Catalyst for chloride ion oxidation reaction, and apparatus and method for producing hypochlorous acid or hypochlorite salts.

Abstract

The object of the present invention is to provide a catalyst for chloride ion oxidation reaction that has high oxidation efficiency of chloride ions in the electrolysis of water containing chloride ions while reducing the amount of precious metals used, to provide an electrode for chloride ion oxidation reaction that has high oxidation efficiency of chloride ions, and to provide a production apparatus and method for hypochlorous acid or hypochlorite that has high production efficiency. [Solution] A catalyst for the oxidation reaction of chloride ions in the electrolysis of water containing chloride ions, wherein the catalyst contains ruthenium, and the ruthenium is contained in the crystal structure of α-type manganese dioxide.

Description

[Technical Field]

[0001] The present invention relates to a catalyst for chloride ion oxidation reactions, ruthenium-composite α-type manganese dioxide, an electrode for chloride ion oxidation reactions, and an apparatus for producing hypochlorous acid or hypochlorite, as well as a method for producing hypochlorous acid or hypochlorite. [Background technology]

[0002] In plants that use large quantities of seawater, the attachment and proliferation of marine organisms such as algae and shellfish to parts that come into contact with seawater, such as intakes, piping, condensers, and various coolers between the seawater intake and discharge ports, is a major problem. As a countermeasure, sodium hypochlorite is generated by electrolysis (hereinafter also called electrolysis) of seawater and injected into the intake to suppress the attachment of marine organisms such as algae and shellfish. In the electrolysis of seawater, chloride ions (Cl) are generated at the anode. - Oxidation of ) produces chlorine (Cl2) and hypochlorite ions (ClO2). - ) and hypochlorous acid (HClO) are generated, and hydrogen (H2) is generated at the cathode. Furthermore, the hypochlorite ions generated at the anode turn into sodium ions (Na +) combines with other metals to produce sodium hypochlorite (NaClO). Conventionally, insoluble electrodes such as DSA® and ANODEC®, which contain a large amount of precious metals (Pt, Ru, Ir, etc.), have been used as anode electrodes. However, even when RuO2 is used as a catalyst for the electrode, the Faraday efficiency of the chloride ion oxidation reaction (COR), which is an indicator of chloride ion oxidation, was only about 60%. This is because the chloride ion oxidation reaction (COR) and the oxygen evolution reaction (OER) compete at the anode. Furthermore, ruthenium (Ru), a precious metal, is also a type of rare metal, and reducing its use is related to the SDGs (Sustainable Development Goals), and is particularly closely linked to Goal 12 "Responsible Consumption and Production" and Goal 9 "Industry, Innovation and Infrastructure". Because the supply of rare metals tends to depend on specific countries, reducing the amount of rare metals used is one of the issues that needs to be addressed both nationally and internationally in Japan. Therefore, in order to lower the cost of catalysts, ensure a stable supply of resources, and mitigate geopolitical risks, there has been a need for catalysts that can reduce the amount of expensive and geographically concentrated precious metals used, while also achieving chlorine generation efficiency equivalent to or better than conventional catalysts.

[0003] In the electrolysis of water, catalysts that reduce the amount of precious metals used have been proposed, for example, the catalyst described in Patent Document 1. Patent Document 1 discloses the use of cobalt-composite γ-type manganese dioxide as a catalyst, but this catalyst was an oxygen evolution catalyst to promote the oxygen evolution reaction. Patent Document 2 proposes the use of layered manganese oxide having sodium ions between layers in the electrolysis of brine, but this also reduces the efficiency of chlorine generation and increases the efficiency of oxygen generation. Patent Document 3 proposes the use of tungsten oxide containing iron and cobalt as a catalyst, but this was also an oxygen evolution catalyst. Non-Patent Document 1 proposes the use of ruthenium-doped α-type manganese dioxide nanorods as a catalyst for oxidizing hydrazine in a weakly alkaline or weakly acidic solution to obtain hydrogen, but this was not related to a catalyst for the chloride ion oxidation reaction in the electrolysis of water containing chloride ions, such as brine. Thus, various catalysts that reduce the amount of precious metals used have been proposed conventionally, but none of them were related to a catalyst for the chloride ion oxidation reaction. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-172487 [Patent Document 2] Japanese Patent Publication No. 2021-107307 [Patent Document 3] Japanese Patent Publication No. 2021-186750 [Non-patent literature]

