JPH02128150A - Perhydroxide detector - Google Patents
Perhydroxide detectorInfo
- Publication number
- JPH02128150A JPH02128150A JP28100788A JP28100788A JPH02128150A JP H02128150 A JPH02128150 A JP H02128150A JP 28100788 A JP28100788 A JP 28100788A JP 28100788 A JP28100788 A JP 28100788A JP H02128150 A JPH02128150 A JP H02128150A
- Authority
- JP
- Japan
- Prior art keywords
- thermistor
- hydrogen peroxide
- oxide
- cover layer
- normally
- 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.)
- Granted
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 53
- 239000011247 coating layer Substances 0.000 claims description 13
- 238000001514 detection method Methods 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 108010015776 Glucose oxidase Proteins 0.000 description 2
- 239000004366 Glucose oxidase Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229940116332 glucose oxidase Drugs 0.000 description 2
- 235000019420 glucose oxidase Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910018654 Mn Ox Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、過酸化水素検出素子に関し、更に詳しく言え
ば、高い濃度感受性をもち小型で安価な過酸化水素検出
素子に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hydrogen peroxide detection element, and more particularly to a hydrogen peroxide detection element that is highly sensitive to concentration, small in size, and inexpensive.
本発明は、化学工業、食品工業、医薬品工業、バイオセ
ンサ等としての医療計測及び環境計測等に利用される。INDUSTRIAL APPLICATION This invention is utilized for a chemical industry, a food industry, a pharmaceutical industry, medical measurement as a biosensor, environmental measurement, etc.
従来の過酸化水素検出素子としては、内部に充填された
所定の電解液、カソード、γノード及びこのカソード表
面に配置された酸素（過酸化水素）が通過可能な樹脂（
テフロン等）膜をもつ酸素電極（過酸化水素電極）から
なるものが知られている（［バイオセンシングＪ、Ｐ、
４２、軽部征夫編・著、啓学出版■発行）。これは、カ
ソード（白金極板）上での過酸化水素の分解反応により
生じる電流又は電位を計測して、過酸化水素濃度を検出
していた。Conventional hydrogen peroxide detection elements include a predetermined electrolyte filled inside, a cathode, a γ node, and a resin (hydrogen peroxide) placed on the surface of the cathode through which oxygen (hydrogen peroxide) can pass.
Oxygen electrodes (hydrogen peroxide electrodes) with membranes (Teflon, etc.) are known ([Biosensing J, P,
42, edited and written by Yukio Karube, published by Keigaku Publishing). This detects the hydrogen peroxide concentration by measuring the current or potential generated by the decomposition reaction of hydrogen peroxide on the cathode (platinum electrode plate).
従来のこの種のバイオセンサとしては、例えば基質（グ
ルコース）の酵素（グルコースオキシダーゼ）による反
応のエンタルピー変化に伴う温度変化をサーミスタの抵
抗変化で計測して、発生する過酸化水素量即ちグルコー
ス濃度を検出するものが知られている。また、上記過酸
化水素電極の白金カソード上にグルコースオキシダーゼ
固定膜を組み合わせたバイオセンサも知られている（「
バイオセンシングＪ、Ｐ、２２、軽部征夫編・著、啓学
出版■発行）。Conventional biosensors of this type measure the temperature change associated with the enthalpy change of the reaction of a substrate (glucose) with an enzyme (glucose oxidase) by the resistance change of a thermistor, and measure the amount of hydrogen peroxide generated, that is, the glucose concentration. What it detects is known. Additionally, a biosensor is known in which a glucose oxidase-immobilized membrane is combined on the platinum cathode of the hydrogen peroxide electrode ("
Biosensing J, P, 22, edited and written by Yukio Karube, published by Keigaku Publishing ■).
上記従来の酸素電極又はこれを用いたバイオセンサでは
小型化に限界がある。There is a limit to miniaturization of the conventional oxygen electrode or a biosensor using the same.
