JP5207472B2 - Electrochemical hydrogen bromide gas sensor - Google Patents
Electrochemical hydrogen bromide gas sensor Download PDFInfo
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- JP5207472B2 JP5207472B2 JP2009057582A JP2009057582A JP5207472B2 JP 5207472 B2 JP5207472 B2 JP 5207472B2 JP 2009057582 A JP2009057582 A JP 2009057582A JP 2009057582 A JP2009057582 A JP 2009057582A JP 5207472 B2 JP5207472 B2 JP 5207472B2
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Description
本発明は、臭化水素を検出するのに適した電気化学式ガスセンサに関する。 The present invention relates to an electrochemical gas sensor suitable for detecting hydrogen bromide.
臭化水素は、通常、特許文献1に見られるようなガス取り入れ口側となるように酸化触媒を通気性撥水性膜に添着した作用極を対極とともに電解液中に配置して構成された電気化学式ガスセンサにより検出されている。
しかしながら検出対象ガスである臭化水素以外のガスに対しても高い感度を有するばかりでなく、臭化水素に対する感度が低いという問題がある。
Hydrogen bromide is an electric battery constructed by arranging a working electrode in which an oxidation catalyst is attached to a breathable water-repellent film together with a counter electrode in an electrolyte so as to be on the gas intake side as normally seen in
However, there is a problem that not only the gas other than hydrogen bromide, which is the detection target gas, has high sensitivity, but also the sensitivity to hydrogen bromide is low.
本発明はこのような問題に鑑みてなされたものであってその目的とするところは、臭化水素を高い感度と選択性で検出することができる電気化学式ガスセンサを提供することである。
本発明の他の目的は上記電気化学式ガスセンサに適した作用極を提供することである。
The present invention has been made in view of such problems, and an object thereof is to provide an electrochemical gas sensor capable of detecting hydrogen bromide with high sensitivity and selectivity.
Another object of the present invention is to provide a working electrode suitable for the electrochemical gas sensor.
このような課題を達成するために本発明においては、通気性と導電性を有する炭素繊維をシート状に形成して構成された基材の一方の面にボロンドープダイヤモンドを添着した作用極を、前記基材の他方の面をガス取り入れ口側となるように対極とともに電解液中に配置して構成されている。 In order to achieve such a problem, in the present invention, a working electrode in which boron-doped diamond is attached to one surface of a substrate formed by forming a carbon fiber having air permeability and conductivity into a sheet shape , The other surface of the base material is arranged in the electrolyte solution together with the counter electrode so as to be on the gas inlet side.
本発明によれば、臭化水素を高い選択性と感度で検出することができる。 According to the present invention, hydrogen bromide can be detected with high selectivity and sensitivity.
本発明の詳細を図示した実施例に基づいて説明する。
図１は本発明のセンサで、図中符号11は、本発明が特徴とする作用極であり、電解液24を収容するケース20のガス取り入れ口21に液密状態で固定されており、被測定ガスの濃度に応じて対極22との間に電解電流を生じるように構成されている。なお図中符号23は参照極である。
Details of the present invention will be described based on the illustrated embodiments.
FIG. 1 shows a sensor according to the present invention. Reference numeral 11 in the figure denotes a working electrode characterized by the present invention, which is fixed in a liquid-tight state to a
作用極11は、図2に示したように例えば炭素繊維をパンチングや圧縮によりシート状に形成して構成された導電性と通気性を有する基材12と、この基材12の一方の面、つまりガス取り入れ口21となる側の表面近傍にボロンドープダイヤモンドの層13を、基材12の周縁部12ａを残すとともにボロンドープダイヤモンドの層13の一部13ａが基材12の外周に到達するように形成して構成されている。
なお、必要に応じて電解液の漏れ出しを防止するために被測定ガス流入側に通気性と撥水性を備えた多孔質シート14を密着させてもよい。
As shown in FIG. 2, the working electrode 11 is made of, for example, carbon fiber formed into a sheet shape by punching or compression, and has a conductive and
If necessary, a
上記ボロンドープダイヤモンドの層13は、通常のボロンドープダイヤモンド成膜法と同様に反応室にアセトン、メタノール、及びトリメトキシボランからなる炭素源となる雰囲気中に基材、例えばカーボンペーパーを収容し、所定電力、この実施例では１３００Ｗのマイクロ波を照射して化学気相成長法（ＣＶＤ）により構成されている。 The boron-doped diamond layer 13 contains a base material, for example, carbon paper, in an atmosphere serving as a carbon source composed of acetone, methanol, and trimethoxyborane in a reaction chamber in the same manner as in a normal boron-doped diamond film forming method. It is configured by chemical vapor deposition (CVD) by irradiating a microwave of a predetermined power, 1300 W in this embodiment.
