JP2020193371A - Ozone generating electrode - Google Patents
Ozone generating electrode Download PDFInfo
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- JP2020193371A JP2020193371A JP2019099826A JP2019099826A JP2020193371A JP 2020193371 A JP2020193371 A JP 2020193371A JP 2019099826 A JP2019099826 A JP 2019099826A JP 2019099826 A JP2019099826 A JP 2019099826A JP 2020193371 A JP2020193371 A JP 2020193371A
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- electrode
- ozone
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- platinum
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 8
- 239000002019 doping agent Substances 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 16
- 229910052787 antimony Inorganic materials 0.000 claims description 15
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 230000002708 enhancing effect Effects 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 86
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- 238000005868 electrolysis reaction Methods 0.000 abstract description 19
- 230000004927 fusion Effects 0.000 abstract 1
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- 238000000034 method Methods 0.000 description 33
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- 238000004519 manufacturing process Methods 0.000 description 8
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- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 6
- -1 platinum group metal oxide Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 4
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- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
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- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
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- 150000003606 tin compounds Chemical class 0.000 description 2
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- 235000005074 zinc chloride Nutrition 0.000 description 2
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 229910004349 Ti-Al Inorganic materials 0.000 description 1
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- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
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- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
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- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
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Abstract
Description
本発明は、工業用又は民生用電解プロセスに使用されるオゾン生成用電極に関する。 The present invention relates to ozone-generating electrodes used in industrial or consumer electrolysis processes.
電気分解によって、余分な試薬を使わずに水中に酸化力の高い殺菌成分を発生させる技術の検討は古くから行われてきた。比較的簡単な方法として食塩を加えた希薄食塩水を電解して陽極に塩素を発生させ、この塩素と水の反応により生成する次亜塩素酸の殺菌性を利用する処理がある。この方法は簡便であり広く使われているが、より殺菌性を高めるためにオゾンを用いた水処理への要望も増してきている。オゾンは酸化力の非常に強い物質であり、オゾンが溶解したオゾン水は、食品加工や医療現場における殺菌、臭気性の有機物あるいは細菌等を含む上下水道や排水の水処理・殺菌、半導体デバイス製造プロセスにおける洗浄等の現場で利用していくことが期待されている。このオゾン水は、水の電気分解の陽極反応によって、水分子をオゾンへ直接変換させて製造することが一般に行われている。 A technique for generating a bactericidal component having high oxidizing power in water by electrolysis without using an extra reagent has been studied for a long time. As a relatively simple method, there is a treatment in which a dilute saline solution containing salt is electrolyzed to generate chlorine at the anode, and the bactericidal property of hypochlorous acid produced by the reaction between the chlorine and water is utilized. Although this method is simple and widely used, there is an increasing demand for water treatment using ozone in order to further improve bactericidal properties. Ozone is a substance with extremely strong oxidizing power, and ozone water in which ozone is dissolved is sterilized in food processing and medical settings, water treatment and sterilization of water and sewage and wastewater containing odorous organic substances or bacteria, and semiconductor device manufacturing. It is expected to be used in the field such as cleaning in the process. This ozone water is generally produced by directly converting water molecules into ozone by the anodic reaction of electrolysis of water.
電気分解の陽極反応によって水分子をオゾンへ直接変換させるための陽極材料として、比較的高い導電性を有しながら、通常の酸素発生用電極より高い酸素過電圧を有する電極触媒材料が求められている。そのような電極の一つとして、白金電極が古くからオゾン発生用電極として用いられてきたが、十分なオゾン発生効率が得られないばかりか、高価であり経済性の問題もある。近年、ホウ素をドープしたダイヤモンド電極が安定であり、優れたオゾン発生効率を示す特徴を有することが知られてきている。しかしながら、現状では極めて高価であり、また形状の自由度がないために用途が限られるという問題点が残されている。 As an anodic material for directly converting water molecules into ozone by an anodic reaction of electrolysis, an electrode catalyst material having a relatively high conductivity and a higher oxygen overvoltage than a normal oxygen-evolving electrode is required. .. As one of such electrodes, a platinum electrode has been used as an ozone generation electrode for a long time, but not only is it not possible to obtain sufficient ozone generation efficiency, but it is also expensive and economical. In recent years, it has been known that a boron-doped diamond electrode is stable and has a feature of exhibiting excellent ozone generation efficiency. However, at present, it is extremely expensive, and there remains a problem that its use is limited due to the lack of freedom in shape.
白金電極やダイヤモンド電極よりも安価でありながら、オゾン発生が可能な導電性と高い酸素過電圧を有する電極材料として酸化スズや酸化鉛が知られている。 Tin oxide and lead oxide are known as electrode materials having conductivity capable of generating ozone and high oxygen overvoltage while being cheaper than platinum electrodes and diamond electrodes.
従来技術として、特許文献１には、電極表面の酸化スズ層に酸化アンチモン、白金族金属酸化物を含有させる電解用電極が開示されている。具体的には、耐食性金属基材上に酸化スズと酸化アンチモン、及び白金族金属酸化物を含む電極物質被膜からなる電極とする。 As a prior art, Patent Document 1 discloses an electrode for electrolysis in which an antimony oxide and a platinum group metal oxide are contained in a tin oxide layer on an electrode surface. Specifically, the electrode is formed of an electrode material coating containing tin oxide, antimony oxide, and a platinum group metal oxide on a corrosion-resistant metal substrate.
特許文献２には、金属基体の表面に耐食中間層と、耐食中間層の表面に触媒層とを有する電解用電極において、触媒層が、酸化鉛層と、その表面に酸化スズ及び酸化アンチモンを含有する積層構造からなる電解用電極が開示されている。 In Patent Document 2, in an electrode for electrolysis having a corrosion-resistant intermediate layer on the surface of a metal substrate and a catalyst layer on the surface of the corrosion-resistant intermediate layer, the catalyst layer comprises a lead oxide layer and tin oxide and antimony oxide on the surface thereof. An electrode for electrolysis having a laminated structure containing the mixture is disclosed.
特許文献３には、水の殺菌のためのオゾン発生器であって、水から電解オゾンを発生させるための陽極材料として、アンチモンとニッケルを添加した酸化スズ材料を用いたオゾン発生器が開示されている。 Patent Document 3 discloses an ozone generator for sterilizing water, which uses a tin oxide material to which antimony and nickel are added as an anode material for generating electrolytic ozone from water. ing.
特許文献４には、基材基体と、基体の表面に被覆層（触媒層）を有する電解用電極において、被覆層がスズ、アンチモン、ニッケルを含む電極が開示されている。 Patent Document 4 discloses an electrode in which a coating layer contains tin, antimony, and nickel in a substrate and an electrode for electrolysis having a coating layer (catalyst layer) on the surface of the substrate.
特許文献５には、Ｔｉ基体上に中間層（アンチモン・スズを含み、さらに、マンガン、コバルトおよびルテニウムのうちの１つ以上の元素がドープされている）を備え、その上に界面活性層（ニッケルとアンチモンとスズを含む）を備えたオゾン生成用電極の製造方法が開示されている。 In Patent Document 5, an intermediate layer (containing antimony / tin and further doped with one or more elements of manganese, cobalt and ruthenium) is provided on a Ti substrate, and a surface active layer (containing one or more elements) is provided on the intermediate layer (containing antimony / tin). A method for producing an electrode for ozone generation including nickel, antimony and tin) is disclosed.
上記特許文献１に開示の電解用電極では、酸化スズ層に白金族金属酸化物、酸化アンチモンを加えることによって電極全体の電気抵抗を小さくし、電解電圧を下降させると共に、大電流を流せるようにする事によって、電力使用量の低減を図る機能が開示されているが、陽極電流に対するオゾン生成効率を高めるための対策が開示されていない。
特許文献２に開示の電解用電極では、酸化鉛層と、その表面に酸化スズ及び酸化アンチモンを含有する積層構造からなる触媒層とすることで、酸化鉛の消耗を抑制して電極の耐久性を向上させる機能が開示されているが、陽極電流に対するオゾン生成効率を高めるための作用については開示されていない。
特許文献４に開示のアンチモンとニッケルを添加した酸化スズ電極では、ニッケル添加によってオゾン生成効率が高まることが開示されているが、オゾン生成効率を高めるための作用については開示されていない。
In the electrode for electrolysis disclosed in Patent Document 1, the electric resistance of the entire electrode is reduced by adding a platinum group metal oxide and antimony oxide to the tin oxide layer, the electrolytic voltage is lowered, and a large current can flow. By doing so, the function of reducing the amount of electric power used is disclosed, but the measures for increasing the ozone generation efficiency with respect to the anodic current are not disclosed.