また、上記サーミスタを用いたバイオセンサでは、酵素
触媒反応におけるエンタルピー変化が５〜１００ＫＪ１
モルと小さいため、通常のサーミスタでは検出は困難で
あり、この微小な温度変化を検出するには、特別のサー
ミスタが必要となり、極めて高価となる。In addition, in the biosensor using the above thermistor, the enthalpy change in the enzyme catalyzed reaction is 5 to 100 KJ1.
Because it is as small as a mole, it is difficult to detect with a normal thermistor, and a special thermistor is required to detect this minute temperature change, which is extremely expensive.
本発明は、上記観点に鑑みて成されたものであり、高い
濃度感受性をもち小型で安価な過酸化水素検出素子を提
供することを目的とする。The present invention has been made in view of the above-mentioned viewpoints, and an object of the present invention is to provide a hydrogen peroxide detection element that is highly sensitive to concentration, small in size, and inexpensive.
本発明は、従来用いられている上記サーミスタにおいて
は、過酸化水素の分解が緩やかなためこれを検出するこ
とは困難であるが、検出可能な程度に過酸化水素を急速
に分解できる活性の高い酸化物を見出して完成されたも
のである。即ち、本発明は、サーミスタの表面に、過酸
化水素分解を促進する酸化物からなる被覆層を形成させ
たことを特徴とする。The present invention provides a highly active thermistor that can rapidly decompose hydrogen peroxide to a detectable extent, although it is difficult to detect hydrogen peroxide because it decomposes slowly in the conventional thermistor. It was completed with the discovery of oxides. That is, the present invention is characterized in that a coating layer made of an oxide that promotes hydrogen peroxide decomposition is formed on the surface of the thermistor.
上記サーミスタとしては、通常、セラミック焼結体が用
いられる。このサーミスタとしては、温度に対する抵抗
の変化が大きな抵抗体又は半導体であればよく、通常、
抵抗温度特性が負のＮＴＣサーミスタが用いられるが、
それが正のＰＴＣサーミスタであってもよい。As the thermistor, a ceramic sintered body is usually used. This thermistor may be any resistor or semiconductor whose resistance changes with respect to temperature, and usually,
NTC thermistors with negative resistance-temperature characteristics are used, but
It may be a positive PTC thermistor.
この酸化物として、ＣｕＯ１Ｃｕ２０、Ｐｂ５０４、Ｐ
ｂＯ１ＰｂＯ２、Ｆｅ０１Ｍ ｎ ｓ Ｏ４、Ｍ ｎ
Ｏ２又はｖ２ｏ、が有用であり、本検出素子は、これら
の酸化物の少なくとも１つからなる被覆層をサーミスタ
の表面に形成させたものである。この被覆層は、目的に
応じて所定の位置に形成される。この被覆層は強度維持
のため、通常、焼成して形成され、その加熱温度も種々
設定される。This oxide includes CuO1Cu20, Pb504, P
bO1PbO2, Fe01M n s O4, M n
O2 or v2o is useful, and the present detection element has a coating layer made of at least one of these oxides formed on the surface of the thermistor. This coating layer is formed at a predetermined position depending on the purpose. In order to maintain strength, this coating layer is usually formed by firing, and the heating temperature is also set at various values.
この膜厚は、特に限定されないが、０．１〜２００μｍ
が好ましい。０．１μｍ未満では過酸化水素の分解効果
が十分でなく、２００μｍを越えると熱伝導が低下する
からである。この範囲内では、この両者の性能のバラン
スがよい。またこの気孔率は、それが大きい程過酸化水
素分解効果に優れ、それが小さい程強度に優れるが、両
者のバランスを考慮して、通常４０〜６０％程度である
が、これに限定されない。例えば、気孔率が小さなもの
であっても、過酸化水素分解の促進効果があるからであ
る。This film thickness is not particularly limited, but is 0.1 to 200 μm.
is preferred. This is because if the thickness is less than 0.1 μm, the effect of decomposing hydrogen peroxide will not be sufficient, and if it exceeds 200 μm, the thermal conductivity will decrease. Within this range, the performance of both is well balanced. The larger the porosity, the better the hydrogen peroxide decomposition effect, and the smaller the porosity, the better the strength. Considering the balance between the two, it is usually about 40 to 60%, but is not limited to this. For example, even if the porosity is small, it has the effect of promoting hydrogen peroxide decomposition.