図3は、基材と、基材にボロンドープダイヤモンドの層を形成したものとのそれぞれのＸＲＤ分析結果で、図中点線の楕円により囲む領域、つまりダイヤモンドの（１１１面）の43.9度でのピークを示すもので、基材だけのものと比較してボロンドープダイヤモンドの層を形成したもののピークが大きくなっていることが確認できる。 Fig. 3 shows the results of XRD analysis of the base material and the base material with a boron-doped diamond layer formed on the base material. It shows a peak, and it can be confirmed that the peak of the boron-doped diamond layer formed is larger than that of the substrate alone.
一方、成膜時間30分で基材にボロンドープダイヤモンドの層を形成し、走査型電子顕微鏡により観察したところ、平均粒径は150ｎｍ程度のボロンドープダイヤモンドの粒子が相互に接触するとともにガスが透過可能な隙間を形成するようにカーボン繊維の表面に添着されている。 On the other hand, a boron-doped diamond layer was formed on the substrate in 30 minutes, and observed with a scanning electron microscope. The boron-doped diamond particles with an average particle size of about 150 nm were in contact with each other and the gas was transmitted. It is attached to the surface of the carbon fiber so as to form a possible gap.
このようにしてダイヤモンド粒子が異なる作用極11をガス取り入れ口に配置して種々のガスに対するセンサ出力を調査したところ、表1に示したように臭化水素に対する感度は、他のガスに比較して極端に高かった。このことから、通気性導電材の表面にボロンドープダイヤモンドを成膜した作用極は臭化水素に対する高い選択性を有することが確認できた。 In this way, the working electrode 11 with different diamond particles was placed at the gas inlet and the sensor output for various gases was investigated. As shown in Table 1, the sensitivity to hydrogen bromide compared to other gases. It was extremely expensive. From this, it was confirmed that the working electrode in which boron-doped diamond was formed on the surface of the air-permeable conductive material had high selectivity for hydrogen bromide.
他方、ボロンドープダイヤモンドの層の密度による影響を確認するため、成膜時間30分乃至120分までを変更しながら基材にボロンドープダイヤモンドの層を形成し、走査型電子顕微鏡により観察したところ平均粒径は150ｎｍ乃至400ｎｍ程度のボロンドープダイヤモンドの粒子がカーボン繊維の表面に添着されていた。
そして、それぞれの作用極により臭化水素に対する検出感度を調査したところ図4のような結果を得た。
このことから、最適な密度が存在することが確認できた。
On the other hand, in order to confirm the influence of the density of the boron-doped diamond layer, the boron-doped diamond layer was formed on the substrate while changing the film formation time from 30 minutes to 120 minutes, and the average was observed with a scanning electron microscope. Boron-doped diamond particles having a particle size of about 150 nm to 400 nm were attached to the surface of the carbon fiber.
When the detection sensitivity for hydrogen bromide was investigated using each working electrode, the results shown in FIG. 4 were obtained.
From this, it was confirmed that an optimum density exists.
作用極の安定性を調査するため一定濃度の臭化水素を連続的に供給してその出力を複数のサンプルについて測定したところ図5に示したように初期段階では出力が時間とともに低下したが、以後は、安定状態に到達した。なお、図中符号ＣＰ−０８２４、ＣＰ−０８３０、ＣＰ−０８３１はそれぞれサンプル番号を示す。 In order to investigate the stability of the working electrode, a constant concentration of hydrogen bromide was continuously supplied, and the output was measured for a plurality of samples.As shown in FIG. Thereafter, a stable state was reached. In the figure, symbols CP-0824, CP-0830, and CP-0831 indicate sample numbers, respectively.
さらに、濃度の異なる臭化水素を測定したところ図6に示したように高い直線性を有することが確認できた。 Furthermore, when hydrogen bromide with different concentrations was measured, it was confirmed that it had high linearity as shown in FIG.
一定濃度の臭化水素を間歇的に供給して応答性を調査したところ図7に示したような結果となった。 When a constant concentration of hydrogen bromide was intermittently supplied to investigate the response, the results shown in FIG. 7 were obtained.
本発明によれば、臭化水素を高い選択性と感度で検出することができる。 According to the present invention, hydrogen bromide can be detected with high selectivity and sensitivity.
11 作用極
12 基材
13 ボロンドープダイヤモンドの層
14 多孔質シート
21 ガス取り入れ口
22 対極
24 電解液
11 Working electrode
12 Base material
13 Boron-doped diamond layer
14 Porous sheet
21 Gas intake
22 Counter electrode
24 electrolyte
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