JP2000051692A - Photocatalyst support and production thereof - Google Patents
Photocatalyst support and production thereofInfo
- Publication number
- JP2000051692A JP2000051692A JP10221228A JP22122898A JP2000051692A JP 2000051692 A JP2000051692 A JP 2000051692A JP 10221228 A JP10221228 A JP 10221228A JP 22122898 A JP22122898 A JP 22122898A JP 2000051692 A JP2000051692 A JP 2000051692A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- titanium oxide
- metal substrate
- base material
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 17
- 239000002585 base Substances 0.000 claims abstract description 13
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000005530 etching Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 230000001464 adherent effect Effects 0.000 claims 4
- 239000000834 fixative Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 239000002390 adhesive tape Substances 0.000 description 22
- 229920000298 Cellophane Polymers 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、廃水や空気の浄
化、有機物の分解などに有効な酸化チタン系光触媒を金
属基材の表面に担持させた光触媒担持物およびその製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst carrier having a titanium oxide photocatalyst, which is effective for purifying wastewater and air, decomposing organic substances, and the like, supported on the surface of a metal substrate, and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化チタンが特定波長の光により光触媒
活性を発現し、その強力な酸化作用によって、廃水や空
気の浄化、有機物の分解などに有効であることは知られ
ている。2. Description of the Related Art It is known that titanium oxide exhibits photocatalytic activity by light of a specific wavelength, and is effective for purifying wastewater and air, decomposing organic substances, and the like due to its strong oxidizing action.
【０００３】そして、その酸化チタン系光触媒の基材表
面への担持方法としては、有機チタン塗布法、ゾル塗布
法、ＣＶＤ法（化学気相法）などが知られている。[0003] As a method for supporting the titanium oxide-based photocatalyst on the substrate surface, there are known an organic titanium coating method, a sol coating method, a CVD method (chemical vapor method) and the like.
【０００４】有機チタン塗布法は、溶媒に溶解した有機
チタン化合物を基材の表面に塗布した後、加熱し、有機
成分を蒸発、分解させて酸化チタン系光触媒層を基材の
表面に形成することにより、基材の表面に酸化チタン系
光触媒を担持させる方法であるが、基材の表面に対する
酸化チタン系光触媒層の固着強度が弱いため、酸化チタ
ン系光触媒層が基材の表面から剥離しやすいという問題
があった。In the organic titanium coating method, an organic titanium compound dissolved in a solvent is applied to the surface of a substrate and then heated to evaporate and decompose organic components to form a titanium oxide-based photocatalyst layer on the surface of the substrate. By this method, a titanium oxide-based photocatalyst is supported on the surface of the base material. There was a problem that it was easy.
【０００５】ゾル塗布法は、酸化チタンゾルを基材の表
面に塗布し、酸化チタンゾル層を形成した後、熱処理し
て上記酸化チタンゾルを酸化チタンに変化させることに
より、酸化チタン系光触媒層を基材の表面に形成する方
法であるが、酸化チタン系光触媒層自体の強度が弱く、
基材の表面から脱落しやすいという問題があった。In the sol coating method, a titanium oxide sol is applied to the surface of a substrate, a titanium oxide sol layer is formed, and then heat treatment is performed to convert the titanium oxide sol into titanium oxide. Is formed on the surface of the titanium oxide photocatalyst layer itself is weak,
There is a problem that the material easily falls off from the surface of the base material.