更に、本検出素子においては、通常、上記サーミスタに
所定の白金線が、電極として２本平行に包埋されている
。また、セラミックスの保護管又は耐熱鋼により外装、
若しくはガラスにより被覆されてもよい。Furthermore, in this detection element, two predetermined platinum wires are usually embedded in the thermistor in parallel as electrodes. In addition, the exterior is made of ceramic protection tube or heat-resistant steel.
Alternatively, it may be covered with glass.
過酸化水素が水と酸素ガスに分解する際、約１８０ＫＪ
１モルのエンタルピー変化に伴う熱が発生する。従来用
いられているサーミスタを構成するセラミックスでは、
過酸化水素の分解が緩やかなためこれを検出することは
困難である。When hydrogen peroxide decomposes into water and oxygen gas, approximately 180KJ
Heat is generated due to the enthalpy change of 1 mole. The ceramics that make up conventionally used thermistors are
Hydrogen peroxide decomposes slowly, making it difficult to detect.
しかし、Ｐｂ５Ｏ＝又はＣｕＯ等の所定の酸化物はいず
れも、過酸化水素を急速に分解できる触媒活性の高い酸
化物である。従って、この酸化物からなる被覆層がサー
ミスタの表面に、形成され、この被覆層に過酸化水素が
触れると、急速に分解されるので、高い温度の上昇がサ
ーミスタにもたらされ、検出に必要な十分な抵抗（又は
電流）の変化が生じる。However, certain oxides such as Pb5O= or CuO are all highly catalytically active oxides that can rapidly decompose hydrogen peroxide. Therefore, a coating layer made of this oxide is formed on the surface of the thermistor, and when hydrogen peroxide comes into contact with this coating layer, it is rapidly decomposed, bringing about a high temperature rise to the thermistor, which is necessary for detection. A sufficient change in resistance (or current) occurs.
本検出素子は、上記作用をもつので高い濃度感受性をも
ち、更に、単にサーミスタに所定の被覆層を形成させる
にすぎないので、構造が簡単で小型でかつ安価である。Since the present detection element has the above-mentioned function, it has high concentration sensitivity.Furthermore, since it simply forms a predetermined coating layer on the thermistor, it has a simple structure, is small in size, and is inexpensive.
又、本検出素子表面にグルコースオキシダーゼ等の酵素
を固定した膜を配置することにより、過酸化水素を発生
する酵素反応でのバイオセンサとしての応用も再論であ
る。特に、この場合は、従来と比べて、高い濃度感受性
をもち小型で安価なものとすることができ、従来にない
有用なものである。Furthermore, by arranging a membrane on which an enzyme such as glucose oxidase is immobilized on the surface of this detection element, application as a biosensor in an enzymatic reaction that generates hydrogen peroxide is also a possibility. In particular, in this case, compared to the conventional one, it can be made smaller and cheaper, with higher concentration sensitivity, and is more useful than ever before.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be specifically explained with reference to Examples.
（１）サーミスタの製作
まず、二酸化マンガン（試薬Ｍｎ Ｏｘ ） ５０ ｇ
、酸化コバルト（試薬Ｃｏｏ）１０ｇ、酸化ニッケル（
試薬ＮＮ１０）ｌＯ及び酸化第２鉄（試薬Ｆｅ２Ｏ３）
３０ｇ、更に脱イオン水６０−、ポリビニルアルコール
２ｇを、２（１ｍｍφのアルミナ珪石３００ｇと共に、
内容積５００−のポリエチレン製ポットに入れ、１２
Ｏｒ ｐｍで４８時間粉砕混合する。こうして得られた
泥漿を２００メツシユの篩に通した後１０時間冷凍乾燥
し、更に３２メツシユの篩に通し粉末とした。(1) Production of thermistor First, 50 g of manganese dioxide (reagent Mn Ox)
, cobalt oxide (reagent Coo) 10g, nickel oxide (
Reagent NN10) lO and ferric oxide (reagent Fe2O3)
30 g, further 60 g of deionized water, 2 g of polyvinyl alcohol,
Place it in a polyethylene pot with an internal volume of 500 mm, and
Grind and mix for 48 hours at Or pm. The slurry thus obtained was passed through a 200-mesh sieve, freeze-dried for 10 hours, and then passed through a 32-mesh sieve to form a powder.