The electrode for electrolysis disclosed in Patent Document 2 has a catalyst layer composed of a lead oxide layer and a laminated structure containing tin oxide and antimony oxide on the surface thereof, thereby suppressing the consumption of lead oxide and the durability of the electrode. However, the action for increasing the ozone generation efficiency with respect to the anode current is not disclosed.
In the tin oxide electrode to which antimony and nickel are added disclosed in Patent Document 4, it is disclosed that the addition of nickel increases the ozone generation efficiency, but the action for increasing the ozone generation efficiency is not disclosed.
酸化スズを触媒層に含む電極は、上記文献に記載されたような改良がなされているが、オゾン発生効率がまだ十分に高いとは言えず、さらなる改善が求められている。 The electrode containing tin oxide in the catalyst layer has been improved as described in the above literature, but the ozone generation efficiency is not yet sufficiently high, and further improvement is required.
本発明の目的は、オゾン発生効率のさらに改善された電解用電極を提供することである。 An object of the present invention is to provide an electrode for electrolysis with further improved ozone generation efficiency.
本発明者らは上記課題の課題を解決すべく鋭意研究した結果、スズ酸化物を触媒層に含む電解用電極において、ニッケル等の活性元素（オゾン発生効率を増強する）の効果をさらに高めるためには、活性元素を触媒層中へ微細にかつ均一に分散化させることが必要であり、そのためには、活性元素と金属間化合物を形成しうる融点が４２０℃以下の安定化元素を触媒層に添加することが効果的であることを見出した。その結果、活性元素を触媒層中へ微細にかつ均一に分散化させることが可能となり、従来よりも高い効率でオゾンを電解生成することが可能であることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors further enhance the effect of active elements such as nickel (enhancing ozone generation efficiency) in electrolytic electrodes containing tin oxide in the catalyst layer. It is necessary to finely and uniformly disperse the active element in the catalyst layer, and for that purpose, a stabilizing element having a melting point of 420 ° C. or less capable of forming an intermetallic compound with the active element is used in the catalyst layer. It was found that it is effective to add to. As a result, it has been found that the active element can be finely and uniformly dispersed in the catalyst layer, and ozone can be electrolyzed and generated with higher efficiency than before, and the present invention has been completed. It was.
具体的には、活性元素としてニッケル、コバルト、セリウム、及び鉄を使用し、さらに安定化元素としてビスマス、亜鉛、及びインジウム等の融点が４２０℃以下と比較的低く、かつ活性元素と金属間化合物を形成しうる金属種を加えることで、触媒層の形成過程において、活性元素に対して低融点金属が溶け込み、Ｎｉ−Ｂｉ、Ｎｉ−Ｂｉ３、Ｎｉ２−Ｚｎ11、Ｎｉ−Ｚｎ３、Ｎｉ５−Ｚｎ２１、Ｎｉ−Ｉｎ、Ｎｉ２−Ｉｎ３、Ｆｅ３−Ｚｎ１０、Ｆｅ５−Ｚｎ２１、Ｆｅ−Ｚｎ７、Ｃｅ−Ｉｎ２、Ｃｅ−Ｉｎ３、Ｃｅ２−Ｉｎ、Ｃｅ３−Ｉｎ、Ｃｅ３−Ｉｎ５、Ｃｅ−Ｂｉ、Ｃｅ−Ｂｉ２、Ｃｅ３−Ｂｉ、Ｃｅ４−Ｂｉ３、Ｃｏ−Ｚｎ、Ｃｏ−Ｚｎ９、Ｃｏ−Ｚｎ１３、Ｃｏ５−Ｚｎ２１等の金属間化合物の形成を促進する。その結果、活性元素が化合物として安定化するとともに活性元素が触媒層全体に均一に分散され、従来よりもオゾン生成効率を高める機能を十分に発揮させることができる電解用電極を完成するに至った。 Specifically, nickel, cobalt, cerium, and iron are used as active elements, and bismuth, zinc, indium, and the like have relatively low melting points of 420 ° C. or lower as stabilizing elements, and the active element and an intermetal compound By adding a metal species capable of forming zinc, a low melting point metal dissolves in the active element in the process of forming the catalyst layer, and Ni-Bi, Ni-Bi 3 , Ni 2 -Zn 11 , Ni-Zn 3 , Ni. 5- Zn 21 , Ni-In 3 , Ni 2 -In 3 , Fe 3 -Zn 10 , Fe 5 -Zn 21 , Fe-Zn 7 , Ce-In 2 , Ce-In 3 , Ce 2 -In, Ce 3- Between metals such as In, Ce 3-In 5 , Ce-Bi, Ce-Bi 2 , Ce 3 -Bi, Ce 4 -Bi 3 , Co-Zn, Co-Zn 9 , Co-Zn 13 , Co5-Zn 21 and the like. Promotes the formation of compounds. As a result, we have completed an electrode for electrolysis in which the active element is stabilized as a compound and the active element is uniformly dispersed in the entire catalyst layer, so that the function of increasing the ozone generation efficiency can be sufficiently exhibited. ..
すなわち、本発明は、金属よりなる電極基体と、前記電極基体表面上の中間層と、前記中間層上の触媒層からなるオゾン生成用電極であって、前記触媒層は、スズの酸化物と、ニッケル、コバルト、セリウム、及び鉄の中から選択される１種又は２種以上の活性元素と、前記活性元素と金属間化合物を形成しうる融点が４２０℃以下の安定化元素を含む、
ことを特徴とするオゾン生成用電極である。
That is, the present invention is an ozone-generating electrode composed of an electrode substrate made of metal, an intermediate layer on the surface of the electrode substrate, and a catalyst layer on the intermediate layer, wherein the catalyst layer is an oxide of tin. , Nickel, cobalt, cerium, and one or more active elements selected from iron, and a stabilizing element having a melting point of 420 ° C. or lower that can form an intermetallic compound with the active element.
It is an electrode for ozone generation.
前記構成において、前記安定化元素が、ビスマス、亜鉛、及びインジウムの中から選択される少なくとも１種を含んでもよい。 In the configuration, the stabilizing element may contain at least one selected from bismuth, zinc, and indium.
前記構成において触媒層が、導電性を高めるためのドーパントを含んでもよい。 In the above configuration, the catalyst layer may contain a dopant for increasing conductivity.
前記構成において、前記ドーパントが、アンチモンであってもよい。 In the configuration, the dopant may be antimony.
また、本発明は、金属よりなる電極基体と、前記電極基体表面上の中間層と、前記中間層表面上の外層とからなる電解用電極において、前記外層が、金属換算で、
（ａ）酸化スズ６０〜９７ｍｏｌ％と、
（ｂ）酸化アンチモン１〜１０ｍｏｌ％と、
（ｃ）元素群Ａとしてニッケル、コバルト、セリウム、鉄の少なくとも一種の元素を０．５〜５ｍｏｌ％と、
（ｄ）元素群Ｂとしてビスマス、亜鉛、インジウムの少なくとも一種の元素を０．５〜５ｍｏｌ％、
とからなることを特徴とするオゾン生成用電極であってもよい。また、前記電極基体が、チタンまたはチタン合金であってもよい。
Further, according to the present invention, in an electrode for electrolysis composed of an electrode substrate made of metal, an intermediate layer on the surface of the electrode substrate, and an outer layer on the surface of the intermediate layer, the outer layer is in terms of metal.
(A) Tin oxide 60-97 mol%,
(B) Antimony oxide 1-10 mol%,
(C) As the element group A, at least one element of nickel, cobalt, cerium, and iron is 0.5 to 5 mol%.
(D) As the element group B, 0.5 to 5 mol% of at least one element of bismuth, zinc, and indium.
