. That is, for example, as shown in FIG. 5, the extension portion 22 and the external power source are electrically connected by attaching the wiring W electrically connected to the external power source to the extension portion 22. Can do.
- the external power source is not particularly limited as long as it can apply a potential to the working electrode portion 20, and for example, a potentiostat can be preferably used.
- the accommodation of the electrolytic solution E in the hollow portion 12 is not particularly limited as long as the sample base portion 21 of the working electrode portion 20 is immersed in the electrolytic solution E. That is, for example, the electrolyte solution E may be filled so that a gas phase is not substantially formed in the sealed hollow portion 12.
- the Raman spectroscopic measurement first, an electric potential is applied from the external power source to the working electrode part 20 via the extending part 22 to start the electrochemical reaction of the sample S held on the sample stage part 20. Further, the sample S is irradiated with excitation light from the lens L of the Raman spectroscopic measurement system through the window portion 11, and Raman scattering emitted in association with the electrochemical reaction of the sample S on the surface 21 a of the sample stage 21. Light is captured in the system optics in backscatter mode to obtain a Raman spectrum.
- in situ Raman spectroscopic measurement (in the example shown in FIG. 5) of an electrochemical reaction on the solid surface in the electrolyte E (the surface 21a of the sample stage 21).
- In situ microscopic Raman spectroscopic measurement can be effectively performed. That is, for example, when the sample S includes a heterogeneous catalyst, the process of the heterogeneous catalytic reaction on the solid surface in the electrolytic solution E can be observed in situ.
- a carbon catalyst made of a carbonized material obtained by carbonizing a raw material containing an organic substance and a metal was prepared.
- a raw material to be carbonized was prepared. That is, a phenol resin (for spinning, manufactured by Gunei Chemical Industry Co., Ltd.) and cobalt phthalocyanine (purity 90%, manufactured by Tokyo Chemical Industry Co., Ltd.) are used so that the weight ratio of cobalt to the phenol resin is 3 wt%.
- a phenol resin for spinning, manufactured by Gunei Chemical Industry Co., Ltd.
- cobalt phthalocyanine purity 90%, manufactured by Tokyo Chemical Industry Co., Ltd.
- the material was carbonized. That is, 1 g of raw material was placed on a quartz boat, and the quartz boat was installed in the center of a quartz reaction tube ( ⁇ 23.5 mm ⁇ 600 mm). The quartz reaction tube was then purged with high purity nitrogen gas for 20 minutes at a flow rate of 500 mL / min. Then, using an infrared image furnace (RHL410P, manufactured by Vacuum Riko Co., Ltd.), the quartz reaction tube was heated under the flow of high purity nitrogen gas (500 mL / min), and the temperature was increased at a rate of temperature increase of 10 ° C./min. Raised to 1000 ° C. And the carbonization material was obtained by hold
- RHL410P infrared image furnace
- this carbonized material was pulverized in a mortar, 500 mg of the pulverized carbonized material and 10 pulverized balls were put in a container, and pulverization was performed for 90 minutes at a rotational speed of 750 rpm using a planetary ball mill. . Thereafter, the pulverized carbonized material was passed through a sieve having an opening of 106 ⁇ m, and the carbonized material that passed through the sieve was collected.
- the carbonized material, concentrated hydrochloric acid, and a stirring bar were put in a vial, stirred for 2 hours using a magnetic stirrer, and further subjected to suction filtration. After repeating this operation three times, the carbonized material was dried under reduced pressure at 80 ° C. overnight. And the carbonized material after drying was obtained as a carbon catalyst. It has been confirmed that this carbon catalyst exhibits redox catalytic activity such as oxygen reduction catalytic activity.