[0005] [Non-Patent Document 1] L. Liu et al., “Defective Ru-doped α-MnO2 nanorods enabling efficient hydrazine oxidation for energy-saving hydrogen production via proton exchange membranes at near-neutral pH”, Chem. Eng. J., 2023, 470, 144050. [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a catalyst for chloride ion oxidation reaction that has high oxidation efficiency of chloride ions in the electrolysis of water containing chloride ions while reducing the amount of precious metals used. Furthermore, the object of the present invention is to provide an electrode for chloride ion oxidation reaction that has high oxidation efficiency of chloride ions in the electrolysis of water containing chloride ions while reducing the amount of precious metals used, and furthermore, to provide a production apparatus and method for hypochlorous acid or hypochlorite with high production efficiency. [Means for solving the problem]

[0007] The inventors have long been working on the development of various catalysts for the electrolysis of water, and have proposed various catalysts utilizing manganese oxides. However, the purpose of these was to improve the efficiency of the oxygen evolution reaction (OER), and all of them were related to catalysts for the oxygen evolution reaction (see Patent Documents 1-3). This time, the inventors focused on the production of hypochlorites such as hypochlorous acid and sodium hypochlorite by electrolysis of seawater, and began investigating catalysts to improve the efficiency of the chloride ion oxidation reaction (COR) rather than the oxygen evolution reaction (OER). Since OER and COR are competing reactions, improving the efficiency of one decreases the efficiency of the other. However, during the investigation, it was unexpectedly discovered that by using manganese oxide, which has been used to decrease the efficiency of COR and increase the efficiency of OER, it is possible to increase the efficiency of COR, the opposite of what has been done conventionally. This effect was achieved by incorporating ruthenium into the crystal structure of α-type manganese dioxide. The COR catalyst thus discovered reduces the amount of Ru, a precious metal, used compared to conventional catalysts, and achieves COR efficiency equivalent to or better than that of RuO2, which has been used conventionally. The electrode for chloride ion oxidation reaction, as well as the apparatus and method for producing hypochlorous acid or hypochlorite using this catalyst, exhibit excellent COR efficiency while reducing the amount of Ru used, and excellent production efficiency of hypochlorous acid or hypochlorite. The present invention is thus completed.

[0008] In other words, the present invention is defined by the following: (1) A catalyst for the oxidation reaction of chloride ions in the electrolysis of water containing chloride ions, wherein the catalyst contains ruthenium, and the ruthenium is contained in the crystal structure of α-type manganese dioxide. (2) The catalyst for the chloride ion oxidation reaction described in (1) above, wherein the ruthenium content in the crystal structure of α-type manganese is 0.004 to 0.3 in terms of the atomic ratio of ruthenium to manganese, i.e., Ru / Mn (atomic ratio). (3) A ruthenium composite α-manganese dioxide which is a catalyst for chloride ion oxidation reaction in the electrolysis of water containing chloride ions, contains ruthenium, and the ruthenium is contained in the crystal structure of α-manganese dioxide, wherein the content of the ruthenium is 0.004 to 0.3 in terms of the atomic ratio of ruthenium to manganese, Ru / Mn (atomic ratio), the Faraday efficiency for the chloride ion oxidation reaction is 60% or more, and the overvoltage for reaching a current density of 10 mA / cm 2 is 310 mV or less, the ruthenium composite α-manganese dioxide. (4) An electrode for chloride ion oxidation reaction in the electrolysis of water containing chloride ions, on which the catalyst for chloride ion oxidation reaction of the above (1) or (2) or the ruthenium composite α-manganese dioxide of the above (3) is supported. (5) A hypochlorous acid or hypochlorite production apparatus which comprises a water electrolysis apparatus and produces hypochlorous acid or hypochlorite by electrolyzing water containing chloride ions and metal ions, wherein the anode in the electrolysis apparatus is the electrode for chloride ion oxidation reaction of the above (4). (6) A method for producing hypochlorous acid or hypochlorite, wherein water containing chloride ions and metal ions is electrolyzed by an electrolysis apparatus having the electrode for chloride ion oxidation reaction of the above (4) as an anode to produce hypochlorous acid or hypochlorite. (7) The method for producing hypochlorous acid or hypochlorite according to the above (6), which produces hypochlorous acid or hypochlorite and produces hydrogen gas near the cathode of the electrolysis apparatus.

Advantages of the Invention

[0009] The catalyst for chloride ion oxidation reaction and the electrode for chloride ion oxidation reaction of the present invention can reduce the usage amount of noble metals and are excellent in the oxidation efficiency of chloride ions in the electrolysis of water containing chloride ions. The hypochlorous acid or hypochlorite production apparatus and production method of the present invention can reduce the usage amount of noble metals as a catalyst and are excellent in the production efficiency of hypochlorous acid or hypochlorite by electrolyzing water containing chloride ions.

Brief Description of the Drawings

[0010] [Figure 1] Figure 1 shows the XRD patterns of Ru-doped MnO2 obtained in Examples 1 to 6. [Figure 2] Figure 2 shows the XRD patterns of Ru-doped MnO2 obtained in Examples 1, 11, and 12, as well as the RuO2 from Comparative Example 1 and the MnO2 obtained in Comparative Example 2. [Figure 3] Figure 3 shows the LSV of Ru-doped MnO2 obtained in Examples 1, 2, and 7-12, as well as the RuO2 of Comparative Example 1 and the MnO2 obtained in Comparative Example 2. [Figure 4] Figure 4 shows the linear sweep voltammetry (LSV) of Ru-doped MnO2 obtained in Examples 3 to 6. [Figure 5] Figure 5 shows the results of constant current electrolysis of Ru-doped MnO2 obtained in Examples 1, 2, and 7-12, as well as RuO2 from Comparative Example 1 and MnO2 obtained in Comparative Example 2. [Figure 6] Figure 6 shows the results of constant current electrolysis of Ru-doped MnO2 obtained in Examples 3 to 6. [Figure 7] Figure 7 shows the relationship between the difference between cathode current and anode current at a predetermined potential and the sweep rate, obtained from the CV measurement results of Ru-doped MnO2 obtained in Examples 1, 11, and 12, as well as RuO2 from Comparative Example 1 and MnO2 obtained in Comparative Example 2. [Figure 8] Figure 8 shows the relationship between the difference between cathode current and anode current at a predetermined potential and the sweep rate, obtained from the CV measurement results of Ru-doped MnO2 obtained in Examples 3 to 6. [Modes for carrying out the invention]

[0011] The chloride ion oxidation catalyst of the present invention is a catalyst for the chloride ion oxidation reaction in the electrolysis of water containing chloride ions, and is a catalyst containing ruthenium, wherein the ruthenium is contained in the crystal structure of α-type manganese dioxide. In the present invention, the water containing chloride ions is chloride ion (Cl- ) Water containing these is not particularly limited. For example, water in which chlorides of alkali metals such as lithium (Li), sodium (Na), potassium (K), etc. are dissolved can be mentioned. As the water containing chloride ions in the present invention, water in which sodium chloride (NaCl) is dissolved is preferable. In the present invention, water in which sodium chloride is dissolved is also referred to as brine. The catalyst for chloride ion oxidation reaction of the present invention is excellent in the oxidation efficiency of chloride ions even in the electrolysis of brine under neutral conditions. As the electrolysis method in the present invention, there is no particular limitation as long as it is a method capable of electrolyzing water, and an electrolysis method usually used for electrolyzing water can be used. The catalyst for chloride ion oxidation reaction of the present invention contains ruthenium in the crystal structure of α-type manganese dioxide. As the amount of ruthenium contained in the crystal structure, the atomic ratio of ruthenium to manganese, Ru / Mn (atomic ratio), is preferably 0.004 to 0.3, more preferably 0.015 to 0.05, and still more preferably 0.02 to 0.045. In the present invention, α-type manganese dioxide containing ruthenium in the crystal structure is also referred to as Ru-doped α-type manganese dioxide.

[0012] The catalyst for chloride ion oxidation reaction of the present invention is a catalyst for promoting the oxidation reaction of chloride ions in the electrolysis of water containing chloride ions. Usually, it is used as the anode in electrolysis, and promotes the oxidation of chloride ions (Cl - ) at the anode, and promotes the generation of chlorine (Cl2), hypochlorite ions (ClO - ) or hypochlorous acid (HClO). In the present invention, as an index representing the oxidation of chloride ions, instead of CER (chlorine evolution reaction: chlorine generation reaction) indicating the generation of chlorine (Cl2), an index COR representing the reaction in which chloride ions are oxidized to Cl2, ClO - and HClO is used. The degree of COR can be determined by the COR faradaic efficiency. The catalyst for chloride ion oxidation reaction of the present invention has the characteristic of showing a high COR faradaic efficiency. For example, using a three-electrode cell, at a current density of 10 mA / cm 2, the amount of electricity passing through for electrolysis is 40 mC / cm 2 When measured using constant current electrolysis with a 0.5 M NaCl solution as the electrolyte, the COR Faraday efficiency ranged from 60-95%, 70-95%, and 80-95%. Furthermore, the current density measured using the same method was 10 mA / cm². 2 Overvoltage at 10 mA / cm², i.e., current density 10 mA / cm². 2 The overpotential required to reach this value is in the range of 110-310mV, 110-180mV, etc. Details of the measurement method for COR Faraday efficiency and overpotential are shown in the examples. Thus, the chloride ion oxidation reaction catalyst of the present invention can achieve excellent COR Faraday efficiency and low overpotential in the electrolysis of water containing chloride ions.

[0013] The overpotential associated with electrode reactions consists of an activation overpotential, which depends on the type of catalyst, and a concentration overpotential, which depends on the concentration gradient generated within the electrode by the ions and molecules produced during the electrode reaction. Of these, the activation overpotential follows Tafel's law in the low current density region; therefore, catalysts with a small Tafel gradient exhibit high activity, and a low overpotential can be expected. For this reason, the chloride ion oxidation reaction catalyst of the present invention preferably has a Tafel gradient of 40 to 130 mV / dec, and more preferably has a Tafel gradient of 40 to 110 mV / dec. Furthermore, the chloride ion oxidation reaction catalyst of the present invention has a Tafel gradient of 40 to 130 mF / cm 2 It is preferable to have an electric double layer capacitance of 40 to 70 mF / cm². 2 It is more preferable to have an electric double layer capacitance. The chloride ion oxidation reaction catalyst of the present invention has a BET specific surface area of ​​40 to 100 m². 2 It is preferable that the amount be / g, which is 45-95m 2 It is more preferable that it be / g.

[0014] In this invention, α-type manganese dioxide containing ruthenium in its crystal structure acts as a catalyst for chloride ion oxidation reactions and possesses the catalytic properties described above. Therefore, only α-type manganese dioxide containing ruthenium in its crystal structure can be used as a catalyst for chloride ion oxidation reactions, but this does not exclude the use of other catalysts that promote chloride ion oxidation reactions. Ruthenium-composite α-type manganese dioxide, which contains ruthenium in its crystal structure, has a ruthenium content of 0.004 to 0.3 in terms of the atomic ratio of ruthenium to manganese (Ru / Mn), a Faraday efficiency of 60% or more for chloride ion oxidation reactions, and a current density of 10 mA / cm². 2 It is preferable that the overvoltage required to reach this point is 310mV or less.

[0015] The electrode for the chloride ion oxidation reaction in the electrolysis of water containing chloride ions according to the present invention is an electrode on which the chloride ion oxidation reaction catalyst of the present invention or ruthenium-composite α-type manganese dioxide is supported. The electrode of the present invention has the chloride ion oxidation reaction catalyst of the present invention supported on a substrate. The substrate for the electrode of the present invention is not particularly limited as long as it is a conductive substrate, but examples of materials include metals such as titanium, zirconium, and tungsten, conductive glass such as FTO glass, carbon fiber, graphite, and carbon-based materials such as artificial graphite. Among these, titanium and titanium alloys are preferred as materials for the conductive substrate because they are commonly used in industry and have high corrosion resistance. Examples of titanium alloys include alloys of titanium with zirconium, niobium, tantalum, etc., and alloys of titanium with palladium. The shape of the conductive substrate in the present invention is not particularly limited, but examples include flat plate shape, curved plate shape, rod shape, mesh shape, lath shape, etc. In the electrode of the present invention, the chloride ion oxidation reaction catalyst of the present invention may be supported on a conductive substrate so as to be in direct contact with the conductive substrate, or the chloride ion oxidation reaction catalyst of the present invention may be supported on a conductive substrate via another substance. The electrode of the present invention can be used not only with seawater containing chloride ions, but also as an anode in the electrolysis of water, etc.

[0016] The method for producing the chloride ion oxidation reaction catalyst of the present invention is not particularly limited, but for example, the following method can be given: Potassium, sodium, ammonium, etc., permanganate (a salt of permanganate), and a salt of manganese such as manganese sulfate, nitrate, or chloride are dissolved in water, the pH of the solution is adjusted with an acid such as nitric acid, and then a salt of ruthenium such as ruthenium chloride, sulfate, or nitrate is added to prepare a precursor solution, and the prepared precursor solution is refluxed while stirring. After that, the catalyst for the chloride ion oxidation reaction of the present invention can be obtained by washing with distilled water or the like and drying by vacuum drying or the like. Furthermore, the catalyst for the chloride ion oxidation reaction of the present invention can be obtained by dissolving permanganate (a salt of permanganate) and manganese salts such as manganese sulfate, nitrate, and chloride in water, adjusting the pH of the solution with an acid such as nitric acid, and then adding ruthenium salts such as ruthenium chloride, sulfate, and nitrate to prepare a precursor solution, placing it in a pressure vessel such as an autoclave, and carrying out a hydrothermal reaction. The resulting product can then be separated by centrifugation or the like, washed with distilled water, and dried by vacuum drying or the like. Potassium permanganate (KMnO4) is preferred as the permanganate, manganese sulfate (MnSO4·H2O) is preferred as the manganese salt, and ruthenium chloride (RuCl3·xH2O) is preferred as the ruthenium salt.

[0017] The present invention relates to a hypochlorous acid or hypochlorite production apparatus, which comprises a water electrolysis apparatus and produces hypochlorous acid or hypochlorite by electrolyzing water containing chloride ions and metal ions, characterized in that the anode in the electrolysis apparatus is the chloride ion oxidation reaction electrode of the present invention. Furthermore, the present invention relates to a method for producing hypochlorous acid or hypochlorite, characterized in that water containing chloride ions and metal ions is electrolyzed using an electrolysis apparatus equipped with the chloride ion oxidation reaction electrode of the present invention as the anode to produce hypochlorous acid or hypochlorite. The electrolysis apparatus in the production apparatus and production method of the present invention is not particularly limited as long as it is an apparatus capable of electrolyzing water, and comprises a water electrolytic cell, an anode and a cathode installed in contact with the water in the electrolytic cell, a water supply port to the electrolytic cell, a water discharge port from the electrolytic cell, and a power supply. The anode in the electrolysis apparatus is the chloride ion oxidation reaction electrode of the present invention. The cathode is not particularly limited, but examples include nickel, copper, stainless steel, titanium, titanium alloy, platinum, graphite, etc. The water containing chloride ions and metal ions in this invention is not particularly limited as long as it contains chloride ions and metal ions, but examples of metal ions include lithium ions (Li + ), sodium ions (Na + ), potassium ions (K + Examples of alkali metal ions include (1) and (2). In the present invention, water containing chloride ions and metal ions is preferably water containing chloride ions and sodium ions in which sodium chloride (NaCl) is dissolved, and sodium hypochlorite, which is hypochlorous acid or a hypochlorite salt, can be produced. Examples of water containing chloride ions and sodium ions include seawater, brine, brackish water, buffer solution, etc.

[0018] The present invention's method for producing hypochlorous acid or hypochlorite may further include a water intake pump for drawing in water to be electrolyzed, such as seawater; a venting tank for removing gases such as hydrogen from the water containing hypochlorous acid or hypochlorite discharged from the electrolytic cell; and an injection pump for injecting the water containing hypochlorous acid or hypochlorite into an injection point. The produced water containing hypochlorous acid or hypochlorite may also be recycled by supplying it back to the electrolysis apparatus. In the production apparatus and method of the present invention, chlorine and hypochlorous acid are generated at the anode, while hydrogen is generated at the cathode, which is the opposite electrode. In the production apparatus and method of the present invention, by using the electrode of the present invention at the anode, the activity of the chloride ion oxidation reaction at the anode can be increased, thereby increasing the efficiency of hydrogen production at the cathode. Therefore, the production apparatus and method of the present invention can be used not only to produce hypochlorous acid or hypochlorite but also as an apparatus or method for producing hydrogen gas near the cathode of an electrolysis apparatus. [Examples]

[0019] The present invention will be described in detail below with reference to examples of the present invention, but the technical scope of the present invention is not limited to these examples.

[0020] [Example 1] 2.29 g of KMnO4 was dissolved in 40 mL of ultrapure water (Milli-Q water). This solution was added to a solution of 3.52 g of MnSO4·H2O (assay 99%) dissolved in 12 mL of ultrapure water (Milli-Q water), and 1.18 mL of nitric acid (69%) was added. Then, 0.242 g of RuCl3·xH2O was added to the above solution to obtain a precursor solution (Ru / Mn (atomic ratio) in the precursor solution = 0.033 / 1). This precursor solution was transferred to a four-necked flask and stirred vigorously with a stirring bar until homogeneous. The precursor solution was refluxed at 100°C for 24 hours using an oil bath while stirring. The obtained product was centrifuged and washed with distilled water until the pH was approximately 7. The residue was then vacuum-dried at 100°C for 12 hours to obtain Ru-doped MnO2.

[0021] [Example 2] The same procedure as in Example 1 was followed until the residue was vacuum-dried at 100°C for 12 hours. The vacuum-dried residue was then heat-treated in a muffle furnace at 200°C for 6 hours to obtain Ru-doped MnO2.

[0022] [Example 3] 2.29 g of KMnO4 was dissolved in 40 mL of ultrapure water (Milli-Q water). This solution was added to a solution of 3.52 g of MnSO4·H2O (assay 99%) dissolved in 12 mL of ultrapure water (Milli-Q water), and 1.18 mL of nitric acid (69%) was added. Then, 0.242 g of RuCl3·xH2O was added to the above solution to obtain a precursor solution (Ru / Mn (atomic ratio) in the precursor solution = 0.033 / 1). This precursor solution was transferred to an autoclave, stirred until homogeneous, and subjected to a hydrothermal reaction at 160 °C for 6 hours. The obtained product was centrifuged and washed with distilled water until the pH was approximately 7. The residue was then vacuum-dried at 100 °C for 12 hours to obtain Ru-doped MnO2.

[0023] [Example 4] Ru-doped MnO2 was obtained by performing the same procedure as in Example 3, except that a hydrothermal reaction was carried out at 160°C for 12 hours.