この粉末をサイズ５ｍｍφ×０．５ （厚さ）ｍｍの円
板形状にプレス成形し、穴の部分に０．１ｍｍφの白金
線３を挿入し、共素地ペーストをこの隙間に充填した。This powder was press-molded into a disc shape with a size of 5 mmφ x 0.5 mm (thickness), a platinum wire 3 of 0.1 mmφ was inserted into the hole, and the gap was filled with the base material paste.
次にこれを大気雰囲気中、１２６０℃で１時間焼成して
、サーミスタ１を製作した。尚、これはＮＴＣサーミス
タである。Next, this was baked at 1260° C. for 1 hour in an air atmosphere to produce thermistor 1. Note that this is an NTC thermistor.
（２）被覆層の形成
、次に、酸化鉛（試薬Ｐｂａ ０４ ）２５ｇ、脱イオ
ン水８ｍｌ及びポリビニルアルコール１ｇを、１０ｍｍ
φのアルミナ珪石１００ｇと共に、内容積２００−のポ
リエチレンポットに入れ２４時時間合粉砕して、ペース
ト状被覆材料を調製した。(2) Formation of a coating layer, then add 25 g of lead oxide (reagent Pba 04 ), 8 ml of deionized water, and 1 g of polyvinyl alcohol to 10 mm
A paste-like coating material was prepared by placing the powder together with 100 g of alumina silica stone having a diameter of φ in a polyethylene pot having an internal volume of 200 mm and pulverizing it for 24 hours.
こうして得られた酸化鉛のペーストを、上記サーミスタ
１の表面に筆で塗布した後、窒素ガス雰囲気中、５８１
）でで０．５時間焼成して、サーミスタｌの表面上に被
覆層２を形成し、実施例１の素子を製作した。この被覆
層２は、厚さが約１００μｍ１平均細孔径が約３μｍ１
気孔率が約５０％であった。The lead oxide paste obtained in this way was applied to the surface of the thermistor 1 with a brush, and then heated at 581° C. in a nitrogen gas atmosphere.
) for 0.5 hours to form a coating layer 2 on the surface of the thermistor 1, thereby producing the element of Example 1. This coating layer 2 has a thickness of about 100 μm and an average pore diameter of about 3 μm.
The porosity was about 50%.
同様な手法にて、酸化第２銅（Ｃｕｂ）の被覆層２を形
成して、実施例２の素子を製作した。尚、焼成は大気雰
囲気中、８１０℃で０．５時間行った。この被覆Ｎ２は
、厚さが約８０μｍ１平均細孔径が約４μｍ１気孔率が
約５５％であった。A covering layer 2 of cupric oxide (Cub) was formed in a similar manner to produce an element of Example 2. Incidentally, the firing was performed at 810° C. for 0.5 hours in an air atmosphere. This coating N2 had a thickness of about 80 μm, an average pore size of about 4 μm, and a porosity of about 55%.
尚、比較例は、上記サーミスタの表面上に被覆層を設け
ないものとした。In the comparative example, no coating layer was provided on the surface of the thermistor.
（３）性能評価
上記各素子の性能を、第２図に示す装置を用いて、評価
した。即ち、脱イオン水に過酸化水素水（ａ度３０％）
を所定量溶解させて、表に示す各過酸化水素濃度の水溶
液４を調製し、試料槽５内に注入されたこの水溶液４中
に各素子を入れ、サーミスタ１に流れる電流値を測定し
た。尚、この；部槽５は２５℃に設定された恒温浴槽６
中に配置されて、水溶液４を恒温としており、更にこの
水溶液４はマグネチックスクーラー７等により攪拌され
ている。この恒温槽６はマグネチックスクーラー７を回
転させうる基台（図示せず）上に置かれている。この結
果を表及び第１図に示した。(3) Performance evaluation The performance of each of the above elements was evaluated using the apparatus shown in FIG. That is, hydrogen peroxide solution (30% A degree) in deionized water.