- a slurry containing a carbon catalyst (catalyst slurry) was prepared. That is, about 5.0 mg of the carbon catalyst was put in a plastic vial. Next, in this vial, glass beads (BZ-1, ⁇ 0.991 to 1.397 mm, manufactured by AS ONE Co., Ltd.) for one micro spatula, 50 ⁇ L of 5% Nafion (registered trademark) dispersion, 150 ⁇ L of ethanol (special grade reagent), 150 ⁇ L of ultrapure water was added. The obtained composition was treated with ultrasonic waves for 15 minutes to obtain a catalyst slurry.
- the catalyst slurry was applied to the sample base portion 21 of the working electrode portion 20.
- a glassy carbon plate (30 mm ⁇ 10 mm ⁇ 0.5 mm, manufactured by Nisshinbo Chemical Co., Ltd.) was used.
- 19.8 ⁇ L of catalyst slurry was applied to the surface 21a of the sample stage 21 which is a part of one end side of the glassy carbon plate, and drying in a desiccator under wet conditions, the area 1 of the surface 21a is reduced.
- a sample S containing a carbon catalyst was fixed in a range of 0.4 cm 2 .
- this reaction container 1 as shown in FIGS. 1-5 was manufactured. That is, first, a window portion 11 made of a quartz glass plate having a thickness of 1 mm is provided, and a hollow portion 12 capable of accommodating the electrolyte E is formed therein. The portion other than the window portion 11 is made of a vinyl chloride resin. A casing 10 that is a rectangular parallelepiped (25 mm ⁇ 25 mm ⁇ 25 mm) was prepared.
- the hollow part 12 of the housing part 10 was filled with an electrolytic solution E (aqueous sulfuric acid solution, 0.5 MH 2 SO 4 ) so that no gas phase was formed, and the hollow part 12 was sealed.
- the electrolytic solution E was purged of dissolved oxygen by bubbling nitrogen gas for 30 minutes before filling the hollow portion 12 of the reaction vessel 1.
- the distance between the window part 11 and the sample stage part 21 of the working electrode part 20 was 2 mm. That is, a layer of the electrolytic solution E having a thickness of 2 mm was formed between the window portion 11 and the sample table portion 21.
- the reaction vessel 1 is designed so that the sample S fixed to the sample stage 21 of the working electrode unit 20 is disposed at the focal point of an optical system provided in a commercially available microscopic laser Raman spectroscopic measurement system described later. It was.
- CV measurement was performed by setting the initial potential to a natural potential, the scanning range to 0 to 1.0 V (vs. NHE), the scanning speed to 50 mV / s, the number of cycles to 5 cycles, and a cyclic voltammogram was obtained.
- cyclic voltammetry was carried out in the same manner except that a tripolar electrochemical cell was used instead of the present reaction vessel 1.
- a tripolar electrochemical cell was used instead of the present reaction vessel 1.
- 4 ⁇ L of the catalyst slurry prepared in the same manner as in Example 1 described above was applied to a disk electrode (glassy carbon, ⁇ 6 mm) and dried in a desiccator under wet conditions. After drying, this disk electrode was attached to a rotating ring disk electrode measuring device.
- a sulfuric acid aqueous solution (0.5 MH 2 SO 4 ) was used as an electrolytic solution
- a reversible hydrogen electrode (RHE) was used as a reference electrode
- a carbon electrode was used as a counter electrode.
- FIG. 6 shows the obtained cyclic voltammogram.
- a solid line shows the result obtained using this reaction container 1
- a broken line shows the result obtained by the conventional method.
- a cyclic voltammogram substantially the same as that obtained by the conventional method was obtained.
- the chronoamperometry using this reaction vessel 1 also gave substantially the same results as the chronoamperometry according to the conventional method. That is, it was confirmed that this reaction container 1 operates normally as an electrochemical device.
- reaction vessel 1 prepared as described above is directly under the objective lens (corresponding to the lens L shown in FIG. 5), the sample stage (the microscope stage shown in FIG. 5). Equivalent to M).
- this reaction container 1 was sufficiently small in height, it could be used without any modification of the commercially available microscopic laser Raman spectroscopic measurement system.
- reaction vessel 1 is connected to a potentiostat, and the electrochemical reaction in the electrolytic solution E is started by holding the potential at 2.0 V (vs. NHE).
- Excitation light laser
- in situ microscopic laser Raman spectroscopy measurement of the electrochemical reaction was performed in the backscattering mode.
- an Ar laser having a wavelength of 532 nm was used as an excitation light source.
- the output of the excitation light was set to 2 mW on the surface of the sample S.
- the objective lens a long focal lens having a magnification of 50 times was used.
- the exposure time was 60 seconds, the number of exposures was 4, the number of background exposures was 16, and the aperture was a 25 ⁇ m pinhole.
- the measurement was performed at six locations selected on the sample S at random.
- FIG. 7 shows the obtained Raman spectrum.
- the solid line (unprocessed) shows the result obtained without applying a potential
- the dotted line (60 s) shows the result obtained when the potential is held for 60 seconds
- the broken line (600 s) shows The result obtained when the potential is held for 600 seconds is shown
- the thick broken line (1800 s) shows the result obtained when the potential is held for 1800 seconds.
- FIG. 8 shows the results of evaluating the intensity of the D band (peak intensity at 1358 cm ⁇ 1 ) in the Raman spectrum shown in FIG.
- the horizontal axis indicates the time (seconds) during which the potential is held
- the vertical axis indicates the intensity of the D band.
- the intensity of the D band was 1.64 before the potential application, whereas it became 2.13 60 seconds after starting the potential application, 2.91 after 600 seconds, After 1800 seconds, it was 3.34. That is, the intensity of the D band increased with time until the time during which the potential was maintained was 1800 seconds.
- Such an increase in the intensity of the Raman band specific to the carbon structure with time was considered to reflect the process in which the carbon structure of the carbon catalyst contained in the sample S is oxidized in the electrolyte solution E. That is, generally, the higher the crystallinity of the carbon structure, the higher the Raman activity and the larger the Raman peak is obtained. For example, the low crystallinity portion present in the carbon structure of the carbon catalyst is reduced by oxidation. It was considered that the Raman activity was increased by increasing the highly crystalline part.
- the carbon catalyst when the carbon catalyst is oxidized by applying a potential in the electrolytic solution E, and then the carbon catalyst is taken out from the electrolytic solution E and the carbon structure is analyzed, the analyzed carbon structure is oxidized. However, it cannot be distinguished whether it is due to the application of the potential or because the carbon catalyst is taken out of the electrolytic solution and brought into contact with air.