It may be an ozone generation electrode characterized by: Further, the electrode substrate may be titanium or a titanium alloy.
本発明によれば、オゾンを高い効率で発生させる電解用電極を提供することができる。 According to the present invention, it is possible to provide an electrode for electrolysis that generates ozone with high efficiency.
以下、本発明のオゾン生成用電極について説明する。 Hereinafter, the ozone-generating electrode of the present invention will be described.
〔１〕オゾン生成用電極
本発明のオゾン生成用電極は、金属よりなる電極基体と、電極基体表面上の中間層と、前記中間層上の触媒層からなるオゾン生成用電極であって、前記触媒層は、スズの酸化物と、ニッケル、コバルト、セリウム、及び鉄の中から選択される１種又は２種以上の活性元素と、前記活性元素と金属間化合物を形成しうる融点が４２０℃以下の安定化元素を含むことを特徴とする。
[1] Ozone generation electrode The ozone generation electrode of the present invention is an ozone generation electrode composed of an electrode substrate made of metal, an intermediate layer on the surface of the electrode substrate, and a catalyst layer on the intermediate layer. The catalyst layer has a melting point of 420 ° C. that can form an oxide of tin, one or more active elements selected from nickel, cobalt, cerium, and iron, and the active element and an intermetallic compound. It is characterized by containing the following stabilizing elements.
＜電極基体＞
本発明の電極において、使用される環境によっては強酸性や酸化性雰囲気に曝されることもあるので、電極基体の材質としては、チタン、ジルコニウム、ニオブ、鉄、タンタル、バナジウム及びそれらの金属を主成分とする合金からなる金属等、その表面に不動態層を形成して防食性を高める金属が好ましく挙げられ、これらの中でも特にチタン又はチタン合金が好ましく挙げられる。チタン合金としては、チタンを主体とする耐食性のある導電性の合金が使用され、例えばＴｉ−Ｔａ−Ｎｂ、Ｔｉ−Ｐｄ、Ｔｉ−Ｚｒ、Ｔｉ−Ｗ、Ｔｉ−Ａｌ等の組合せからなる、通常電極材料として使用されているＴｉ基合金が挙げられる。これらの電極材料は板状、有孔板状、棒状、網板状等の所望形状に加工して電極基体として用いることができる。
<Electrode substrate>
Since the alloy of the present invention may be exposed to a strongly acidic or oxidizing atmosphere depending on the environment in which it is used, titanium, zirconium, niobium, iron, tantalum, vanadium and their metals are used as the material of the electrode substrate. Metals such as a metal composed of an alloy as a main component, which forms a passivation layer on the surface thereof to enhance corrosion resistance, are preferably mentioned, and among these, titanium or a titanium alloy is particularly preferable. As the titanium alloy, a corrosion-resistant conductive alloy mainly composed of titanium is used, and is usually composed of a combination of, for example, Ti-Ta-Nb, Ti-Pd, Ti-Zr, Ti-W, Ti-Al and the like. Examples thereof include Ti-based alloys used as electrode materials. These electrode materials can be processed into a desired shape such as a plate shape, a perforated plate shape, a rod shape, or a net plate shape and used as an electrode substrate.
上記の如き電極基体には、予め前処理をするのが望ましい。電極基体の前処理方法としては、研削材を吹き付けて機械的に粗面化するブラスト処理方法や、シュウ酸など酸溶液の流動浴又は静止浴に浸漬させて、電極基体の表面を溶解させる化学的エッチング法などがある。 It is desirable to pretreat the electrode substrate as described above in advance. As a pretreatment method for the electrode substrate, a blast treatment method in which an abrasive is sprayed to mechanically roughen the surface, or a chemistry in which the surface of the electrode substrate is dissolved by immersing it in a liquid bath or a static bath of an acid solution such as oxalic acid. There is a target etching method.
＜中間層＞
本発明に用いる中間層としては、中間層に貴金属を含むものを用いることができる。例えば、貴金属又はその合金からなる耐食中間層、又は貴金属酸化物等を挙げることができる。貴金属としては、イリジウム、ルテニウム、ロジウム、金、銀、パラジウム、白金が挙げられる。貴金属としては、白金、イリジウム、ロジウムが好ましい。これらの中でも特に白金が好ましい。合金としては、前記貴金属を二種類以上混合したものが挙げられる。貴金属酸化物としては酸化イリジウム、酸化ルテニウム、酸化パラジウムなどが挙げられ、その他耐食性材料として公知のタンタル、酸化タンタル、酸化ニオブ、酸化チタン等が挙げられる。
<Middle layer>
As the intermediate layer used in the present invention, a layer containing a precious metal in the intermediate layer can be used. For example, a corrosion-resistant intermediate layer made of a noble metal or an alloy thereof, a noble metal oxide, or the like can be mentioned. Precious metals include iridium, ruthenium, rhodium, gold, silver, palladium and platinum. Platinum, iridium, and rhodium are preferable as the noble metal. Of these, platinum is particularly preferable. Examples of the alloy include a mixture of two or more of the precious metals. Examples of the noble metal oxide include iridium oxide, ruthenium oxide, palladium oxide and the like, and other known corrosion-resistant materials include tantalum, tantalum oxide, niobium oxide, titanium oxide and the like.
中間層の製造方法について説明する。 A method for manufacturing the intermediate layer will be described.
本発明のオゾン生成用電極の製造方法において、中間層を形成する方法としては、気相中におけるスパッタ法、イオンプレーティング法等の方法のほか、液相中におけるめっき法によってもよく、塗布液を用いて塗布・乾燥・焼成する熱分解法によっても良い。特に、貴金属からなる中間層の製造方法としては電気めっき法が好ましい。 In the method for producing an ozone-generating electrode of the present invention, as a method for forming an intermediate layer, a method such as a sputtering method in a gas phase, an ion plating method, or a plating method in a liquid phase may be used, and a coating liquid may be used. It may also be a thermal decomposition method of coating, drying and firing using. In particular, an electroplating method is preferable as a method for producing an intermediate layer made of a precious metal.
一例として、白金からなる中間層の製造方法について説明する。粗面化した金属基体の表面に白金被覆層を形成するには通常電気めっき法により行うことができる。この電気めっき法に使用しうるめっき浴の組成としては、たとえばＨ２ＰｔＣｌ６、（ＮＨ4)２ＰｔＣｌ６、Ｋ２ＰｔＣｌ６、Ｐｔ（ＮＨ３)２(ＮＯ２)２等の白金化合物を、硫酸溶液（ｐＨ１〜３）又はアンモニア水溶液に、白金換算で２〜２０ｇ／Ｌ、特に５〜１０ｇ／Ｌの濃度になるように溶解し、さらに必要に応じて浴の安定化のために硫酸ナトリウム（酸性浴の場合）、亜硫酸ナトリウム、硫酸ナトリウム（アルカリ性浴の場合）等を少量添加した酸性又はアルカリ性のめっき浴が挙げられる。 As an example, a method for producing an intermediate layer made of platinum will be described. The platinum coating layer can be formed on the surface of the roughened metal substrate by an electroplating method. The composition of the plating bath that can be used in this electroplating method includes, for example, platinum compounds such as H 2 PtCl 6 , (NH4) 2 PtCl 6 , K 2 PtCl 6 , Pt (NH 3 ) 2 (NO 2 ) 2 . Dissolve in sulfuric acid solution (pH 1-3) or aqueous ammonia solution to a concentration of 2 to 20 g / L in terms of platinum, especially 5 to 10 g / L, and if necessary, sodium sulfate to stabilize the bath. Examples thereof include an acidic or alkaline plating bath in which a small amount of sodium sulfate, sodium sulfate (in the case of an alkaline bath) or the like is added (in the case of an acidic bath).