A predetermined amount of hydrogen peroxide was dissolved to prepare an aqueous solution 4 having each concentration of hydrogen peroxide shown in the table, each element was placed in the aqueous solution 4 injected into a sample tank 5, and the value of the current flowing through the thermistor 1 was measured. Note that this section 5 is a thermostatic bath 6 set at 25°C.
The aqueous solution 4 is kept at a constant temperature, and the aqueous solution 4 is further stirred by a magnetic cooler 7 or the like. This constant temperature bath 6 is placed on a base (not shown) on which a magnetic cooler 7 can be rotated. The results are shown in the table and FIG.
これらの結果によれば、活性酸化物で被覆した実施例１
及び２は、その濃度に応じた電流値を示しその濃度の検
出ができた。しかし、比較例は、その濃度をかえても電
流値の変化はほとんどなく、その濃度の検出はできなか
った。また、実施例１及び２は、比較例と比べて、例え
ば濃度が１０２モル／ｌの場合には各々約１５倍、９倍
の電流値、１０−’モル／ｌの場合には双方ともに約２
倍の電流値を示し、高い濃度感受性を示した。特に、Ｐ
ｂ、０４で被覆した実施例１は一層その性能が優れた。According to these results, Example 1 coated with active oxide
and 2 showed a current value corresponding to the concentration, and the concentration could be detected. However, in the comparative example, there was almost no change in the current value even when the concentration was changed, and the concentration could not be detected. In addition, in Examples 1 and 2, when the concentration is 102 mol/l, the current values are approximately 15 times and 9 times higher, respectively, and when the concentration is 10-' mol/l, both are approximately 2
It showed double the current value and high concentration sensitivity. In particular, P
Example 1 coated with b.04 had even better performance.
また、本実施例の被覆層は焼成されており、かつその膜
厚が８０〜１００μｍ１その気孔率が約５０〜５５％の
ため、強度に優れるとともに触媒活性にも優れる。Further, the coating layer of this example is fired and has a thickness of 80 to 100 μm and a porosity of about 50 to 55%, so it has excellent strength and catalytic activity.
尚、他の酸化物（ＣｕｚＯｌＰｂＯ，ＰｂＯ２、ＦｅＯ
ｌＭｎ、０１、ＭｎＯ２又はＶ ２ｏ ｓ ＞を用いて
も、被覆しない場合と比べて、上記と同様に触媒活性に
優れた。In addition, other oxides (CuzOlPbO, PbO2, FeO
Even when 1Mn, 01, MnO2 or V2os> was used, the catalytic activity was excellent as in the above case compared to the case without coating.