【０００６】また、ＣＶＤ法は、高真空中で酸化チタン
を高温に加熱して、基材の表面に酸化チタンを蒸着させ
ることにより、酸化チタン系光触媒層を基材の表面に形
成する方法であるが、広範囲に酸化チタン系光触媒層を
形成するには、大規模でかつ高度な真空装置が必要であ
るという問題があった。The CVD method is a method in which titanium oxide is heated to a high temperature in a high vacuum to deposit titanium oxide on the surface of the substrate, thereby forming a titanium oxide-based photocatalyst layer on the surface of the substrate. However, there is a problem that a large-scale and sophisticated vacuum device is required to form a titanium oxide-based photocatalyst layer over a wide range.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記のよう
な基材表面への酸化チタン系光触媒の担持方法に関する
従来技術の問題点を解決し、金属基材の表面に強固に固
着する酸化チタン系光触媒を担持させた光触媒担持物お
よびその製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention solves the problems of the prior art relating to the above-mentioned method of supporting a titanium oxide-based photocatalyst on the surface of a substrate, and solves the problem of oxidation which is firmly fixed to the surface of a metal substrate. It is an object of the present invention to provide a photocatalyst-supported material supporting a titanium-based photocatalyst and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意研究を重ねた結果、金属基材の表面
を酸またはアルカリでエッチング処理した後、上記金属
基材を硫酸チタニル水溶液または硫酸チタン水溶液中に
浸漬しながら上記硫酸チタニルまたは硫酸チタンを加水
分解させて金属基材の表面に高固着性の酸化チタン系光
触媒層を形成することにより、金属基材の表面に強固に
固着する酸化チタン系光触媒を担持させた光触媒担持物
が得られることを見出し、本発明を完成するにいたっ
た。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, after etching the surface of the metal base with an acid or an alkali, the metal base was treated with titanyl sulfate. The titanium oxide or titanium sulfate is hydrolyzed while being immersed in an aqueous solution or an aqueous solution of titanium sulfate to form a titanium oxide-based photocatalytic layer having high fixation on the surface of the metal substrate, so that the surface of the metal substrate is firmly adhered to. The present inventors have found that a photocatalyst-carrying material carrying a fixed titanium oxide-based photocatalyst can be obtained, and have completed the present invention.
【０００９】[0009]
【発明の実施の形態】本発明において、基材とする金属
の種類は、酸またはアルカリによるエッチング処理が可
能なものであれば特に限定されることなく、いずれも使
用することができるが、実用上、アルミニウム、鉄、ス
テンレス鋼、亜鉛などが適していて、特にアルミニウム
が適している。また、金属基材の表面のエッチング処理
にあたってエッチング液としては、金属基材がアルミニ
ウムの場合、アルカリ性エッチング液としては金属水酸
化物、特に水酸化ナトリウムの水溶液が好ましく、また
酸性エッチング液としては、強酸、特にリン酸水溶液が
好ましい。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the kind of metal used as a base material is not particularly limited as long as it can be etched with an acid or an alkali. Above, aluminum, iron, stainless steel, zinc and the like are suitable, and aluminum is particularly suitable. Further, in etching the surface of the metal substrate, as an etchant, when the metal substrate is aluminum, an alkaline etchant is preferably a metal hydroxide, particularly an aqueous solution of sodium hydroxide, and as an acidic etchant, A strong acid, especially an aqueous phosphoric acid solution is preferred.
【００１０】上記のようなエッチング液によりエッチン
グ処理された金属基材の表面に酸化チタン系光触媒を担
持させるには、上記金属基材を硫酸チタニル水溶液また
は硫酸チタン水溶液中に浸漬しながら上記硫酸チタニル
または硫酸チタンを加熱による加水分解、水希釈による
加水分解または中和処理による加水分解（アルカリ性物
質の添加による中和処理により加水分解する）などによ
って酸化チタン系のコロイド状物質を生成させ、その酸
化チタン系微粒子を金属基材の表面に沈積させればよ
い。In order to carry a titanium oxide-based photocatalyst on the surface of a metal substrate etched with the above-mentioned etching solution, the metal substrate is immersed in an aqueous solution of titanyl sulfate or an aqueous solution of titanium sulfate. Alternatively, a titanium oxide-based colloidal substance is generated by hydrolysis of titanium sulfate by heating, hydrolysis by dilution with water or hydrolysis by neutralization treatment (hydrolysis by neutralization treatment by adding an alkaline substance), and the oxidation thereof. Titanium-based fine particles may be deposited on the surface of the metal substrate.
【００１１】上記のように表面がエッチング処理された
金属基材を硫酸チタニル水溶液または硫酸チタン水溶液
中に浸漬した状態で、硫酸チタニルまたは硫酸チタンを
加水分解するには、硫酸チタニルまたは硫酸チタンの濃
度がＴｉＯ2 換算で０．５〜２５重量％の硫酸チタニル
水溶液または硫酸チタン水溶液が好ましく、特に加熱に
よる加水分解の場合には１．５〜１５重量％の水溶液と
し、それを６０〜１００℃でゆっくりと加熱して最高温
度で数分〜数時間程度保持するのが好ましい。また、中
和処理による加水分解によって酸化チタン系コロイド状
物質を生成させるには、濃度が０．５〜５０重量％の水
酸化ナトリウム水溶液を添加するのが好ましい。In order to hydrolyze titanyl sulfate or titanium sulfate in a state in which the metal substrate whose surface has been etched as described above is immersed in an aqueous solution of titanyl sulfate or titanium sulfate, the concentration of titanyl sulfate or titanium sulfate is determined. in There 0.5-25 wt% aqueous solution of titanyl or titanium sulfate aqueous sulfuric acid are preferable in terms of TiO 2, an aqueous solution of 1.5 to 15 wt% in the case of hydrolysis with particular heating, 60 to 100 [° C. it It is preferable to heat slowly and hold at the maximum temperature for several minutes to several hours. In addition, in order to generate a titanium oxide-based colloidal substance by hydrolysis by a neutralization treatment, it is preferable to add an aqueous solution of sodium hydroxide having a concentration of 0.5 to 50% by weight.
【００１２】上記の加水分解によって生成する酸化チタ
ン系コロイド状物質は、主としてメタチタン酸、オルト
チタン酸などであるが、加熱脱水処理によって含水酸化
チタンを経て酸化チタンまでの任意の段階に調製するこ
とが可能である。The titanium oxide-based colloidal substance produced by the above-mentioned hydrolysis is mainly metatitanic acid, orthotitanic acid and the like. Is possible.
【００１３】本発明においては、金属基材の表面に高固
着性の酸化チタン系光触媒を担持させることを要件とし
ているが、この高固着性とは金属基材の表面に対して酸
化チタン系光触媒が７０％以上の固着性で固着している
ことを意味しており、特に８０％以上が好ましい。In the present invention, it is required that a titanium oxide-based photocatalyst having high adhesion is supported on the surface of the metal substrate. Means 70% or more, and particularly preferably 80% or more.
【００１４】本発明において、この固着性は、ＪＩＳ
Ｋ ５４００−１９９０ 塗料一般試験方法の付着性試
験に準じた「テープはくり試験」によって求める。この
テープはくり試験の方法は次の通りである。In the present invention, this fixability is determined according to JIS
K 5400-1990 Determined by a "tape peel test" according to the adhesion test of the general paint test method. The method of the tape peeling test is as follows.
【００１５】 光触媒担持物の酸化チタン系光触媒層
の表面に幅１．８ｃｍ、長さ８ｃｍのセロハン粘着テー
プを接着する。 上記で接着したセロハン粘着テープに沿って幅
１．８ｃｍ、長さ８ｃｍのセロハン粘着テープを光触媒
担持物の酸化チタン系光触媒層の表面に接着する（セロ
ハン粘着テープの接着面積：幅３．６ｃｍ×長さ８ｃ
ｍ）。この状態を図１に示す。図中、１は光触媒担持物
の酸化チタン系光触媒層を示し、２はセロハン粘着テー
プである。ただし、幅３．６ｃｍのセロハン粘着テープ
を入手できれば、上記のように幅１．８ｃｍのセロハン
粘着テープを２枚並べて接着するのに代えて、その幅
３．６ｃｍのセロハン粘着テープを８ｃｍの長さで光触
媒担持物の酸化チタン系光触媒層の表面に接着してもよ
い。 １分放置後、それぞれのセロハン粘着テープをそれ
らの一方の端部から瞬間的に引きはがす。 セロハン粘着テープを引きはがした面を幅２．５ｃ
ｍ×長さ８ｃｍの寸法に切断して試験用の試料とする。
上記幅は３．６ｃｍ幅のうちの中央部の２．５ｃｍ幅を
選ぶ。この状態を図２に示す。図２中、３は試験用試料
とする部分で、この部分３には網目を入れて他の部分と
識別できるようにしている。 上記で得られた試料のテープはくり試験前後の酸
化チタン系光触媒層のＴｉ（チタン）濃度をＥＳＣＡ
（Ｘ線光電子）分析によって測定し、その測定結果に基
づき、固着性を下記の式により算出する。ただし、テー
プはくり試験前のＴｉ濃度はあらかじめ測定しておく。 A cellophane adhesive tape having a width of 1.8 cm and a length of 8 cm is adhered to the surface of the titanium oxide photocatalyst layer of the photocatalyst carrier. A cellophane adhesive tape having a width of 1.8 cm and a length of 8 cm is adhered to the surface of the titanium oxide photocatalyst layer of the photocatalyst carrying material along the cellophane adhesive tape adhered as described above (adhesive area of cellophane adhesive tape: width 3.6 cm × Length 8c
m). This state is shown in FIG. In the figure, 1 indicates a titanium oxide-based photocatalyst layer of a photocatalyst-carrying material, and 2 indicates a cellophane adhesive tape. However, if a cellophane adhesive tape having a width of 3.6 cm can be obtained, instead of adhering two cellophane adhesive tapes having a width of 1.8 cm side by side as described above, the cellophane adhesive tape having a width of 3.6 cm may be replaced with an adhesive tape having a length of 8 cm. The photocatalyst carrier may be adhered to the surface of the titanium oxide photocatalyst layer. After standing for 1 minute, the respective cellophane adhesive tapes are momentarily peeled off from one of their ends. 2.5c width on the side where the cellophane adhesive tape was peeled off
It is cut into a size of mx 8 cm in length to obtain a test sample.
As the width, a 2.5 cm width at the center of the 3.6 cm width is selected. This state is shown in FIG. In FIG. 2, reference numeral 3 denotes a portion to be used as a test sample. The portion 3 is meshed so that it can be distinguished from other portions. The tape of the sample obtained above was tested for ESCA concentration of the titanium oxide-based photocatalyst layer before and after the peel test.
It is measured by (X-ray photoelectron) analysis, and based on the measurement result, the sticking property is calculated by the following equation. However, the Ti concentration before the tape peeling test is measured in advance.
【００１６】なお、後記の実施例では、光触媒担持物の
酸化チタン系光触媒層の光触媒活性をガス分解能および
酢酸減少率で評価するが、それらの評価も上記テープは
くり試験後の試料について行う。In the examples described later, the photocatalytic activity of the titanium oxide photocatalyst layer of the photocatalyst carrier is evaluated by the gas resolution and the acetic acid reduction rate. These evaluations are also performed on the sample after the tape peeling test.
【００１７】[0017]
【実施例】以下実施例に基づいて本発明をより具体的に
説明するが、本発明はかかる実施例のみに限定されるも
のではない。なお、以下の実施例などにおいて溶液や分
散液などの濃度を示す％は、特に単位を付記しないかぎ
り、重量％である。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples below,% indicating the concentration of a solution or a dispersion liquid is% by weight unless otherwise specified.
【００１８】実施例１ アルミニウム板〔日本テストパネル（株）製、寸法：幅
×長さ×厚み＝７ｃｍ×１５ｃｍ×０．５ｃｍ〕を５％
水酸化ナトリウム水溶液中に浸漬し、室温で５分間エッ
チング処理した後、水洗した。この表面をエッチング処
理したアルミニウム板を硫酸チタニル水溶液〔テイカ
（株）製、硫酸チタニルのＴｉＯ2 換算濃度：８％、Ｈ
2 ＳＯ4 換算濃度：１３％〕中に浸漬し、７０℃で５分
間加熱して硫酸チタニルを熱加水分解した後、水洗し、
４０℃で乾燥して、アルミニウム板の表面に酸化チタン
系光触媒層を形成することにより、アルミニウム板の表
面に酸化チタン系光触媒を担持させた光触媒担持物を製
造した。Example 1 5% of an aluminum plate [manufactured by Japan Test Panel Co., Ltd., dimensions: width × length × thickness = 7 cm × 15 cm × 0.5 cm]
After being immersed in an aqueous sodium hydroxide solution and subjected to an etching treatment at room temperature for 5 minutes, the substrate was washed with water. The titanyl sulfate aqueous solution to an etching treatment with aluminum plate surface [Tayca Co., TiO 2 concentration calculated titanyl sulfate: 8%, H
2 SO 4 concentration calculated: 13%] immersed in the titanyl sulfate was pyrohydrolysis, washed with water and heated for 5 minutes at 70 ° C.,
By drying at 40 ° C. and forming a titanium oxide-based photocatalyst layer on the surface of the aluminum plate, a photocatalyst carrier in which the titanium oxide-based photocatalyst was supported on the surface of the aluminum plate was manufactured.
【００１９】実施例２ 実施例１と同様のアルミニウム板を１０％リン酸水溶液
中に浸漬し、室温で５分間エッチング処理した後、水洗
した。この表面をエッチング処理したアルミニウム板を
実施例１と同様の硫酸チタニル水溶液中に浸漬し、７０
℃で５分間加熱して硫酸チタニルを熱加水分解した後、
水洗し、４０℃で乾燥して、アルミニウム板の表面に酸
化チタン系光触媒層を形成することにより、アルミニウ
ム板の表面に酸化チタン系光触媒を担持させた光触媒担
持物を製造した。Example 2 The same aluminum plate as in Example 1 was immersed in a 10% phosphoric acid aqueous solution, etched at room temperature for 5 minutes, and washed with water. The aluminum plate whose surface was etched was immersed in the same aqueous solution of titanyl sulfate as in Example 1,
After heating at 5 ° C for 5 minutes to thermally hydrolyze titanyl sulfate,
After washing with water and drying at 40 ° C., a titanium oxide-based photocatalyst layer was formed on the surface of the aluminum plate, thereby producing a photocatalyst-carrying material having a titanium oxide-based photocatalyst supported on the surface of the aluminum plate.
【００２０】実施例３ 実施例１で得られた光触媒担持物を４００℃で１時間加
熱処理した。Example 3 The photocatalyst carrier obtained in Example 1 was heat-treated at 400 ° C. for 1 hour.
【００２１】実施例４ 実施例２で得られた光触媒担持物を４００℃で１時間加
熱処理した。Example 4 The photocatalyst carrier obtained in Example 2 was heated at 400 ° C. for 1 hour.
【００２２】比較例１ 実施例１でエッチング処理を行わない以外は同様に操作
した。Comparative Example 1 The procedure of Example 1 was repeated except that no etching treatment was performed.
【００２３】比較例２ 実施例２でエッチング処理を行わない以外は同様に操作
した。Comparative Example 2 The procedure of Example 2 was repeated except that no etching treatment was performed.
【００２４】比較例３ 実施例１でアルミニウム板のエッチング処理のみ実施し
た。Comparative Example 3 In Example 1, only the etching treatment of the aluminum plate was performed.
【００２５】比較例４ 実施例２でアルミニウム板のエッチング処理のみ実施し
た。Comparative Example 4 In Example 2, only the etching of the aluminum plate was performed.
【００２６】比較例５ アルミニウム板のエッチング処理および硫酸チタニル水
溶液中への浸漬を行わなかったもの。Comparative Example 5 An aluminum plate which was not subjected to etching treatment and immersion in an aqueous solution of titanyl sulfate.
【００２７】比較例６ アルミニウム板の代わりに、ガラス板〔成分：ソーダガ
ラス〕を用いた以外は実施例１と同様に操作した。Comparative Example 6 The procedure of Example 1 was repeated, except that a glass plate (component: soda glass) was used instead of the aluminum plate.
【００２８】比較例７ アルミニウム板の代わりに、比較例６と同様のガラス板
を用いた以外は実施例３と同様に操作した。Comparative Example 7 The same operation as in Example 3 was performed, except that the same glass plate as in Comparative Example 6 was used instead of the aluminum plate.
【００２９】上記実施例１〜４および比較例１〜７で得
られた光触媒担持物の光触媒活性および酸化チタン系光
触媒層の基材に対する固着性を以下に示す方法で評価し
た。なお、光触媒活性はガス分解能および酢酸減少率に
よって評価した。このガス分解能および酢酸減少率の評
価は前記のようにテープはくり試験後の試料について行
うので、まず、酸化チタン系光触媒層の固着性試験から
先に説明する。The photocatalytic activities of the photocatalyst supports obtained in Examples 1 to 4 and Comparative Examples 1 to 7 and the adhesion of the titanium oxide photocatalyst layer to the substrate were evaluated by the following methods. The photocatalytic activity was evaluated based on the gas resolution and the acetic acid reduction rate. Since the evaluation of the gas resolution and the acetic acid reduction rate is performed on the sample after the tape peeling test as described above, the adhesion test of the titanium oxide photocatalyst layer will be described first.
【００３０】〔酸化チタン系光触媒層の固着性試験〕ま
ず、実施例１〜４および比較例１〜７で得られた光触媒
担持物の酸化チタン系光触媒層についてＪＩＳ−Ｋ−５
４００−１９９０ 塗料一般試験方法の付着性試験に準
じたテープはくり試験を行う。テープはくり試験の方法
は次の通りである。 光触媒担持物の酸化チタン系光触媒層の表面に幅
１．８ｃｍ、長さ８ｃｍのセロハン粘着テープを接着す
る。 上記で接着したセロハン粘着テープに沿って幅
１．８ｃｍ、長さ８ｃｍのセロハン粘着テープを光触媒
担持物の酸化チタン系光触媒層の表面に接着する（セロ
ハン粘着テープの接着面積：幅３．６ｃｍ×長さ８ｃ
ｍ）。 １分放置後、それぞれのセロハン粘着テープをそれ
らの一方の端部から瞬間的に引きはがす。 セロハン粘着テープを引きはがした面を幅２．５ｃ
ｍ×長さ８ｃｍの寸法に切断して試料とする。上記幅は
３．６ｃｍ幅のうちの中央部の２．５ｃｍ幅を選ぶ。 上記で得られた試料のテープはくり試験前後の酸
化チタン系光触媒層のＴｉ（チタン）濃度をＥＳＣＡ
（Ｘ線光電子）分析によって測定し、その測定結果に基
づき、固着性を下記の式により算出する。。ただし、テ
ープはくり試験前のＴｉ濃度はあらかじめ測定してお
く。 [Titanium oxide photocatalyst layer adhesion test] First, the titanium oxide photocatalyst layers of the photocatalyst carriers obtained in Examples 1 to 4 and Comparative Examples 1 to 7 were subjected to JIS-K-5.
A tape peeling test is performed according to the adhesion test of the 400-1990 paint general test method. The method of the tape peeling test is as follows. A cellophane adhesive tape having a width of 1.8 cm and a length of 8 cm is adhered to the surface of the titanium oxide photocatalyst layer of the photocatalyst carrier. A cellophane adhesive tape having a width of 1.8 cm and a length of 8 cm is adhered to the surface of the titanium oxide photocatalyst layer of the photocatalyst carrying material along the cellophane adhesive tape adhered as described above (adhesive area of cellophane adhesive tape: width 3.6 cm × Length 8c
m). After standing for one minute, the respective cellophane adhesive tapes are momentarily peeled off from one of their ends. 2.5c width on the side where the cellophane adhesive tape was peeled off
The sample is cut into a size of mx 8 cm in length to obtain a sample. As the width, a 2.5 cm width at the center of the 3.6 cm width is selected. The tape of the sample obtained above was tested for ESCA concentration of the titanium oxide-based photocatalyst layer before and after the peel test.
It is measured by (X-ray photoelectron) analysis, and based on the measurement result, the sticking property is calculated by the following equation. . However, the Ti concentration before the tape peeling test is measured in advance.
【００３１】〔ガス分解能〕上記テープはくり試験でセ
ロハン粘着テープ引きはがし後の幅２．５ｃｍ×長さ８
ｃｍの試料を４００ｍｌのガラス容器に入れ、その中に
１０００ｐｐｍのメチルメルカプタンガスを封入した
後、高圧水銀灯（照射強度：３．７ｍＷ／ｃｍ 2 ）にて
１５ｃｍ離れた位置から１時間照射した後、ガス濃度を
ガス検知管を用いて測定し、その結果に基づき、ガス分
解能を下記の式により求めた。[Gas Resolution]
2.5cm wide x 8cm long after peeling off Rohan adhesive tape
cm sample in a 400 ml glass container,
1000 ppm of methyl mercaptan gas was sealed
After that, a high-pressure mercury lamp (irradiation intensity: 3.7 mW / cm TwoAt)
After irradiating for 1 hour from a position 15 cm away, the gas concentration
Measure using a gas detector tube, and based on the result,
The resolution was determined by the following equation.
【００３２】 [0032]
【００３３】〔酢酸減少率〕上記テープはくり試験でセ
ロハン粘着テープ引きはがし後の幅２．５ｃｍ×長さ８
ｃｍの試料を２００ｍｌのマヨネーズビンに入れ、その
中に５ｐｐｍの酢酸水溶液を４０ｍｌ添加した。これに
高圧水銀灯（照射強度：３．７ｍＷ／ｃｍ2）にて上方
１５ｃｍ離れた位置から３時間照射した。酢酸水溶液中
の酢酸量はイオンクロマトグラフィーにて定量し、照射
前後の酢酸量からその減少率を算出した。[Acetic acid reduction rate] In the above tape peeling test, width 2.5 cm × length 8 after peeling off the cellophane adhesive tape.
The cm sample was placed in a 200 ml mayonnaise bottle, into which 40 ml of a 5 ppm acetic acid aqueous solution was added. This was irradiated with a high-pressure mercury lamp (irradiation intensity: 3.7 mW / cm 2 ) from a position 15 cm above for 3 hours. The amount of acetic acid in the acetic acid aqueous solution was quantified by ion chromatography, and the decrease rate was calculated from the amount of acetic acid before and after irradiation.
【００３４】上記酸化チタン系光触媒層の基材表面に対
する固着性、ガス分解能および酢酸減少率の評価結果を
表１にエッチング液の組成、加熱処理の有無（加熱処理
した場合は温度で表示）と共に示す。The results of evaluation of the adhesion of the titanium oxide-based photocatalyst layer to the substrate surface, the gas resolution, and the acetic acid reduction rate are shown in Table 1 together with the composition of the etching solution and the presence or absence of heat treatment (when heat treatment is performed, the temperature is indicated). Show.
【００３５】[0035]
【表１】 ＊：Ｔｉ検出されず。[Table 1] *: Ti was not detected.
【００３６】表１に示す結果から明らかなように、実施
例１〜４の光触媒担持物の酸化チタン系光触媒は、ガス
分解能、酢酸減少率などの光触媒活性に関して、この種
の酸化チタン系光触媒が有する光触媒活性と同等または
それ以上の光触媒活性を有すると共に、酸化チタン系光
触媒層が基材の表面に対して８４〜８８％という非常に
高い固着性で強固に固着していた。また、これらの実施
例間で比較すると、加熱処理した実施例３〜４の方が加
熱処理をしていない実施例１〜２より固着性がわずかな
がら高く、加熱処理により固着性が向上することが明ら
かにされていた。As is evident from the results shown in Table 1, the titanium oxide photocatalysts of the photocatalyst carriers of Examples 1 to 4 were different from each other in terms of photocatalytic activity such as gas resolution and acetic acid reduction rate. The titanium oxide-based photocatalyst layer had a photocatalytic activity equal to or higher than the photocatalyst activity, and the titanium oxide-based photocatalyst layer was firmly fixed to the surface of the substrate with a very high sticking property of 84 to 88%. In addition, when comparing these examples, the heat treatment of Examples 3 and 4 has slightly higher adhesion than the heat treatment of Examples 1 and 2 and the heat treatment improves the adhesion. Was revealed.
【００３７】これに対して、エッチング処理をしていな
い比較例１〜２は、光触媒活性、基材の表面に対する固
着性とも低く、もとより、酸化チタン系光触媒を担持さ
せていない比較例３〜５は、光触媒活性が低く、基材の
表面にＴｉが検出されなかった。また、基材としてガラ
ス板を用いた比較例６〜７は、光触媒活性、基材の表面
に対する固着性とも低かった。On the other hand, Comparative Examples 1 and 2 which were not subjected to the etching treatment had low photocatalytic activity and low adhesion to the surface of the substrate, and Comparative Examples 3 to 5 which did not carry a titanium oxide photocatalyst. Has low photocatalytic activity, and no Ti is detected on the surface of the substrate. Comparative Examples 6 and 7 using a glass plate as the substrate had low photocatalytic activity and low adhesion to the surface of the substrate.
【００３８】[0038]
【発明の効果】以上説明したように、本発明では、金属
基材の表面に対する固着性が高い酸化チタン系光触媒を
担持させた光触媒担持物を提供することができた。As described above, according to the present invention, it is possible to provide a photocatalyst carrier carrying a titanium oxide-based photocatalyst having high adhesion to the surface of a metal substrate.
【００３９】また、上記光触媒担持物は、金属基材の表
面へのエッチング処理、酸化チタン系光触媒層の形成処
理とも、所定溶液への浸漬、加水分解という簡単な操作
で行うことができるので、種々の形状の金属基材の表面
に広い面積で酸化チタン系光触媒を担持させることがで
き、しかもその基材表面に対する固着性が高いので、酸
化チタン系光触媒を担持させた後でも容易に種々の形状
に加工することができる。In addition, the photocatalyst-carrying material can be subjected to both the etching treatment on the surface of the metal substrate and the formation treatment of the titanium oxide-based photocatalyst layer by simple operations such as immersion in a predetermined solution and hydrolysis. The titanium oxide-based photocatalyst can be supported over a wide area on the surface of a metal substrate of various shapes, and the adhesion to the substrate surface is high. It can be processed into a shape.
【００４０】そして、得られた光触媒担持物は、その光
触媒活性を利用して、有害物質、悪臭物質などを効率よ
く除去することができ、例えば、廃水や空気の浄化な
ど、工業用、一般家庭用のいずれにも有効に使用するこ
とができる。The resulting photocatalyst carrier can efficiently remove harmful substances and odorous substances by utilizing its photocatalytic activity. For example, it can be used for industrial and household purposes such as purification of wastewater and air. It can be used effectively for any of the applications.
【図１】光触媒担持物の酸化チタン系光触媒層にセロハ
ン粘着テープを接着した状態を模式的に示す平面図であ
る。FIG. 1 is a plan view schematically showing a state in which a cellophane adhesive tape is adhered to a titanium oxide photocatalyst layer of a photocatalyst carrier.
【図２】図１に示す状態からセロハン粘着テープを引き
はがし、試験用試料とする部分を模式的に示す平面図で
ある。FIG. 2 is a plan view schematically showing a portion used as a test sample by peeling a cellophane adhesive tape from the state shown in FIG.
１ 光触媒担持物の酸化チタン系光触媒層 ２ セロハン粘着テープ ３ 試験用試料とする部分 1 titanium oxide photocatalyst layer of photocatalyst carrier 2 cellophane adhesive tape 3 part to be used as test sample
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安原 正 岡山県岡山市西幸西1072番地 テイカ株式 会社岡山研究所内 Ｆターム(参考） 4G069 AA03 AA08 BA04A BA04B BA17 BA48A BB02A BB02B BB05C BB10C BB14C BC02C BC16A BC16B CA01 CA05 CA10 CA11 CA17 EA11 EB15Y ED03 FA04 FB08 FB48 FB49 FC02 FC04 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tadashi Yasuhara 1072 Nishi Konishi, Okayama City, Okayama Prefecture F-term in Okayama Research Laboratory, Inc. CA10 CA11 CA17 EA11 EB15Y ED03 FA04 FB08 FB48 FB49 FC02 FC04
Claims (4)
ッチング処理した後、上記金属基材を硫酸チタニル水溶
液または硫酸チタン水溶液中に浸漬しながら上記硫酸チ
タニルまたは硫酸チタンを加水分解して金属基材の表面
に高固着性の酸化チタン系光触媒層を形成することによ
り、金属基材の表面に高固着性の酸化チタン系光触媒を
担持させたことを特徴とする光触媒担持物。After the surface of a metal substrate is etched with an acid or an alkali, the metal substrate is hydrolyzed while the metal substrate is immersed in an aqueous solution of titanyl sulfate or an aqueous solution of titanium sulfate to hydrolyze the metal substrate. A photocatalyst carrier, wherein a highly adherent titanium oxide photocatalyst is supported on the surface of a metal substrate by forming a highly adherent titanium oxide photocatalyst layer on the surface of a material.
としてリン酸を用いるか、または、アルカリとして水酸
化ナトリウムを用いた請求項１記載の光触媒担持物。2. The photocatalyst carrier according to claim 1, wherein the metal substrate is an aluminum plate, and phosphoric acid is used as an acid, or sodium hydroxide is used as an alkali.
ッチング処理した後、上記金属基材を硫酸チタニル水溶
液または硫酸チタン水溶液中に浸漬しながら上記硫酸チ
タニルまたは硫酸チタンを加水分解して金属基材の表面
に高固着性の酸化チタン系光触媒層を形成することによ
り、金属基材の表面に高固着性の酸化チタン系光触媒を
担持させることを特徴とする光触媒担持物の製造方法。3. After etching the surface of the metal base material with an acid or an alkali, the metal base material is hydrolyzed while immersing the metal base material in an aqueous solution of titanyl sulfate or an aqueous solution of titanium sulfate. A method for producing a photocatalyst-supported material, wherein a highly adherent titanium oxide-based photocatalyst is supported on the surface of a metal substrate by forming a highly adherent titanium oxide-based photocatalyst layer on the surface of a material.
酸としてリン酸を用いるか、または、アルカリとして水
酸化ナトリウムを用いる請求項３記載の光触媒担持物の
製造方法。4. An aluminum plate as a metal substrate,
The method according to claim 3, wherein phosphoric acid is used as the acid, or sodium hydroxide is used as the alkali.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10221228A JP2000051692A (en) | 1998-08-05 | 1998-08-05 | Photocatalyst support and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10221228A JP2000051692A (en) | 1998-08-05 | 1998-08-05 | Photocatalyst support and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000051692A true JP2000051692A (en) | 2000-02-22 |
Family
ID=16763485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10221228A Pending JP2000051692A (en) | 1998-08-05 | 1998-08-05 | Photocatalyst support and production thereof |
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| Country | Link |
|---|---|
| JP (1) | JP2000051692A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014128742A (en) * | 2014-04-11 | 2014-07-10 | Hitachi Maxell Ltd | Electric shaver |
-
1998
- 1998-08-05 JP JP10221228A patent/JP2000051692A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014128742A (en) * | 2014-04-11 | 2014-07-10 | Hitachi Maxell Ltd | Electric shaver |
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