かかる組成のめっき浴を用いての白金電気めっき工程では、所謂ストライクめっき等の高速めっき法を用い約３０〜約６０℃の範囲内の比較的低温で行うのが望ましい。この電気めっきにより、物理的密着強度の優れた白金被覆層を形成せしめることができる。その際の白金被覆層の見掛け密度は８〜１９ｇ／ｃｍ３、好ましくは１２〜１８ｇ／ｃｍ３の範囲内にあるのが適当である。該白金被覆層の見掛け密度が８ｇ／ｃｍ３より小さいと白金の結合強度が低下して剥離しやすくなり、反対に１９ｇ／ｃｍ３を越えると後述する熱分解で得られる触媒層の安定な担持が困難となる。該白金被覆層の見掛け密度のコントロールは、例えば金属基体の前処理条件、白金めっき浴の浴組成及び／又はめっき条件（電流密度や電流波形等）を経験的に調節することによって行うことができる。 In the platinum electroplating step using a plating bath having such a composition, it is desirable to use a high-speed plating method such as so-called strike plating at a relatively low temperature in the range of about 30 to about 60 ° C. By this electroplating, a platinum coating layer having excellent physical adhesion strength can be formed. At that time, the apparent density of the platinum coating layer is preferably in the range of 8 to 19 g / cm 3 , preferably 12 to 18 g / cm 3 . If the apparent density of the platinum coating layer is less than 8 g / cm 3 , the bond strength of platinum decreases and it becomes easy to peel off. On the contrary, if it exceeds 19 g / cm 3 , the catalyst layer obtained by thermal decomposition described later is stably supported. Becomes difficult. The apparent density of the platinum coating layer can be controlled, for example, by empirically adjusting the pretreatment conditions of the metal substrate, the bath composition of the platinum plating bath and / or the plating conditions (current density, current waveform, etc.). ..
このようにして、基体上に設けられた見掛密度が8〜19g/cm3の範囲内にある多孔性白金被覆層からなる中間層を得ることができる。 In this way, an intermediate layer made of a porous platinum-coated layer having an apparent density of 8 to 19 g / cm 3 provided on the substrate can be obtained.
多孔性白金被覆層を設ける代わりに、分散被覆された白金を設けることもできる。分散被覆された白金の形成にあたっては、上述と同じ浴組成のめっき浴を用いる。所謂ストライクめっき等の高速めっき法を用い約３０〜約６０℃の範囲内の比較的低温で行うのが望ましい。 Instead of providing the porous platinum coating layer, dispersion-coated platinum can also be provided. In forming the dispersion-coated platinum, a plating bath having the same bath composition as described above is used. It is desirable to use a high-speed plating method such as so-called strike plating at a relatively low temperature within the range of about 30 to about 60 ° C.
その際の白金の分散状態のコントロールは、例えばメツキ条件（電流密度や電流波形等）を経験的に調整することによって行なうことができる。 かくして、チタン基体上にその基体表面が部分的に露出する程度に分散被覆された白金を析出せしめる。その分散被覆の状態は、５０００倍の電子顕微鏡で観察すると、白金がチタン基体表面上に、点状、線状、網目状に分散していることがわかる。白金の析出量としては、一般０．０１〜２ｍｇ／ｃｍ２、好ましくは０．０２〜０．５ｍｇ／ｃｍ２とすることができる。 At that time, the dispersion state of platinum can be controlled, for example, by empirically adjusting the squeezing conditions (current density, current waveform, etc.). Thus, platinum dispersed and coated is precipitated on the titanium substrate to the extent that the surface of the substrate is partially exposed. When the state of the dispersion coating is observed with a 5000x electron microscope, it can be seen that platinum is dispersed on the surface of the titanium substrate in a dot-like, linear, or mesh-like manner. The amount of platinum precipitated can be generally 0.01 to 2 mg / cm 2 , preferably 0.02 to 0.5 mg / cm 2 .
白金の分散被覆の程度は、被覆率で表わして、１０〜８０％の範囲内とするのが適当である。本明細書において白金の「被覆率」は、白金を分散被覆したチタンを基体表面を例えば４０，０００倍の電子顕微鏡写真にとり、その写真よりチタン基体表面１μｍ２当りの白金の被覆面積を測定し下記式により算出される値をいう。
被覆率（％）＝（写真平面での白金被覆面積）／（写真平面でのチタン基体表面積）×１００
The degree of dispersion coating of platinum is appropriately expressed in the range of 10 to 80% in terms of coverage. In the present specification, the "coating ratio" of platinum is defined by taking an electron micrograph of a base surface of titanium dispersed and coated with platinum, for example, at a magnification of 40,000, and measuring the coating area of platinum per 1 μm 2 of the titanium base surface from the photo. The value calculated by the following formula.
Coverage (%) = (Platinum coating area on the photographic plane) / (Titanium substrate surface area on the photographic plane) x 100
このようにして、基体上に設けられた１０〜８０％の被覆率で分散被覆された白金からなる中間層を得ることができる。 In this way, an intermediate layer made of platinum dispersedly coated on the substrate with a coverage of 10 to 80% can be obtained.
＜触媒層＞
本発明の触媒層は、少なくともスズの酸化物と、ニッケル、コバルト、セリウム、及び鉄の中から選択される１種又は２種以上の活性元素と、前記活性元素と金属間化合物を形成しうる融点が４２０℃以下の安定化元素からなることを特徴としている。さらに、導電性を高めるためのドーパントを含んでいてもよい。触媒層の厚さは、特に限定されるものではないが、０．０５μｍ〜１００μｍであることが好ましく、０．１μｍ〜１０μｍであることがより好ましい。
<Catalyst layer>
The catalyst layer of the present invention may form at least an oxide of tin, one or more active elements selected from nickel, cobalt, cerium, and iron, and the active element and an intermetallic compound. It is characterized by being composed of stabilizing elements having a melting point of 420 ° C. or lower. Further, it may contain a dopant for increasing the conductivity. The thickness of the catalyst layer is not particularly limited, but is preferably 0.05 μm to 100 μm, and more preferably 0.1 μm to 10 μm.
（１）スズの酸化物
スズ酸化物は、酸化物としては比較的高い導電性を有しながら、通常の酸素発生電極より高い酸素過電圧を有する電極触媒材料であるので、水分子の陽極反応過程において、オゾン分子の吸着中間体と酸素分子の吸着中間体が競争的に電極触媒表面に形成される。しかしながら、スズ酸化物を単独で触媒層として使用するだけでは、酸素分子の吸着中間体の形成から酸素発生する反応が極めて優勢となる。したがって、スズ酸化物にオゾン分子形成を促進させる活性元素を含有させた触媒層とすることで、オゾン発生効率を十分に高めることが有効となる。
(1) Oxide of tin Tin oxide is an electrode catalyst material having a relatively high conductivity as an oxide but having a higher oxygen overvoltage than a normal oxygen generating electrode. Therefore, an anode reaction process of water molecules. In, an adsorption intermediate of ozone molecules and an adsorption intermediate of oxygen molecules are competitively formed on the surface of the electrode catalyst. However, when tin oxide is used alone as a catalyst layer, the reaction of generating oxygen from the formation of an adsorption intermediate of oxygen molecules becomes extremely predominant. Therefore, it is effective to sufficiently increase the ozone generation efficiency by forming the catalyst layer in which the tin oxide contains an active element that promotes the formation of ozone molecules.
（２）活性元素
本発明の活性元素は、スズ酸化物のオゾン生成活性を高めるための、いわば助触媒的作用を有する。メカニズムは明らかでないが、活性元素が、近接するスズ酸化物の電子密度に影響を及ぼすことでスズ酸化物に特定の反応選択性が付与されること（リガンド効果）、あるいは活性元素自身が前述したオゾン分子の吸着中間体を形成しやすい活性サイトとして作用することにより、オゾン生成活性が高められていると考えられる。オゾン生成活性を高めることに寄与する元素としては、ニッケル、コバルト、セリウム、及び鉄の中から選択される１種もしくは２種以上であることが好ましい。
(2) Active element The active element of the present invention has a so-called co-catalytic action for enhancing the ozone-producing activity of tin oxide. Although the mechanism is not clear, the active element gives a specific reaction selectivity to the tin oxide by affecting the electron density of the adjacent tin oxide (ligand effect), or the active element itself is described above. It is considered that the ozone generation activity is enhanced by acting as an active site that easily forms an adsorption intermediate of ozone molecules. The element that contributes to enhancing the ozone generation activity is preferably one or more selected from nickel, cobalt, cerium, and iron.
（３）安定化元素
本発明の安定化元素は、前述の活性元素のオゾン生成活性をさらに高める作用を有する。
活性元素は触媒層形成時に凝集することによって活性増強効果が偏在してしまいオゾン生成の活性サイトとして有効に作用しなくなる問題が生じうる。そこで、活性元素を触媒層中へ微細分散化させるとともに、酸化物や水酸化物への変化を防止する効果が期待できる安定化元素を導入することで、これらの問題が解消されて、従来よりも高い効率でオゾンを電解生成することが可能となる。活性元素と相乗作用を示す安定化元素としては、融点が４２０℃以下と比較的低く、かつ活性元素と金属間化合物を形成しうる金属種であることが好ましい。触媒層形成時に、安定化元素が活性元素に拡散して部分的にでも金属間化合物を形成することで、活性元素は触媒層形成時に凝集することによって活性増強効果が偏在することによるオゾン生成活性の低下を抑制する効果を発揮する。活性元素へ十分に拡散するには、バルク状態の融点が４２０℃以下である必要がある。融点が４２０℃超だと、触媒層形成時に活性元素相に十分に拡散しない恐れがある。具体的に、上記のような効果を発揮する安定化元素としては、ビスマス（融点：２７１℃）、亜鉛（融点：４１９℃）、及びインジウム（融点：１５７℃）から選択される１種又は２種以上が例示できるが、安定化元素は、前記効果を発揮するものであれば上記例示に限定されるものではない。
(3) Stabilizing element The stabilizing element of the present invention has an action of further enhancing the ozone generation activity of the above-mentioned active element.
When the active element aggregates during the formation of the catalyst layer, the activity enhancing effect is unevenly distributed, which may cause a problem that the active element does not effectively act as an active site for ozone generation. Therefore, by finely dispersing the active element in the catalyst layer and introducing a stabilizing element that can be expected to have the effect of preventing changes to oxides and hydroxides, these problems have been solved and compared to the past. It is possible to electrolyze ozone with high efficiency. The stabilizing element that exhibits synergistic action with the active element is preferably a metal species having a relatively low melting point of 420 ° C. or lower and capable of forming an intermetallic compound with the active element. During the formation of the catalyst layer, the stabilizing element diffuses into the active element to form an intermetallic compound even partially, and the active element aggregates during the formation of the catalyst layer, resulting in uneven distribution of the activity enhancing effect. It exerts the effect of suppressing the decrease of. The melting point in the bulk state must be 420 ° C. or lower in order to sufficiently diffuse into the active element. If the melting point exceeds 420 ° C., it may not sufficiently diffuse into the active element phase when the catalyst layer is formed. Specifically, as the stabilizing element exhibiting the above effects, one or 2 selected from bismuth (melting point: 271 ° C.), zinc (melting point: 419 ° C.), and indium (melting point: 157 ° C.). Species and above can be exemplified, but the stabilizing element is not limited to the above examples as long as it exerts the above-mentioned effect.
（４）導電性を高めるためのドーパント
本発明の触媒層は、導電性を高めるためのドーパントを含ませることによって、電極全体の電気抵抗を小さくし、電解電圧を下降させると共に、大電流を流せるようにする事によって、電力使用量の低減を図りつつ、オゾン発生効率を高まることも可能である。具体的に、導電性を高めることに寄与する元素としては、アンチモン、ストロンチウムの中から選択される１種もしくは２種以上が例示できるが、ドーパントは、スズ酸化物の導電性に関わるキャリヤ濃度や移動度を高めるためのものであれば上記例示に限定されるものではない。
(4) Dopant for enhancing conductivity By including a dopant for enhancing conductivity, the catalyst layer of the present invention can reduce the electrical resistance of the entire electrode, lower the electrolytic voltage, and allow a large current to flow. By doing so, it is possible to increase the efficiency of ozone generation while reducing the amount of electricity used. Specifically, as an element that contributes to increasing the conductivity, one or more selected from antimony and strontium can be exemplified, but the dopant is the carrier concentration related to the conductivity of the tin oxide and the carrier concentration. It is not limited to the above example as long as it is for increasing mobility.
（５）触媒層の組成
本発明の触媒層は、上記の通り、少なくともスズの酸化物と、ニッケル、コバルト、セリウム、及び鉄の中から選択される１種又は２種以上の活性元素と、前記活性元素と金属間化合物を形成しうる融点が４２０℃以下の安定化元素からなる。さらに、導電性を高めるためのドーパントを含んでいてもよい。
(5) Composition of catalyst layer As described above, the catalyst layer of the present invention contains at least an oxide of tin and one or more active elements selected from nickel, cobalt, cerium, and iron. It is composed of a stabilizing element having a melting point of 420 ° C. or lower, which can form a compound between the active element and the metal. Further, it may contain a dopant for increasing the conductivity.
触媒層において、スズの酸化物の含有量は、５０〜９９ｍｏｌ％が好ましく、８０〜９７．５ｍｏｌ％がより好ましい。スズの酸化物の割合が５０ｍｏｌ％未満であると、水分子の陽極反応過程において、吸着中間体をオゾン分子へと形成させるための電極表面積が十分でなくなり、オゾン発生効率が著しく低下する恐れがある。一方、９９ｍｏｌ％を超えると、活性元素と安定化元素の相乗作用によるオゾン生成活性の増強効果が十分に発揮されなくなる。
活性元素の含有量は、０．１〜２０ｍｏｌ％が好ましく、０．５〜５ｍｏｌ％がより好ましい。活性元素の割合が０．１ｍｏｌ％未満であると、オゾン生成活性を十分に高めることができなくなり、オゾン発生効率が著しく低下する。一方、２０ｍｏｌ％を超えると、活性元素の凝集が進みすぎて微細分散化と化合状態の安定化が困難となり、場合によっては水溶液中に活性元素が溶出していく恐れが生じる。
安定化元素の含有量は、０．２〜２０ｍｏｌ％が好ましく、０．５〜５ｍｏｌ％がより好ましい。安定化元素の割合が０．２ｍｏｌ％未満であると、活性元素に対して十分に拡散しきらずに、活性元素の微細分散化と化合状態の安定化が困難になる。一方、２０ｍｏｌ％を超えると、未反応の安定化元素の増加によって実効的な電極表面積を低下させたり、場合によっては水溶液中に安定化元素が溶出したりする恐れが生じる。
ドーパントの含有量は、０．５〜２０ｍｏｌ％が好ましく、１〜１０ｍｏｌ％がより好ましい。ドーパントの割合が０．５ｍｏｌ％未満、あるいは２０ｍｏｌ％を超えると、導電性に関わるキャリヤ濃度や移動度の調整に適した濃度範囲を逸脱してしまって、電極全体の電気抵抗を下げる効果が十分に発揮されなくなる。
ただし、これら含有モル比率は、スズの酸化物、活性元素、安定化元素、及びドーパントの総量に対する比率とする。
In the catalyst layer, the tin oxide content is preferably 50 to 99 mol%, more preferably 80 to 97.5 mol%. If the proportion of tin oxide is less than 50 mol%, the surface area of the electrode for forming the adsorption intermediate into ozone molecules becomes insufficient in the anodic reaction process of water molecules, and the ozone generation efficiency may be significantly reduced. is there. On the other hand, if it exceeds 99 mol%, the effect of enhancing the ozone generation activity due to the synergistic action of the active element and the stabilizing element is not sufficiently exhibited.
The content of the active element is preferably 0.1 to 20 mol%, more preferably 0.5 to 5 mol%. If the ratio of the active element is less than 0.1 mol%, the ozone generation activity cannot be sufficiently increased, and the ozone generation efficiency is significantly lowered. On the other hand, if it exceeds 20 mol%, the agglutination of the active element progresses too much, making it difficult to finely disperse and stabilize the compounded state, and in some cases, the active element may elute into the aqueous solution.
The content of the stabilizing element is preferably 0.2 to 20 mol%, more preferably 0.5 to 5 mol%. If the ratio of the stabilizing element is less than 0.2 mol%, the active element is not sufficiently diffused to the active element, and it becomes difficult to finely disperse the active element and stabilize the compounded state. On the other hand, if it exceeds 20 mol%, the effective electrode surface area may be lowered due to the increase of unreacted stabilizing elements, and in some cases, the stabilizing elements may be eluted in the aqueous solution.