第１図は実施例において過酸化水素濃度と電流値との関
係を示すグラフ、第２図は実施例において用いた電流値
測定装置の模式図である。
１；サーミスタ、２：被覆層、３；白金線、４；水溶液
、５；試料慢、６：恒温浴槽、７；マグネチックスター
ラー
特許出願人 日本特殊陶業株式会社
代 理 人 弁理士 小島清路
弔１
図
第２図FIG. 1 is a graph showing the relationship between hydrogen peroxide concentration and current value in Examples, and FIG. 2 is a schematic diagram of a current value measuring device used in Examples. 1: Thermistor, 2: Covering layer, 3: Platinum wire, 4: Aqueous solution, 5: Sample temperature, 6: Constant temperature bath, 7: Magnetic stirrer Patent applicant: NGK Spark Plug Co., Ltd. Representative: Patent attorney Kiyoji Kojima 1 Figure 2
Claims (1)
ＣｕＯ、Ｃｕ＿２Ｏ、Ｐｂ＿３Ｏ＿４、ＰｂＯ、ＰｂＯ
＿２、ＦｅＯ、Ｍｎ＿３Ｏ＿４、ＭｎＯ＿２及びＶ＿２
Ｏ＿５のうちの少なくとも１つからなる被覆層と、を具
備することを特徴とする過酸化水素検出素子。(1) a thermistor, formed on the surface of the thermistor,
CuO, Cu_2O, Pb_3O_4, PbO, PbO
_2, FeO, Mn_3O_4, MnO_2 and V_2
A hydrogen peroxide detection element comprising: a coating layer made of at least one of O_5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28100788A JP2670693B2 (en) | 1988-11-07 | 1988-11-07 | Hydrogen peroxide detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28100788A JP2670693B2 (en) | 1988-11-07 | 1988-11-07 | Hydrogen peroxide detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02128150A true JPH02128150A (en) | 1990-05-16 |
| JP2670693B2 JP2670693B2 (en) | 1997-10-29 |
Family
ID=17632977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28100788A Expired - Fee Related JP2670693B2 (en) | 1988-11-07 | 1988-11-07 | Hydrogen peroxide detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2670693B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005020459A1 (en) * | 2005-04-29 | 2006-11-09 | Sig Technology Ag | Method and device for the detection of substances in aqueous, gaseous media |
| CN107064252A (en) * | 2017-03-24 | 2017-08-18 | 广东工业大学 | A kind of hydrogen peroxide sensor and preparation method and application |
| CN109293343A (en) * | 2018-08-24 | 2019-02-01 | 西南科技大学 | Pyromagnetic composite sensing resistance material of negative temperature coefficient and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101029329B1 (en) | 2008-11-26 | 2011-04-15 | 고려대학교 산학협력단 | Eelectrochemical sensor based on a CuO nanoflowers-modified electrode for hydrogen peroxide detection |
-
1988
- 1988-11-07 JP JP28100788A patent/JP2670693B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005020459A1 (en) * | 2005-04-29 | 2006-11-09 | Sig Technology Ag | Method and device for the detection of substances in aqueous, gaseous media |
| CN107064252A (en) * | 2017-03-24 | 2017-08-18 | 广东工业大学 | A kind of hydrogen peroxide sensor and preparation method and application |
| CN109293343A (en) * | 2018-08-24 | 2019-02-01 | 西南科技大学 | Pyromagnetic composite sensing resistance material of negative temperature coefficient and preparation method thereof |
| CN109293343B (en) * | 2018-08-24 | 2021-06-25 | 西南科技大学 | Negative temperature coefficient thermomagnetic composite sensitive resistance material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2670693B2 (en) | 1997-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6155061B2 (en) | ||
| JP3350686B2 (en) | Tin oxide gas sensor and manufacturing method | |
| JPH02128150A (en) | Perhydroxide detector | |
| JP2005134251A (en) | Thin-film gas sensor | |
| JP3841513B2 (en) | Hydrocarbon sensor | |
| JPS5814043B2 (en) | humidity sensor element | |
| JPH01201149A (en) | Composite gas sensor | |
| JP3427600B2 (en) | Disposable pH sensor | |
| JP3696494B2 (en) | Nitrogen oxide sensor | |
| JPH03165253A (en) | Oxygen sensor | |
| JPS604849A (en) | Nitrogen oxide detecting element | |
| JPH0147740B2 (en) | ||
| JP3395957B2 (en) | Carbon monoxide detection sensor and carbon monoxide detection method using the same | |
| JPS6034062B2 (en) | Air fuel ratio detection device | |
| JPS5937456A (en) | Detecting element of co | |
| JP3379748B2 (en) | Solid electrolyte type nitrogen oxide sensor | |
| JPS58118953A (en) | Preparation of gas sensitive element | |
| JPH0735716A (en) | Thick film gas sensor and manufacture thereof | |
| JPS63165746A (en) | Gas sensor | |
| JPS5885151A (en) | Air-fuel ratio measurement sensor | |
| JP2000111519A (en) | Gas sensor | |
| JPH10274636A (en) | Co gas detection element | |
| JPS639178B2 (en) | ||
| JPH01197646A (en) | Gas sensor | |
| JPH0197854A (en) | Sensor for burning control |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |