JP7367435B2 - electrochemical reaction device - Google Patents

Description

The present invention relates to electrochemical reaction devices.

By electrically connecting the oxidation reaction electrode and the reduction reaction electrode and applying a bias voltage, the oxidation reaction electrode oxidizes water to generate oxygen, and the reduction reaction electrode generates carbon dioxide. Electrochemical reaction devices that generate formic acid and the like by reduction are known (for example, Patent Document 1).

Further, Non-Patent Document 1 discloses an electrode for oxidation reaction using manganese oxide as an oxidation catalyst.

Further, Non-Patent Document 2 discloses an electrode for an oxidation reaction using iridium oxide as an oxidation catalyst.

Japanese Patent Application Publication No. 2017-125242

Dr. Zaki N. Zahran, Dr. Eman A. Mohamed, Dr. Takehiro Ohta, Prof. Yoshinori Naruta, “Electrocatalytic Water Oxidation by a Highly Active and Robust α-Mn2O3Thin Film Sintered on a Fluorine-Doped Tin Oxide Electrode”, ChemCatChem , Vol.8, No.3, pp.532-535, 2016 Takeo Arai et al, “A monolithic device for CO2 photoreduction to generate liquid organic substances in a single-compartment reactor”, Energy Environ. Sci., 2-15, 8, 1998-2002

By the way, in the electrodes for oxidation reactions described in Non-Patent Documents 1 and 2, the catalytic activity of the oxidation catalyst is low, so the overvoltage becomes high and it is difficult to perform a good electrode reaction. That is, unless the voltage is increased, no electrode reaction will occur at the oxidation reaction electrode, and even if the electrode reaction occurs, the current flowing through the oxidation reaction electrode will be small. As a result, the power consumption of the electrochemical reaction device may increase, and in order to perform the electrode reaction efficiently, it is necessary to increase the amount of catalyst or enlarge the electrode area, which increases the cost and reduces the device size. There are concerns about larger size, etc.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an electrochemical reaction device capable of causing an electrode reaction at an oxidation reaction electrode at a low voltage and increasing the current flowing through the oxidation reaction electrode.

An electrochemical reaction device according to an embodiment of the present invention includes an electrode for an oxidation reaction that oxidizes water, an electrode for a reduction reaction that reduces a carbon compound or a proton, and an electrolytic solution with a pH of 4 or more, The electrode has an oxidation catalyst, and the oxidation catalyst is selected from titanium phosphorus-containing compound particles represented by MTiP (M is selected from the group consisting of Ni, Fe, Cy, Co, and Mn) and iridium oxide particles . At least one of them and ruthenium oxide particles are included.

Further, in the electrochemical reaction device, the oxidation catalyst includes the ruthenium oxide particles and the titanium phosphorus-containing compound particles represented by NiTiP, and the ruthenium oxide particles and the titanium phosphorus-containing compound particles represented by FeTiP. comprising the ruthenium oxide particles , the titanium phosphorus-containing compound particles represented by the NiTiP, and the iridium oxide particles, or the ruthenium oxide particles and the titanium phosphorus-containing compound particles represented by the FeTiP, and the iridium oxide particles . It is preferable to include.

According to the embodiments of the present invention, it is possible to provide an electrochemical reaction device that can cause an electrode reaction in the oxidation reaction electrode at a low voltage and increase the current flowing through the oxidation reaction electrode.

FIG. 1 is a diagram showing the configuration of an electrochemical reaction device according to the present embodiment. FIG. 1 is a schematic cross-sectional view showing the configuration of an oxidation reaction electrode according to the present embodiment. 3 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Example 1. FIG. 3 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Comparative Example 1. FIG. 3 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Example 2. FIG. FIG. 7 is a diagram showing the results of measuring the amount of current of the electrode for oxidation reaction in Example 3. FIG. 7 is a diagram showing the results of measuring the amount of current of the electrode for oxidation reaction in Example 4. FIG. 7 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Example 5. FIG. 7 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Example 6. FIG. 7 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Example 7. FIG. 7 is a diagram showing the results of measuring the amount of current of the electrode for oxidation reaction in Example 8. FIG. 7 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Example 9. FIG. 7 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Example 10. FIG. 7 is a diagram showing the results of measuring the amount of current of the oxidation reaction electrode of Example 11.

Embodiments of the present invention will be described below. This embodiment is an example of implementing the present invention, and the present invention is not limited to this embodiment.

FIG. 1 is a diagram showing the configuration of an electrochemical reaction device according to this embodiment. As shown in FIG. 1, the electrochemical reaction device 100 includes a reduction reaction electrode 102, an oxidation reaction electrode 104, and an electrolyte 106. Further, the electrochemical reaction device 100 shown in FIG. 1 includes a solar cell 108, a window material 110, and a frame material 112.

The reduction reaction electrode 102 is an electrode used to reduce a carbon compound or proton by a reduction reaction. The form of the reduction reaction electrode 102 is not particularly limited as long as it is an electrode capable of reducing carbon compounds or protons, but for example, it may include a substrate, a conductive layer disposed on the substrate, or a conductive layer disposed on the conductive layer. and a conductor layer.

The substrate is a member that structurally supports the reduction reaction electrode 102, and is not particularly limited in material, but may be, for example, a glass substrate. Further, the substrate may include, for example, a metal or a semiconductor. Metals used as the substrate are not particularly limited, but include silver (Ag), gold (Au), copper (Cu), zinc (Zn), indium (In), cadmium (Cd), and tin (Sn). , palladium (Pd), and lead (Pb). Semiconductors used as the substrate are not particularly limited, but include titanium oxide (TiO ₂ ), silicon (Si), strontium titanate (SrTiO ₃ ), zinc oxide (ZnO), and tantalum oxide (Ta ₂ O ₅ ). etc. is preferable.

The conductive layer is provided to effectively collect current at the reduction reaction electrode 102. The conductive layer is not particularly limited, but is preferably made of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), or the like. In particular, in consideration of thermal and chemical stability, it is preferable to use fluorine-doped tin oxide (FTO).

The conductor layer is composed of a conductor containing a reduction catalyst. The conductor layer can be formed by supporting a reduction catalyst on a conductor. The conductor can be made of a material containing a carbon material (C), for example. The carbon material preferably includes at least one of carbon nanotubes, graphene, and graphite, for example. In the case of graphene and graphite, the size is preferably 1 nm or more and 1 μm or less. In the case of carbon nanotubes, it is preferable that the diameter is 1 nm or more and 40 nm or less. The conductor can be formed by spraying a carbon material mixed with a liquid such as ethanol and heating the mixture. Instead of spraying, it may be applied by spin coating. Alternatively, the solution may be directly dropped and dried without using spin coating.

The reduction catalyst is not particularly limited as long as it is a material that has a reduction catalyst function, but for example, a complex catalyst is suitable. The complex catalyst is preferably a ruthenium complex, for example. The complex catalyst is, for example, [Ru{4,4'-di(1-H-1-pyrrolypropyl carbonate)-2,2'-bipyridine}(CO)(MeCN)Cl ₂ ], [Ru{4,4' -di(1-H-1-pyrrolypropyl carbonate)-2,2'-bipyridine}(CO) ₂ Cl ₂ ], [Ru{4,4'-di(1-H-1-pyrrolypropyl carbonate)-2, 2'-bipyridine}(CO) ₂ ] _n , [Ru{4,4'-di(1-H-1-pyrrolypropyl carbonate)-2,2'-bipyridine}(CO)(CH ₃ CN) Cl ₂ ] etc.

The conductor layer can be produced, for example, by applying a solution prepared by dissolving a complex catalyst in an acetonitrile (MeCN) solution onto the conductor. Moreover, the conductor layer can also be produced by an electrolytic polymerization method. For example, a conductive electrode is used as the working electrode, a glass substrate coated with fluorine-containing tin oxide (FTO) is used as the counter electrode, and an Ag/ ^{Ag + electrode} is used as the reference electrode. It can be manufactured by passing a cathode current so as to have a negative voltage with respect to the Ag/Ag ⁺ electrode, and then passing an anode current so as to have a positive potential with respect to the Ag/Ag + electrode. For the electrolyte solution, for example, acetonitrile (MeCN) can be used, and for the electrolyte, for example, Tetrabutylammonium perchlorate (TBAP) can be used.

The conductive layer formed in this way is supported, coated, or pasted on the conductive layer disposed on the substrate. As a result, a reduction reaction electrode including a substrate, a conductive layer disposed on the substrate, and a conductive layer disposed on the conductive layer is produced.

The oxidation reaction electrode 104 is an electrode used to oxidize water by an oxidation reaction. FIG. 2 is a schematic cross-sectional view showing the configuration of the oxidation reaction electrode according to this embodiment. As shown in FIG. 2, the oxidation reaction electrode 104 includes a substrate 114, a conductive layer 115, and an oxidation catalyst layer 116. In the electrochemical reaction device 100 shown in FIG. 1, the oxidation catalyst layer 116 of the oxidation reaction electrode 104 is arranged to face the conductor layer of the reduction reaction electrode 102. The substrate 114 of the oxidation reaction electrode 104 may be made of the same material as the substrate of the reduction reaction electrode 102.

The conductive layer 115 is provided to effectively collect current at the oxidation reaction electrode 104. The conductive layer 115 is preferably made of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), or the like, although it is not particularly limited. In particular, in consideration of thermal and chemical stability, it is preferable to use fluorine-doped tin oxide (FTO).

The oxidation catalyst layer 116 includes an oxidation catalyst. The oxidation catalyst is a material that has an oxidation catalyst function. The oxidation catalyst includes at least one of a titanium phosphorus-containing compound represented by MTiP (M is selected from the group consisting of Ni, Fe, Cr, Co, and Mn) and iridium oxide (IrOx), and ruthenium oxide ( RuOx). That is, the oxidation catalyst includes (1) ruthenium oxide and iridium oxide, (2) ruthenium oxide and titanium phosphorus represented by MTiP (M is selected from the group consisting of Ni, Fe, Cr, Co, and Mn). or (3) ruthenium oxide, a titanium phosphorus-containing compound represented by MTiP (M is selected from the group consisting of Ni, Fe, Cr, Co, and Mn), and iridium oxide. Note that, hereinafter, (1) and (2) above will be referred to as a two-way catalyst, and (3) above will be referred to as a three-way catalyst.

The oxidation catalyst layer 116 is formed by applying a slurry in which a compound containing ruthenium oxide, iridium oxide, and titanium phosphorus is dispersed onto the conductive layer 115, and drying the slurry by maintaining it at a predetermined temperature and time in a drying oven. Note that after drying, it is preferable to wash with ultrapure water. Further, the application and drying of the slurry may be repeated multiple times.

The electrolytic solution 106 is not particularly limited as long as it has a pH of 4 or more, but is preferably, for example, a phosphate buffered aqueous solution or a boric acid buffered aqueous solution in terms of suppressing pH fluctuations during the redox reaction. Note that when a carbon compound is reduced in the reduction reaction electrode 102, a carbon compound such as carbon dioxide is dissolved in the electrolytic solution 106. In the electrochemical reaction device 100 shown in FIG. 1, for example, a tank for supplying an electrolytic solution 106 is provided, and a pump supplies the electrolytic solution 106 in the tank between the reduction reaction electrode 102 and the oxidation reaction electrode 104. supply to the gap.

The solar cell 108 shown in FIG. 1 is a device that applies an appropriate bias voltage between the reduction reaction electrode 102 and the oxidation reaction electrode 104. As shown in FIG. 1, the oxidation reaction electrode 104 is connected to the positive electrode of the solar cell 108, and the reduction reaction electrode 102 is connected to the negative electrode of the solar cell 108, thereby applying a bias voltage to both electrodes. The device that applies the bias voltage is not limited to the solar cell 108, and includes, for example, a chemical battery (including a primary battery, a secondary battery, etc.), a constant voltage source, and the like.

The window material 110 shown in FIG. 1 is a member that protects the solar cell 108. For the solar cell 108, it is preferable to provide a window material 110 on the light-receiving surface side. The window material 110 is a member that transmits light of a wavelength that contributes to power generation in the solar cell 108, and can be made of, for example, glass, plastic, or the like.

The reduction reaction electrode 102, the oxidation reaction electrode 104, the solar cell 108, and the window material 110 are structurally supported by a frame material 112.

In the electrochemical reaction device 100 shown in FIG. 1, while an electrolytic solution 106 having a pH of 4 or more is supplied to the surfaces of the reduction reaction electrode 102 and the oxidation reaction electrode 104, the reduction reaction electrode 102 and the oxidation reaction electrode 102 are A bias voltage is applied between the reaction electrode 104 and the reaction electrode 104 . As a result, at the oxidation reaction electrode 104, water in the electrolyte 106 is oxidized to generate oxygen (formula (1)), and at the reduction reaction electrode 102, carbon compounds in the electrolyte 106, such as CO ₂ is reduced to produce carbon monoxide, formic acid, etc. (formulas (2), (3)), or protons are reduced to produce hydrogen (formula (4)). The products generated at both electrodes are discharged from the electrochemical reaction device 100 and collected in an external collection tank.
Oxidation reaction: 2H ₂ O → O ₂ +4H ⁺ +4e ^- (1)
Reduction reaction: CO ₂ + 2H ⁺ + 2e ^- → CO + H ₂ O (2)
:CO ₂ +2H ⁺ +2e ^- →HCOOH (3)
:2H ⁺ +2e ^- →H ₂ (4)

Here, in the oxidation reaction electrode 104 in this embodiment, the aforementioned two-way catalyst or three-way catalyst is used as the oxidation catalyst. Since such an oxidation catalyst has high catalytic activity, the overvoltage of the oxidation reaction becomes low, making it possible to perform a good electrode reaction. That is, the electrode reaction (the reaction (1) above) occurs at the oxidation reaction electrode 104 at a low voltage, and the current flowing through the oxidation reaction electrode 104 can be increased. As a result, for example, it is possible to reduce the power consumption of the electrochemical reaction device, reduce the amount of catalyst, and reduce the area of the electrodes, resulting in lower costs and smaller devices.

The oxidation catalyst can increase the current flowing through the oxidation reaction electrode 104, and includes, for example, ruthenium oxide and NiTiP, ruthenium oxide and FeTiP, ruthenium oxide, NiTiP, and iridium oxide. Alternatively, it is preferable to include ruthenium oxide, FeTiP, and iridium oxide.

When the oxidation catalyst is a binary catalyst, the content of ruthenium oxide in the oxidation catalyst is preferably in the range of 10% by mass or more and 90% by mass or less, and the content of iridium oxide or titanium phosphorus-containing compound in the oxidation catalyst is , preferably in a range of 10% by mass or more and 90% by mass or less. Furthermore, when the oxidation catalyst is a three-way catalyst, the content of ruthenium oxide in the oxidation catalyst is preferably in the range of 10% by mass or more and 90% by mass or less, and the content of iridium oxide in the oxidation catalyst is preferably 10% by mass or more. The content of the titanium phosphorous compound in the oxidation catalyst is preferably in the range of 90% by mass or less, and preferably in the range of 10% by mass or more and 90% by mass or less. When the content of each component in the oxidation catalyst satisfies the above range, the amount of current flowing through the oxidation reaction electrode 104 may increase compared to the case where the content does not meet the above range.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

<Example 1>
<Preparation of electrode for oxidation reaction>
A 10 wt% sodium hydroxide (NaOH) aqueous solution was added to a mixed solution of 25 ml of a 1 mM potassium chloride iridate (IV) (K ₂ IrCl ₆ ) aqueous solution and 25 ml of a 1 mM ruthenium chloride (RuCl ₃ ) aqueous solution to adjust the pH to 13. A prepared solution was obtained. After cooling the solution with ice water for 1 hour, a 3M nitric acid (HNO ₃ ) aqueous solution was added dropwise to adjust the pH to 1 to obtain an iridium oxide (IrOx)/ruthenium oxide (RuOx) nanocolloid aqueous solution. A 1.5 wt % NaOH aqueous solution was added dropwise to this solution to adjust the pH to 12.

100 μl of the above solution was applied onto the FTO substrate and dried at 60° C. in a drying oven. After drying, the precipitated salt was washed with ultrapure water to obtain an electrode for oxidation reaction. The size of the oxidation reaction electrode is 10 cm x 10 cm.

<Comparative example 1>
A mixed solution of 25 ml of 1 mM potassium chloriridate (IV) chloride (IV) (K ₂ IrCl ₆ ) aqueous solution and 25 ml of 1 mM ruthenium chloride (RuCl ₃ ) aqueous solution was added to 25 ml of 1 mM potassium chloriridate (IV) potassium chloride (IV) (K ₂ IrCl ₆ ) aqueous solution. An oxidation reaction electrode was produced in the same manner as in Example 1, except that an aqueous nanocolloidal solution of iridium oxide (IrOx) was obtained instead.

(Measurement of current amount)
The current flowing through the oxidation reaction electrodes of Example 1 and Comparative Example 1 was measured using an electrochemical analyzer (ALS610) using a three-electrode method. In the three-electrode method, a container was filled with an electrolytic solution, and the oxidation reaction electrode prepared above as a working electrode, a platinum electrode as a counter electrode, and Hg/Hg ₂ SO ₄ as a reference electrode were immersed in the electrolytic solution. As the electrolytic solution, a 0.1 mol phosphate buffer aqueous solution (K ₂ HPO ₄ +KH ₂ PO ₄ ) having a pH of 6.8 was used. Each electrode was connected to an electrochemical analyzer, the voltage was swept to 1.2 V, and the value of the current flowing through the oxidation reaction electrode was measured.

FIG. 3 is a diagram showing the results of measuring the amount of current of the electrode for oxidation reaction of Example 1, and FIG. 4 is a diagram showing the results of measuring the amount of current of the electrode for oxidation reaction of Comparative Example 1. The current density (mA/cm ² ) on the vertical axis is the value obtained by dividing the measured current value by the area of the oxidation reaction electrode.

As shown in FIG. 3, in Example 1, electrode reaction occurred at a lower voltage than in Comparative Example 1, and at the same voltage, a large amount of current flowed. Therefore, as in Example 1, it was shown that by using an oxidation catalyst containing iridium oxide and ruthenium oxide, the oxidation reaction at the oxidation reaction electrode could be performed efficiently.

<Example 2>
A 10 wt % sodium hydroxide (NaOH) aqueous solution was added to 25 ml of a 1 mM ruthenium chloride (RuCl ₃ ) aqueous solution to obtain a solution adjusted to pH 13. After cooling the solution with ice water for 1 hour, a 3M nitric acid (HNO ₃ ) aqueous solution was added dropwise to adjust the pH to 1 to obtain a nanocolloidal aqueous solution of ruthenium oxide (RuOx). After adjusting the pH to 12 by dropping a 1.5 wt % NaOH aqueous solution into this solution, 40 parts by mass of NiTP particles (particle size 150 nm) were added.

100 μl of the above solution was applied onto the FTO substrate and dried at 60° C. in a drying oven. After drying, the precipitated salt was washed with ultrapure water to obtain an electrode for oxidation reaction. The size of the oxidation reaction electrode is 10 cm x 10 cm.

<Example 3>
An electrode for oxidation reaction was produced in the same manner as in Example 2, except that the NiTP particles were replaced with FeTiP particles (particle size: 180 nm).

<Example 4>
An electrode for oxidation reaction was produced in the same manner as in Example 2, except that the NiTP particles were replaced with CrTiP particles (particle size: 170 nm).

<Example 5>
An electrode for oxidation reaction was produced in the same manner as in Example 2, except that the NiTP particles were replaced with CoTiP particles (particle size: 140 nm).

<Example 6>
An electrode for oxidation reaction was produced in the same manner as in Example 2, except that the NiTP particles were replaced with MnTiP particles (particle size: 160 nm).

<Example 7>
A 10 wt% sodium hydroxide (NaOH) aqueous solution was added to a mixed solution of 25 ml of a 1 mM potassium chloride iridate (IV) (K ₂ IrCl ₆ ) aqueous solution and 25 ml of a 1 mM ruthenium chloride (RuCl ₃ ) aqueous solution to adjust the pH to 13. A prepared solution was obtained. After cooling the solution with ice water for 1 hour, a 3M nitric acid (HNO ₃ ) aqueous solution was added dropwise to adjust the pH to 1 to obtain an iridium oxide (IrOx)/ruthenium oxide (RuOx) nanocolloid aqueous solution. After adjusting the pH to 12 by dropping a 1.5 wt % NaOH aqueous solution into this solution, 40 parts by mass of NiTP particles (particle size 150 nm) were added.

100 μl of the above solution was applied onto the FTO substrate and dried at 60° C. in a drying oven. After drying, the precipitated salt was washed with ultrapure water to obtain an electrode for oxidation reaction. The size of the oxidation reaction electrode is 10 cm x 10 cm.

<Example 8>
An electrode for oxidation reaction was produced in the same manner as in Example 7 except that NiTP particles were replaced with FeTiP particles (particle size 180 nm).

<Example 9>
An electrode for oxidation reaction was produced in the same manner as in Example 7, except that the NiTP particles were replaced with CrTiP particles (particle size: 170 nm).

<Example 10>
An electrode for oxidation reaction was produced in the same manner as in Example 7, except that the NiTP particles were replaced with CoTiP particles (particle size: 140 nm).

<Example 11>
An electrode for oxidation reaction was produced in the same manner as in Example 7, except that the NiTP particles were replaced with MnTiP particles (particle size: 160 nm).

As in Example 1, the amount of current flowing through the oxidation reaction electrodes of Examples 2 to 11 was measured. 5 to 14 are diagrams showing the results of measuring the amount of current of the oxidation reaction electrodes of Examples 2 to 11. As shown in FIGS. 5 to 14, in Examples 2 to 11, electrode reactions occurred at lower voltages than in Comparative Example 1, and more current flowed at the same voltage. Therefore, as in Examples 2 to 11, an oxidation catalyst containing a titanium phosphorus-containing compound represented by MTiP (M is selected from the group consisting of Ni, Fe, Cr, Co, and Mn) and ruthenium oxide, or MTiP By using an oxidation catalyst containing a titanium phosphorus-containing compound represented by (M is selected from the group consisting of Ni, Fe, Cr, Co, and Mn), ruthenium oxide, and iridium oxide, oxidation at the oxidation reaction electrode is possible. It was shown that the reaction could be carried out efficiently. Furthermore, among Examples 1 to 11, a larger amount of current flowed in Examples 2, 3, 7, and 8 than in the other Examples when the same voltage was applied.

(Evaluation of pH of electrolyte)
<Example 12>
A three-electrode cell was prepared by filling a container with an electrolytic solution and immersing the oxidation reaction electrode of Example 1 as a working electrode, a platinum electrode as a counter electrode, and Hg/Hg ₂ SO ₄ as a reference electrode in the electrolytic solution. As the electrolytic solution, a 0.1 mol phosphate buffer aqueous solution (K ₂ HPO ₄ +KH ₂ PO ₄ ) having a pH of 6.8 was used. Each electrode was connected to an electrochemical analyzer, a voltage of 1.3 V was applied for 3600 seconds, and the current value was measured.

<Comparative example 2>
The current value was measured in the same manner as in Example 12, except that a 0.1 molar lithium citrate buffer having a pH of 2.4 was used as the electrolyte.

Comparing Example 12 and Comparative Example 2, the current value of Comparative Example 2 after 1 hour was 17% of the current value of Example 12. In Comparative Example 2, the pH of the electrolytic solution was low and the acidity was strong, so it is thought that ruthenium oxide was eluted from the oxidation reaction electrode, resulting in a low current value.

Reference Signs List 100 electrochemical reaction device, 102 electrode for reduction reaction, 104 electrode for oxidation reaction, 106 electrolyte, 108 solar cell, 110 window material, 112 frame material, 114 substrate, 115 conductive layer, 116 oxidation catalyst layer.

Claims (2)

An oxidation reaction electrode that oxidizes water;
a reduction reaction electrode that reduces a carbon compound or proton;
An electrolytic solution with a pH of 4 or more,
The oxidation reaction electrode has an oxidation catalyst,
The oxidation catalyst includes at least one of titanium phosphorus-containing compound particles represented by MTiP (M is selected from the group consisting of Ni, Fe, Cr, Co, and Mn) and iridium oxide particles , and ruthenium oxide particles . An electrochemical reaction device comprising: The oxidation catalyst includes the ruthenium oxide particles and the titanium phosphorus-containing compound particles represented by NiTiP, and the ruthenium oxide particles and the NiTiP, which include the ruthenium oxide particles and the titanium phosphorus-containing compound particles represented by FeTiP. A claim characterized in that the titanium phosphorus - containing compound particles represented by : 1. The electrochemical reaction device according to 1.

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