The content of the dopant is preferably 0.5 to 20 mol%, more preferably 1 to 10 mol%. If the proportion of the dopant is less than 0.5 mol% or more than 20 mol%, it deviates from the concentration range suitable for adjusting the carrier concentration and mobility related to conductivity, and the effect of lowering the electrical resistance of the entire electrode is sufficient. Will not be exhibited.
However, these molar ratios are the ratios to the total amount of tin oxides, active elements, stabilizing elements, and dopants.
（６）触媒層の製造方法
本発明のオゾン生成用電極の製造方法において、触媒層を形成する方法としては、気相中におけるスパッタ法、イオンプレーティング法等の方法のほか、液相中におけるめっき法によってもよく、塗布液を用いて成膜後、熱分解法によっても良い。特に、熱分解法と電気めっき法が好ましい。
(6) Method for producing catalyst layer In the method for producing an ozone-generating electrode of the present invention, the method for forming the catalyst layer includes a sputtering method in a gas phase, an ion plating method, and the like, as well as a method in a liquid phase. It may be a plating method, or it may be a thermal decomposition method after forming a film using a coating liquid. In particular, the pyrolysis method and the electroplating method are preferable.
熱分解法によって触媒層を形成する工程としては、スズの化合物、活性元素としてニッケル、コバルト、セリウム、及び鉄の中から選択される１種又は２種以上の化合物、安定化元素としてビスマス、亜鉛、及びインジウムの中から選択される少なくとも１種を含む化合物をアルコール溶媒に溶解させて塗布液を作製し、前記中間層表面に該塗布液を塗布、乾燥、熱分解し、スズの酸化物、活性元素、及び安定化元素を含有する触媒層を形成する工程を有する方法が挙げられる。また、塗布液には、触媒層の導電性を高めるための添加剤を加えてもよく、例えば、アンチモン、ストロンチウム、等を含有する化合物が挙げられる。 In the step of forming the catalyst layer by the thermal decomposition method, one or more compounds selected from tin compounds, nickel, cobalt, cerium as active elements, and iron, and bismuth and zinc as stabilizing elements. , And a compound containing at least one selected from indium are dissolved in an alcohol solvent to prepare a coating liquid, and the coating liquid is applied to the surface of the intermediate layer, dried, and thermally decomposed to obtain tin oxide. Examples thereof include a method having a step of forming a catalyst layer containing an active element and a stabilizing element. Further, an additive for increasing the conductivity of the catalyst layer may be added to the coating liquid, and examples thereof include compounds containing antimony, strontium, and the like.
該化合物の形態として、塩化物、酸化物、フッ化物、臭化物、金属アルコキシド、有機金属化合物、酢酸塩、炭酸塩、硝酸塩、炭酸水素塩、リン酸塩、及び硫酸塩等が挙げられるが、塗布液の保存安定性、環境負荷およびコストの観点から、好ましくは塩化物が挙げられる。 Examples of the form of the compound include chlorides, oxides, fluorides, bromides, metal alkoxides, organic metal compounds, acetates, carbonates, nitrates, bicarbonates, phosphates, sulfates and the like. Chloride is preferably used from the viewpoint of storage stability of the liquid, environmental load and cost.
塗布工程は、スプレー塗布法、噴霧法、刷毛塗り法、カーテンフローコート法、ドクターブレード法、ディップ法により塗布し、塗布膜を得ることができる。乾燥工程は、常温における風乾でもよいが、５０〜１５０℃ の加熱下で１０分程度行うのが好ましく挙げられる。熱分解工程は、２００〜６５０℃の温度で、５分から３００分の焼成時間で行うのが好ましいが、４００〜６５０℃ の温度で、１０〜６０分で行うのが好ましく挙げられる。この塗布・乾燥・焼成を複数回繰り返して、触媒層を積層させてもよい。 The coating step can be applied by a spray coating method, a spray method, a brush coating method, a curtain flow coating method, a doctor blade method, or a dip method to obtain a coating film. The drying step may be air-dried at room temperature, but is preferably carried out for about 10 minutes under heating at 50 to 150 ° C. The pyrolysis step is preferably carried out at a temperature of 200 to 650 ° C. and a firing time of 5 to 300 minutes, but preferably at a temperature of 400 to 650 ° C. for 10 to 60 minutes. The catalyst layer may be laminated by repeating this coating, drying, and firing a plurality of times.
電気めっき法によって触媒層を形成する工程としては、スズの化合物、活性元素としてニッケル、コバルト、セリウム、及び鉄の中から選択される１種又は２種以上の化合物、安定化元素としてビスマス、亜鉛、及びインジウムの中から選択される少なくとも１種を含む化合物を溶解させためっき浴を作製し、めっき浴中に設けられた対極と金属基体との間に電位を加えることにより、前記中間層表面にスズの酸化物、活性元素、及び安定化元素を含有する触媒層を電気めっきによって形成する工程を有する方法が挙げられる。また、めっき浴には、触媒層の導電性を高めるための添加剤を加えてもよく、例えば、アンチモン、ストロンチウム等を含有する化合物が挙げられる。 In the step of forming the catalyst layer by the electroplating method, one or more compounds selected from tin compounds, nickel, cobalt, cerium as active elements, and iron as active elements, and bismuth and zinc as stabilizing elements. , And a plating bath in which a compound containing at least one selected from indium is dissolved is prepared, and a potential is applied between the counter electrode provided in the plating bath and the metal substrate to apply a potential to the surface of the intermediate layer. Examples thereof include a method having a step of forming a catalyst layer containing a tin oxide, an active element, and a stabilizing element by electroplating. Further, an additive for increasing the conductivity of the catalyst layer may be added to the plating bath, and examples thereof include compounds containing antimony, strontium and the like.
該化合物の形態として、塩化物、酢酸塩、炭酸塩、硝酸塩、炭酸水素塩、リン酸塩、及び硫酸塩等が挙げられるが、金属酸化物のめっき効率の観点から、好ましくは硝酸塩が挙げられる。 Examples of the form of the compound include chlorides, acetates, carbonates, nitrates, bicarbonates, phosphates, sulfates and the like, but from the viewpoint of plating efficiency of metal oxides, nitrates are preferable. ..
電気めっき工程中の電流密度は、０．００１〜１Ａ／ｃｍ２が好ましく、０．０１〜０．１Ａ／ｃｍ２程度がより好ましく、直流のほかパルス電流とすることもできる。めっき浴の温度は、１０〜７０℃が好ましく、３０〜６０℃がより好ましい。高温になるほどめっき速度は速くなり、低温になるほどめっき膜が平滑化する傾向がある。めっき時間は、１〜１８０分程度が好ましく、１０〜１２０分程度がより好ましい。使用される対極材料としては、白金、カーボン、酸化イリジウム等の棒状・板状・網状の電極が例示できるが、これらの中でも特に白金が好ましく挙げられる。 The current density during the electroplating step is preferably 0.001 to 1 A / cm 2 , more preferably 0.01 to 0.1 A / cm 2 , and can be a pulse current in addition to direct current. The temperature of the plating bath is preferably 10 to 70 ° C, more preferably 30 to 60 ° C. The higher the temperature, the faster the plating speed, and the lower the temperature, the smoother the plating film tends to be. The plating time is preferably about 1 to 180 minutes, more preferably about 10 to 120 minutes. Examples of the counter electrode material used include rod-shaped, plate-shaped, and net-shaped electrodes such as platinum, carbon, and iridium oxide, and among these, platinum is particularly preferable.
〔２〕オゾン生成用電極の用途
本発明のオゾン生成用電極の用途としては、水電解により生成したオゾンの強力な酸化作用を利用する用途が主に挙げられる。金属電極基体と、該金属基体表面上の中間層と、該中間層上にスズの酸化物と、活性元素と、安定化元素からなる触媒層を有する電極を用いることで、スズの酸化物に活性元素のみを付与した触媒層を有する電極を用いる場合よりも、オゾン発生効率を大きく向上して、高濃度のオゾンを含有したオゾン水を簡便に製造することが可能となる。製造したオゾン水は、強力な酸化作用によって殺菌、消臭、廃棄汚水の浄化、半導体材料の洗浄等に利用することができる。さらに、発生したオゾンは短時間で無害化するので、薬剤を投入する方法と比較して低環境負荷の処理とすることができる。
[2] Uses of Ozone Generation Electrode The use of the ozone generation electrode of the present invention mainly includes the use of the strong oxidizing action of ozone generated by water electrolysis. By using a metal electrode substrate, an intermediate layer on the surface of the metal substrate, and an electrode having a catalyst layer composed of a tin oxide, an active element, and a stabilizing element on the intermediate layer, a tin oxide can be obtained. Compared with the case of using an electrode having a catalyst layer to which only an active element is applied, the ozone generation efficiency is greatly improved, and ozone water containing a high concentration of ozone can be easily produced. The produced ozone water can be used for sterilization, deodorization, purification of wastewater, cleaning of semiconductor materials, etc. due to its strong oxidizing action. Furthermore, since the generated ozone is detoxified in a short time, it can be treated with a low environmental load as compared with the method of adding a chemical.
本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
［実施例１］
金属基体としてチタン板、中間層として白金、触媒層としてスズ酸化物、活性元素であるニッケル、安定化元素であるインジウム、ドーパントとしてアンチモンからなる電極を製造した。
（１）金属基体の調製
チタンを基体として、ＪＩＳ１種チタン板素材（ｔ0.5ｍｍ×100ｍｍ×100ｍｍ）をアセトンに浸漬させ10分間超音波洗浄して脱脂した後、２０℃の８重量％弗化水素酸水溶液中で２分間処理し、次いで、１２０℃の６０重量％硫酸水溶液中で３分間処理した。次いでチタン基体を硫酸水溶液から取りだし、窒素雰囲気中で冷水を噴霧し急冷した。更に２０℃の０．３重量％弗化水素酸水溶液中に２分間浸漬した後水洗した。
[Example 1]
An electrode composed of a titanium plate as a metal substrate, platinum as an intermediate layer, tin oxide as a catalyst layer, nickel as an active element, indium as a stabilizing element, and antimony as a dopant was produced.
(1) Preparation of metal substrate Using titanium as a substrate, JIS class 1 titanium plate material (t0.5 mm × 100 mm × 100 mm) is immersed in acetone, ultrasonically cleaned for 10 minutes to degreas, and then fluorinated at 8% by weight at 20 ° C. The treatment was carried out in an aqueous hydrogen hydride solution for 2 minutes and then in a 60 wt% aqueous sulfuric acid solution at 120 ° C. for 3 minutes. Next, the titanium substrate was taken out from the sulfuric acid aqueous solution, and cold water was sprayed in a nitrogen atmosphere to quench it. Further, it was immersed in a 0.3 wt% hydrofluoric acid aqueous solution at 20 ° C. for 2 minutes and then washed with water.
（２）中間層の調製
前記チタン基体上に、ジニトロジアンミン白金を硫酸溶液に溶解して白金含有量５ｇ／Ｌ、ｐＨ≒２、５０℃に調整した状態の白金めっき浴中で、３０ｍＡ／ｃｍ２で約６分間のめっきを行って、電着量が１．７ｍｇ／ｃｍ２の多孔性白金被覆層（厚み０．５μｍ程度）をチタン基体上に形成した。
(2) Preparation of intermediate layer 30 mA / cm in a platinum plating bath in which dinitrodiammine platinum was dissolved in a sulfuric acid solution on the titanium substrate and the platinum content was adjusted to 5 g / L and pH ≈2.5 ° C. Plating was carried out in step 2 for about 6 minutes to form a porous platinum coating layer (thickness of about 0.5 μm) having an electrodeposition amount of 1.7 mg / cm 2 on a titanium substrate.
（３）触媒層の調製
触媒層形成用塗布液として、エタノールに塩化スズ（ＩＶ）五水和物２８８ｇ／Ｌ、塩化ニッケル（ＩＩ）六水和物２．１ｇ／Ｌ、塩化インジウム（ＩＩＩ）四水和物４．９ｇ／Ｌ、塩化アンチモン（ＩＩＩ）１２．３ｇ／Ｌを溶解した溶液を作製した。
前記白金被覆層を形成したチタン基体上に、前記触媒層形成用塗布液を刷毛にて塗布後、６０℃１０分乾燥し、さらに５５０℃の大気中で１０分間焼成した。この塗布・乾燥・焼成を１０回繰り返すことで、実施例１の電極を作製した。
(3) Preparation of catalyst layer As a coating solution for forming a catalyst layer, ethanol contains 288 g / L of tin (IV) chloride pentahydrate, 2.1 g / L of nickel (II) chloride hexahydrate, and indium (III) chloride. A solution was prepared in which 4.9 g / L of tetrahydrate and 12.3 g / L of antimony chloride (III) were dissolved.
The coating liquid for forming the catalyst layer was applied with a brush on the titanium substrate on which the platinum coating layer was formed, dried at 60 ° C. for 10 minutes, and further fired in the air at 550 ° C. for 10 minutes. The electrode of Example 1 was produced by repeating this coating, drying, and firing 10 times.
［実施例２］
金属基体としてチタン板、中間層として白金、触媒層としてスズ酸化物、活性元素である鉄、安定化元素である亜鉛、ドーパントとしてアンチモンからなる電極を製造した。
（１）金属基体の調製
実施例１と同様にして、チタン基体を得た。
[Example 2]
An electrode made of a titanium plate as a metal substrate, platinum as an intermediate layer, tin oxide as a catalyst layer, iron as an active element, zinc as a stabilizing element, and antimony as a dopant was produced.
(1) Preparation of Metal Substrate A titanium substrate was obtained in the same manner as in Example 1.
（２）中間層の調製
実施例１と同様にして、チタン基体上に白金被覆層を形成した。
(2) Preparation of Intermediate Layer A platinum coating layer was formed on the titanium substrate in the same manner as in Example 1.
（３）触媒層の調製
塩化ニッケル（ＩＩ）六水和物の代わりに塩化鉄(III)六水和物２．４ｇ／Ｌ、塩化インジウム（ＩＩＩ）四水和物の代わりに塩化亜鉛（ＩＩ）１．２ｇ／Ｌとして、塩化アンチモン（ＩＩＩ）を２．５ｇ／Ｌ添加した以外は実施例１と同様にして、実施例２の電極を作製した。
(3) Preparation of catalyst layer Iron (III) chloride hexahydrate 2.4 g / L instead of nickel (II) chloride hexahydrate, zinc chloride (II) instead of indium (III) chloride tetrahydrate ) 1.2 g / L, 2.5 g / L of antimony chloride (III) was added, and the electrode of Example 2 was prepared in the same manner as in Example 1.
［実施例３］
金属基体としてチタン板、中間層として白金、触媒層としてスズ酸化物、活性元素であるセリウム、安定化元素であるビスマス、ドーパントとしてアンチモンからなる電極を製造した。
（１）金属基体の調製
実施例１と同様にして、チタン基体を得た。
[Example 3]
An electrode composed of a titanium plate as a metal substrate, platinum as an intermediate layer, tin oxide as a catalyst layer, cerium as an active element, bismuth as a stabilizing element, and antimony as a dopant was produced.
(1) Preparation of Metal Substrate A titanium substrate was obtained in the same manner as in Example 1.
（２）中間層の調製
実施例１と同様にして、チタン基体上に白金被覆層を形成した。
(2) Preparation of Intermediate Layer A platinum coating layer was formed on the titanium substrate in the same manner as in Example 1.
（３）触媒層の調製
塩化ニッケル（ＩＩ）六水和物の代わりに塩化セリウム(III)七水和物３．３ｇ／Ｌ、塩化インジウム（ＩＩＩ）四水和物の代わりに塩化ビスマス（ＩＩＩ）２．８ｇ／Ｌとした以外は実施例１と同様にして、実施例３の電極を作製した。
(3) Preparation of catalyst layer 3.3 g / L of cerium (III) chloride heptahydrate instead of nickel (II) chloride hexahydrate, bismuth chloride (III) instead of indium (III) chloride tetrahydrate ) The electrode of Example 3 was produced in the same manner as in Example 1 except that the value was 2.8 g / L.
［実施例４］
金属基体としてチタン板、中間層として白金、触媒層としてスズ酸化物、活性元素であるコバルト、安定化元素である亜鉛、ドーパントとしてアンチモンからなる電極を製造した。
（１）金属基体の調製
実施例１と同様にして、チタン基体を得た。
[Example 4]
An electrode composed of a titanium plate as a metal substrate, platinum as an intermediate layer, tin oxide as a catalyst layer, cobalt as an active element, zinc as a stabilizing element, and antimony as a dopant was produced.
(1) Preparation of Metal Substrate A titanium substrate was obtained in the same manner as in Example 1.
（２）中間層の調製
実施例１と同様にして、チタン基体上に白金被覆層を形成した。
(2) Preparation of Intermediate Layer A platinum coating layer was formed on the titanium substrate in the same manner as in Example 1.
（３）触媒層の調製
塩化ニッケル（ＩＩ）六水和物の代わりに塩化コバルト(II)六水和物２．１ｇ／Ｌ、塩化インジウム（ＩＩＩ）四水和物の代わりに塩化亜鉛（ＩＩ）１.２ｇ／Ｌとして、塩化アンチモン（ＩＩＩ）を２．５ｇ／Ｌ添加した以外は実施例１と同様にして、実施例４の電極を作製した。
(3) Preparation of catalyst layer Cobalt (II) chloride hexahydrate 2.1 g / L instead of nickel (II) chloride hexahydrate, zinc chloride (II) instead of indium (III) chloride tetrahydrate ) The electrode of Example 4 was prepared in the same manner as in Example 1 except that 2.5 g / L of antimony chloride (III) was added at 1.2 g / L.
［比較例１］
塩化ニッケル（ＩＩ）六水和物、塩化インジウム（ＩＩＩ）四水和物、塩化アンチモン（ＩＩＩ）を使用しない以外は実施例１と同様にして電極を製造した。
[Comparative Example 1]
Electrodes were produced in the same manner as in Example 1 except that nickel (II) chloride hexahydrate, indium (III) chloride tetrahydrate, and antimony chloride (III) were not used.
［比較例２］
塩化ニッケル（ＩＩ）六水和物、塩化インジウム（ＩＩＩ）四水和物を使用しない以外は実施例１と同様にして電極を製造した。
[Comparative Example 2]
Electrodes were produced in the same manner as in Example 1 except that nickel (II) chloride hexahydrate and indium (III) chloride tetrahydrate were not used.
［比較例３］
塩化インジウム（ＩＩＩ）四水和物を使用しない以外は実施例１と同様にして電極を製造した。
[Comparative Example 3]
Electrodes were produced in the same manner as in Example 1 except that indium (III) chloride tetrahydrate was not used.
［電極分析と電極性能評価の方法］
＜電極分析方法＞
成分分析は、主に蛍光Ｘ線分析装置を用いて元素含有量の評価を行った。必要に応じて、電極の触媒層を削り取った試験片の誘導結合プラズマ発光分光分析（ＩＣＰ分析）も行って、定量分析した。補足評価として、エネルギー分散型Ｘ線分光装置（ＥＤＸ）、Ｘ線光電子分光分析装置（ＸＰＳ）、及びＸ線源としてＣｕＫαを用いたＸ線回折分析装置（ＸＲＤ）による評価を行い、元素の分布と化合状態を評価した。また、電極構造の観察は、走査型電子顕微鏡（ＳＥＭ）により行った。
[Method of electrode analysis and electrode performance evaluation]
<Electrode analysis method>
In the component analysis, the element content was evaluated mainly using a fluorescent X-ray analyzer. If necessary, inductively coupled plasma emission spectroscopic analysis (ICP analysis) of the test piece from which the catalyst layer of the electrode was scraped was also performed for quantitative analysis. As a supplementary evaluation, an energy dispersive X-ray spectroscope (EDX), an X-ray photoelectron spectroscope (XPS), and an X-ray diffraction analyzer (XRD) using CuKα as an X-ray source are used for evaluation, and the distribution of elements is performed. And the compounding state was evaluated. The electrode structure was observed with a scanning electron microscope (SEM).
＜電極性能評価方法＞
作製した電極（電解面積８ｃｍ２）を陽極として電解装置（セル）に設置した。電解装置は、処理槽と、陽極（アノード）と、陰極（カソード）、これら電極に直流電流を印加する電源とから構成される。そして、これら電極間に位置して、処理槽内の陽極の存する一方の領域と陰極の存する他方の領域とに区画する陽イオン交換膜（隔膜：デュポン社製Ｎａｆｉｏｎ（商品名））が設けられる。また、この処理槽内には、電解液（電解質溶液）として０．５Ｍ Ｈ２ＳＯ４が貯溜される。陽極領域の電解液量は１５０ｍｌ、陰極領域の電解液量は１５０ｍｌとした。そして、電源により１６００ｍＡ、電流密度約２００ｍＡ／ｃｍ２の定電流にて１３．５秒電解した。また、溶液の温度は常温とした。得られた陽極水のオゾン量をヨウ素法により求め、オゾン発生効率を求めた。
<Electrode performance evaluation method>
The prepared electrode (electrolysis area 8 cm 2 ) was used as an anode and installed in an electrolysis device (cell). The electrolyzer is composed of a processing tank, an anode (anode), a cathode (cathode), and a power source for applying a direct current to these electrodes. Then, a cation exchange membrane (septum: Nafion (trade name) manufactured by DuPont) is provided between these electrodes to partition one region where the anode exists and the other region where the cathode exists in the treatment tank. .. Further, 0.5 MH 2 SO 4 is stored as an electrolytic solution (electrolyte solution) in this treatment tank. The amount of electrolyte in the anode region was 150 ml, and the amount of electrolyte in the cathode region was 150 ml. Then, electrolysis was performed for 13.5 seconds at a constant current of 1600 mA and a current density of about 200 mA / cm 2 by a power source. The temperature of the solution was normal temperature. The amount of ozone in the obtained anode water was determined by the iodine method, and the ozone generation efficiency was determined.
実施例４〜７、及び比較例１〜３で作製した電極の諸元および電極性能を評価した結果を表１に示す。 Table 1 shows the results of evaluating the specifications and electrode performance of the electrodes produced in Examples 4 to 7 and Comparative Examples 1 to 3.
［評価結果に対する考察］
表１に示されるように、実施例１〜４では、オゾン発生効率が全て１１．５％以上であり、オゾン発生用として良好な電極であると評価できる。一方、比較例１〜３では、安定化元素が添加されていないため、活性元素の微細分散化と化合状態安定化の作用が十分に発揮されず、良好なオゾン発生効率を示さなかった。
このように、本発明の電極を用いることで、オゾン発生効率を大きく向上させることが可能であることが確認された。
[Discussion on evaluation results]
As shown in Table 1, in Examples 1 to 4, the ozone generation efficiency is all 11.5% or more, and it can be evaluated that the electrode is good for ozone generation. On the other hand, in Comparative Examples 1 to 3, since the stabilizing element was not added, the effects of fine dispersion of the active element and stabilization of the compounded state were not sufficiently exhibited, and good ozone generation efficiency was not exhibited.
As described above, it was confirmed that the ozone generation efficiency can be greatly improved by using the electrode of the present invention.
Claims (4)
前記電極基体表面上の中間層と、
前記中間層上の触媒層からなるオゾン生成用電極であって、
前記触媒層は、スズの酸化物と、ニッケル、コバルト、セリウム、及び鉄の中から選択される１種又は２種以上の活性元素と、前記活性元素と金属間化合物を形成しうる融点が４２０℃以下の安定化元素を含む、
ことを特徴とするオゾン生成用電極。 An electrode substrate made of metal and
The intermediate layer on the surface of the electrode substrate and
An ozone generation electrode composed of a catalyst layer on the intermediate layer.
The catalyst layer has a melting point of 420, which can form an oxide of tin, one or more active elements selected from nickel, cobalt, cerium, and iron, and an intermetallic compound with the active element. Contains stabilizing elements below ° C,
An electrode for ozone generation, which is characterized in that.
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| WO2024004776A1 (en) * | 2022-06-27 | 2024-01-04 | 石福金属興業株式会社 | Electrode for ozone generation |
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