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Abstract
Description
不均一系触媒として、有機物と金属とを含む原料を炭素化して得られる炭素化材料からなる炭素触媒を調製した。
まず、炭素触媒を含むスラリー(触媒スラリー)を調製した。すなわち、炭素触媒 約5.0 mgをプラスチック製のバイアルに入れた。次いで、このバイアルに、ガラスビーズ(BZ-1、φ0.991~1.397mm、アズワン株式会社製)をミクロスパチュラ一杯分、5%Nafion(登録商標)分散溶液50μL、エタノール(特級試薬)150μL、超純水150μLを加えた。得られた組成物を超音波で15分処理することにより、触媒スラリーを得た。
上述のようにして準備した本反応容器1が、電気化学装置として正常に作動することを確認するため、ポテンショスタット(ALS700シリーズ電気化学アナライザー、BAS株式会社製)を使用して、サイクリックボルタンメトリー(CV)を実施した。電解液Eとしては、窒素を飽和させた硫酸溶液(0.5MH2SO4)を使用した。
市販の顕微レーザラマン分光測定システム(顕微レーザラマンシステム Nicolet Almega XR、Thermo Fisher Scientific株式会社製)と本反応容器1とを使用して、in situ顕微レーザラマン分光測定を行った。
Claims (9)
- 透明な窓部を有し、電解液を収容するための中空部が形成された筐体部と、
前記電解液中で電気化学的に不活性な導電性材料から構成され、その一部が試料を保持するために前記中空部内で前記窓部に対向して配置され、他の一部が外部電源に接続されるために前記筐体部外まで延設された作用極部と
を備えた
ことを特徴とするラマン分光測定用反応容器。 - 前記作用極部は、前記窓部に対して平行に延びる部材である
ことを特徴とする請求項1に記載のラマン分光測定用反応容器。 - 前記導電性材料は、導電性炭素材料、導電性セラミックス、金及び金メッキ導電性材料からなる群より選択される1種以上である
ことを特徴とする請求項1又は2に記載のラマン分光測定用反応容器。 - 顕微ラマン分光測定に使用される
ことを特徴とする請求項1乃至3のいずれかに記載のラマン分光測定用反応容器。 - 透明な窓部を有し、電解液を収容するための中空部が形成された筐体部と、
前記電解液中で電気化学的に不活性な導電性材料から構成され、その一部が前記中空部内で前記窓部に対向して配置され、他の一部が前記筐体部外まで延設された作用極部と、
を備えた反応容器を準備すること、
前記作用極部の前記窓部に対向して配置された前記一部に試料を保持すること、
前記作用極部の前記筐体部外まで延設された前記他の一部を外部電源に接続すること、
前記中空部に前記電解液を収容すること、及び
前記電解液中における前記試料の電気化学反応中のラマン分光測定を行うこと
を含む
ことを特徴とするラマン分光測定方法。 - 前記作用極部は、前記窓部に対して平行に延びる部材である
ことを特徴とする請求項5に記載のラマン分光測定法。 - 前記導電性材料は、導電性炭素材料、導電性セラミクス、金及び金メッキ導電性材料からなる群より選択される1種以上である
ことを特徴とする請求項5又は6に記載のラマン分光測定方法。 - 前記ラマン分光測定は、顕微ラマン分光測定である
ことを特徴とする請求項5乃至7のいずれかに記載のラマン分光測定方法。 - 前記反応容器を、励起光を照射するためのレンズと、前記レンズに対向して配置された顕微鏡ステージとの間に配置して、前記顕微ラマン分光測定を行う
ことを特徴とする請求項8に記載のラマン分光測定方法。
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US14/359,762 US20140346052A1 (en) | 2011-11-25 | 2012-11-01 | Reaction vessel for raman spectrophotometry, and raman spectrophotometry method using same |
CA2855926A CA2855926C (en) | 2011-11-25 | 2012-11-01 | Reaction vessel for raman spectrophotometry, and raman spectrophotometry method using same |
EP12850794.4A EP2784488B1 (en) | 2011-11-25 | 2012-11-01 | Reaction vessel for raman spectrophotometry, and raman spectrophotometry method using the same |
KR1020147013820A KR101495809B1 (ko) | 2011-11-25 | 2012-11-01 | 라만 분광측정용 반응 용기 및 이것을 이용한 라만 분광측정 방법 |
CN201280057745.0A CN104011533A (zh) | 2011-11-25 | 2012-11-01 | 用于拉曼分光光度测定的反应容器、以及使用该反应容器的拉曼分光光度测定方法 |
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KR102349963B1 (ko) | 2015-04-30 | 2022-01-11 | 삼성전자주식회사 | 실시간 분석을 위한 인-시츄 코인 셀과 이를 포함하는 측정 시스템과 인-시츄 코인 셀의 제조방법 및 광을 이용한 그 측정방법 |
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KR20140080555A (ko) | 2014-06-30 |
KR101495809B1 (ko) | 2015-02-25 |
EP2784488A1 (en) | 2014-10-01 |
US20140346052A1 (en) | 2014-11-27 |
CA2855926A1 (en) | 2013-05-30 |
EP2784488A4 (en) | 2015-07-15 |
CN104011533A (zh) | 2014-08-27 |
JP2013113620A (ja) | 2013-06-10 |
EP2784488B1 (en) | 2018-01-03 |
JP5731960B2 (ja) | 2015-06-10 |
CA2855926C (en) | 2015-02-24 |
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