[0024] [Example 5] The same procedure as in Example 3 was followed until the residue was vacuum-dried at 100°C for 12 hours. The vacuum-dried residue was then heat-treated in a muffle furnace at 200°C for 6 hours to obtain Ru-doped MnO2.

[0025] [Example 6] The same procedure as in Example 4 was followed until the residue was vacuum-dried at 100°C for 12 hours. The vacuum-dried residue was then heat-treated in a muffle furnace at 200°C for 6 hours to obtain Ru-doped MnO2.

[0026] [Example 7] Except for adding 0.146 g of RuCl3·xH2O (Ru / Mn (atomic ratio) in the precursor solution = 0.020 / 1), the same procedure as in Example 1 was performed to obtain Ru-doped MnO2.

[0027] [Example 8] Except for adding 0.073 g of RuCl3·xH2O (Ru / Mn (atomic ratio) in the precursor solution = 0.010 / 1), the same procedure as in Example 1 was performed to obtain Ru-doped MnO2.

[0028] [Example 9] The same procedure as in Example 7 was followed until the residue was vacuum-dried at 100°C for 12 hours. The vacuum-dried residue was then heat-treated in a muffle furnace at 200°C for 6 hours to obtain Ru-doped MnO2.

[0029] [Example 10] The same procedure as in Example 8 was followed until the residue was vacuum-dried at 100°C for 12 hours. The vacuum-dried residue was then heat-treated in a muffle furnace at 200°C for 6 hours to obtain Ru-doped MnO2.

[0030] [Example 11] Except for adding 0.800 g of RuCl3·xH2O (Ru / Mn (atomic ratio) in the precursor solution = 0.11 / 1), the same procedure as in Example 1 was performed to obtain Ru-doped MnO2.

[0031] [Example 12] Except for adding 0.0362 g of RuCl3·xH2O (Ru / Mn (atomic ratio) in the precursor solution = 0.0049 / 1), the same procedure as in Example 1 was performed to obtain Ru-doped MnO2.

[0032] [Comparative Example 1] Commercially available RuO2 (99.9%, manufactured by Sigma-Aldrich) was used as the catalyst in Comparative Example 1.

[0033] [Comparative Example 2] 2.29 g of KMnO4 was dissolved in 40 mL of ultrapure water (Milli-Q water). This solution was added to a solution of 3.52 g of MnSO4·H2O (assay 99%) dissolved in 12 mL of ultrapure water (Milli-Q water), and 1.18 mL of nitric acid (69%) was added. The mixture was then transferred to a four-necked flask and stirred vigorously with a stirring bar until homogeneous. The mixture was refluxed at 100°C for 24 hours using an oil bath while stirring. The resulting product was centrifuged and washed with distilled water until the pH was approximately 7. The residue was then vacuum-dried at 100°C for 12 hours to obtain MnO2.

[0034] (X-ray diffraction (XRD)) X-ray diffraction measurements were performed on the Ru-doped MnO2 obtained in the examples, the MnO2 obtained in Comparative Example 2, and the commercially available RuO2 from Comparative Example 1. The measurements were performed using an X-ray diffractometer (Ultima4, Rigaku Corporation) equipped with Cu-Kα radiation (1.54051 Å, 40 kV, 30 mA) at a rate of 2°min. -1 The scan was performed in a 2θ region from 10 to 80° at the specified scan speed. The results are shown in Figures 1 and 2.

[0035] From the results in Figures 1 and 2, the Ru-doped MnO2 obtained in the example could be classified as cryptomelene-type (tetragonal) α-type manganese dioxide (α-MnO2: ICSD No. 00-044-0141). The MnO2 obtained in Comparative Example 2 could also be classified as α-MnO2 (ICSD No. 00-044-0141). Furthermore, the absence of peaks originating from ruthenium oxide in the XRD pattern obtained from X-ray diffraction, and the broadening observed when the ruthenium ratio is high, indicates that ruthenium (Ru) is contained in the crystal structure of α-type manganese dioxide.

[0036] (Measurement of the atomic ratio of Ru and Mn) The atomic ratio of Ru atoms to Mn atoms (Ru / Mn) in the Ru-doped MnO2 obtained in the examples was determined by X-ray fluorescence analysis (XRF) (Supermini200, Rigaku Corporation). The results are shown in Table 1. In Table 1, the blending ratio is the Ru / M (atomic ratio) in the raw material blending, and the composition ratio is the Ru / M (atomic ratio) in the obtained MnO2. The detection of Ru atoms in this measurement indicates that the Ru-doped MnO2 obtained in the examples is α-type manganese dioxide and contains Ru in its crystal structure.

[0037] [Table 1]

[0038] (Linear sweep voltammetry) Linear sweep voltammetry (LSV) was performed on Ru-doped MnO2 obtained in the Examples, MnO2 obtained in Comparative Example 2, and commercially available RuO2 from Comparative Example 1. A three-electrode cell was used, with a graphite rod as the counter electrode and Ag / AgCl (saturated KCl) as the reference electrode. 5 mg of each sample and 5 mg of acetylene carbon black (conductive carbon, 99.99%, manufactured by STREM CHEMICALS) were added to a mixed solution containing 350 μL of ethanol, 350 μL of water, and 95 μL of Nafion®, and ultrasonically dispersed for 30 minutes. 10 μL of the resulting dispersion was added dropwise to a glassy carbon rotating disk electrode (5 mm in diameter) polished with alumina (active material amount: 0.32 mg·cm). -2 ). Subsequently, to maintain reproducibility, the disk electrode was dried at room temperature in air at a rotational speed of 700 rpm for 30 minutes, and this was used as the working electrode. A 0.5 M NaCl solution purged with O2 for 30 minutes was used as the electrolyte. The sweep rate was set to 1 mV / s, and the rotational speed was set to 1600 rpm to remove oxygen bubbles on the working electrode. The solution resistance between the working electrode and the reference electrode was compensated with a feedback rate of 85%. The results are shown in Figures 3 and 4.

[0039] (Tafel gradient) To analyze the rising portion in Figures 3 and 4, the Tafel gradient was calculated. The Tafel gradient calculated from Figure 3 is shown in Table 2, and the Tafel gradient calculated from Figure 4 is shown in Table 3. From the results in Tables 2 and 3, it can be seen that the Ru-doped MnO2 obtained in the examples has a reaction rate that is approximately the same as or faster than commercially available RuO2.

[0040] [Table 2]

[0041] [Table 3]

[0042] (Constant current electrolysis) Constant current electrolysis was performed to measure the COR Faraday efficiency of Ru-doped MnO2 obtained in the example, MnO2 obtained in Comparative Example 2, and commercially available RuO2 from Comparative Example 1. A three-electrode cell was used, with a graphite rod as the counter electrode and Ag / AgCl (saturated KCl) as the reference electrode. The working electrode was prepared in the same manner as in LSV, with a current density of 10 mA / cm². 2 Constant current electrolysis was performed at a rotation speed of 1600 rpm. 120 mL of 0.5 M NaCl solution, purged with O2 for 30 minutes, was used as the electrolyte. The solution resistance between the working electrode and the reference electrode was compensated with a feedback rate of 85%. The generated ClO... - The amount of HClO was determined based on the visible peak intensity at 551 nm using diethyl-paraphenylenediamine (DPD) reagent and a UV-vis spectrophotometer (V-670, JASCO Corporation). The COR Faraday efficiency was calculated using the following formula (1). In the following formula (1), [chlorine oxide species] (mol / L) is ClO - And the amount of HClO, V is the volume of the electrolyte, and Q is the amount of electricity passed through during electrolysis (40C / cm³). 2 ), A is the geometric area of ​​the electrode (cm²) 2), where n is the number of reaction electrons (n=2 in the case of COR), and F is the Faraday constant (96,485 C / mol). This measurement uses an electrolyte solution that is close to neutral, but as COR or OER proceeds, the pH shifts to acidic. Therefore, in this measurement, the COR product exists as hypochlorous acid or hypochlorite ions. The results of constant current electrolysis are shown in Figures 5 and 6.

[0043]

number

[0044] Current density 10mA / cm 2 The potential at is calculated from the potential at 4000 seconds (s) in Figures 5 and 6, and the overvoltage is calculated by converting the measured potential (vs. SHE) to the RHE reference (E RHE =E SHE The overpotential (+0.059 pH) was calculated by subtracting it from the standard electrode potential of the COR reaction, 1.49 V vs. RHE (neutral conditions). The overpotential and COR Faraday efficiency obtained from constant current electrolysis are shown in Tables 4 and 5. In the table, "η" COR (mV) at 10mA / cm 2 " indicates a current density of 10 mA / cm² 2 The overpotential required to reach a certain level is referred to as the "COR efficiency," which indicates the COR Faraday efficiency. From the results in Tables 4 and 5, the Ru-doped MnO2 obtained in the examples showed a higher COR Faraday efficiency than the commercially available RuO2 in Comparative Example 1. On the other hand, the COR Faraday efficiency of the undoped MnO2 in Comparative Example 2 was significantly lower than that of the commercially available RuO2 in Comparative Example 1. Regarding overpotential, the samples obtained in the examples were higher than those in the commercially available RuO2 in Comparative Example 1, but the difference was not significant enough to hinder the improvement in the efficiency of hypochlorite ion and hypochlorous acid generation due to the COR Faraday efficiency.

[0045] [Table 4]

[0046] [Table 5]

[0047] (Electrochemical effective surface area (electrochemical double layer capacitance)) The electrochemical double-layer capacitances of Ru-doped MnO2 obtained in the example, MnO2 obtained in Comparative Example 2, and commercially available RuO2 from Comparative Example 1 were measured. A three-electrode cell was used, with a graphite rod as the counter electrode and Hg / HgO (1M NaOH) as the reference electrode. The working electrode was prepared in the same manner as LSV. A 1M KOH solution purged with O2 for 30 minutes was used as the electrolyte. Cyclic voltammetry (CV) was performed in the non-Faraday region (0.01-0.1V vs. Hg / HgO) potential range. The sweep rate was set to 2-10 mV / s and the rotation speed to 1600 rpm. Figures 7 and 8 show the difference Δj (=j) between the cathode current and anode current at a predetermined potential (0.05V vs. Hg / HgO) obtained from the CV measurements of each catalyst. anodic -j cathodic The plots shown have the vertical axis representing the capacitance (C) and the horizontal axis representing the sweep rate. The slope of the approximation curve obtained from the plots in Figures 7 and 8 is defined as the electrochemical double layer capacitance (C). dl ) was assumed. Tables 6 and 7 show the values ​​of the electrochemical double layer capacitance obtained. As shown in Tables 6 and 7, the electrochemical double layer capacitance of the Ru-doped MnO2 obtained in the example was significantly larger than that of the commercially available RuO2 in Comparative Example 1. Furthermore, although the electrochemical double layer capacitance is proportional to the size of the electrochemically usable surface area, no clear correlation is observed between it and the overpotential or COR Faraday efficiency shown in Tables 4 and 5. Therefore, the measurement results of the electrochemical double layer capacitance are considered to reflect the change in reactivity due to the combination of Mn and Ru.

[0048] [Table 6]

[0049] [Table 7]

[0050] (BET specific surface area) The BET specific surface area of ​​Ru-doped MnO2 obtained in the examples was measured using FlowSorbIII (Micrometrics). The measurement was based on the BET single-point method, and degassing pretreatment was performed at 80°C for 3 hours in a nitrogen stream. The results are shown in Table 8.

[0051] [Table 8] [Industrial applicability]

[0052] The chloride ion oxidation reaction catalyst of the present invention reduces the amount of precious metals used and, while using inexpensive materials, exhibits excellent oxidation efficiency of chloride ions, making it suitable for use in the electrolysis of water containing chloride ions, such as seawater. The hypochlorous acid or hypochlorite production apparatus and production method of the present invention, by using the chloride ion oxidation reaction catalyst of the present invention, exhibits excellent production efficiency of hypochlorous acid or hypochlorite while using inexpensive materials as a catalyst, making it suitable for use in the production of hypochlorous acid or hypochlorite injected into parts in contact with seawater to suppress the attachment of marine organisms in thermal power plants, LNG / LPG terminals, desalination plants, nuclear power plants, oil refining plants, fertilizer plants, chemical plants, offshore plants, coastal water treatment plants, etc.

Claims

1. A catalyst for the oxidation reaction of chloride ions in the electrolysis of water containing chloride ions, wherein the catalyst contains ruthenium, the ruthenium is contained in the crystal structure of α-type manganese dioxide, and the ruthenium content is 0.004 to 0.3 in terms of the atomic ratio of ruthenium to manganese (Ru / Mn).

2. A ruthenium-composite α-type manganese dioxide catalyst for the chloride ion oxidation reaction in the electrolysis of water containing chloride ions, wherein the ruthenium is contained within the crystal structure of α-type manganese dioxide, and the ruthenium content is 0.004 to 0.3 in terms of the atomic ratio of ruthenium to manganese (Ru / Mn), the Faraday efficiency for the chloride ion oxidation reaction is 60% or more, and the current density is 10 mA / cm². ２ Ruthenium composite α-type manganese dioxide, in which the overvoltage required to reach this state is 310 mV or less.

3. An electrode for the chloride ion oxidation reaction in the electrolysis of water containing chloride ions, wherein the catalyst for the chloride ion oxidation reaction according to claim 1 or the ruthenium-composite α-type manganese dioxide according to claim 2 is supported.

4. A hypochlorous acid or hypochlorite production apparatus comprising a water electrolysis device, wherein hypochlorous acid or hypochlorite is produced by electrolyzing water containing chloride ions and metal ions, and the anode in the electrolysis device is the chloride ion oxidation reaction electrode described in claim 3.

5. A method for producing hypochlorous acid or hypochlorite by electrolyzing water containing chloride ions and metal ions using an electrolysis apparatus equipped with the chloride ion oxidation reaction electrode described in claim 3 as the anode.

6. A method for producing hypochlorous acid or hypochlorite according to claim 5, which involves producing hypochlorous acid or hypochlorite and producing hydrogen gas near the cathode of an electrolysis apparatus.

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