WO2014203923A1 - Catalyseur en métal noble et capteur d'électrolyte gazeux à potentiel constant - Google Patents

Catalyseur en métal noble et capteur d'électrolyte gazeux à potentiel constant Download PDF

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Publication number
WO2014203923A1
WO2014203923A1 PCT/JP2014/066129 JP2014066129W WO2014203923A1 WO 2014203923 A1 WO2014203923 A1 WO 2014203923A1 JP 2014066129 W JP2014066129 W JP 2014066129W WO 2014203923 A1 WO2014203923 A1 WO 2014203923A1
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WIPO (PCT)
Prior art keywords
electrode
gas
noble metal
gold
metal catalyst
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PCT/JP2014/066129
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English (en)
Japanese (ja)
Inventor
皆越知世
前川亨
石橋研二
宮崎洋
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新コスモス電機株式会社
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Priority claimed from JP2013127648A external-priority patent/JP6326670B2/ja
Priority claimed from JP2013127650A external-priority patent/JP6233562B2/ja
Application filed by 新コスモス電機株式会社 filed Critical 新コスモス電機株式会社
Publication of WO2014203923A1 publication Critical patent/WO2014203923A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

Definitions

  • the present invention provides a working electrode for electrochemically reacting a gas to be detected as a gas electrode for detecting a gas, a counter electrode for the working electrode, and a reference electrode for controlling the potential of the working electrode.
  • the present invention relates to a noble metal catalyst used in a constant potential electrolytic gas sensor provided facing a housing portion, and the constant potential electrolytic gas sensor.
  • a conventional constant potential electrolytic gas sensor is configured such that an electrode is provided facing an electrolytic solution storage part of an electrolytic cell in which an electrolytic solution is densely stored. For example, an electrode is detected as a gas electrode that detects gas.
  • an electrode is detected as a gas electrode that detects gas.
  • a potentiostat circuit for setting the potential is connected.
  • As the material of the three electrodes a gas-permeable porous PTFE film having water repellency is coated with a noble metal catalyst such as platinum, gold, palladium, etc.
  • an electrolyte an acidic aqueous solution such as sulfuric acid or phosphoric acid is used. Was used.
  • the constant potential electrolytic gas sensor generates a current corresponding to a change in the surrounding environment between the working electrode and the counter electrode by controlling the potential of the working electrode to be constant with respect to a change in the surrounding environment.
  • the gas can be selectively detected depending on the set potential of the potentiostat circuit. Further, by changing the catalyst used for the gas electrode, it is possible to have high selectivity for the target gas.
  • a carbon having a particle diameter of several tens of nanometers supported with gold fine particles of about several hundred nanometers may be used.
  • an immersion support method may be used.
  • the support is immersed in an aqueous solution of a metal salt, the metal component is adsorbed on the support surface, and drying, firing, and reduction are performed.
  • an electrode was produced by applying it to a porous PTFE membrane.
  • constant potential electrolytic gas sensor which is a conventional technique in the present invention, is a general technique, and thus does not show conventional technical documents such as patent documents.
  • the gold-adhered carbon produced by the above-mentioned method has a particle size of gold fine particles larger than that of carbon as a carrier and tends to aggregate in an aqueous solution, so that it is difficult to uniformly disperse the gold fine particles. there were.
  • the gold-adhered carbon produced in such a state that the gold fine particles are not uniform is used as a noble metal catalyst, there are cases where the gas detection performance varies.
  • the firing temperature in the immersion support method may be about 600 ° C., when the carrier is carbon, if the firing temperature is such a high temperature, there is a risk that the carbon as the carrier will burn. there were.
  • an object of the present invention is to provide a noble metal catalyst that hardly causes variations in gas detection performance when used as a noble metal catalyst for each of the electrodes in a potentiostatic gas sensor, and a gas detection performance that hardly varies.
  • An object of the present invention is to provide a potentiostatic gas sensor equipped with a noble metal catalyst capable of keeping the firing temperature low.
  • the first characteristic configuration of the noble metal catalyst according to the present invention for achieving the above object is that gold nanoparticles having an average particle size equal to or smaller than the average particle size of the carbon powder are supported on the carbon powder as a support. is there.
  • the noble metal catalyst of this configuration supports gold nanoparticles having an average particle size equal to or less than the average particle size of the carbon powder, the gold nanoparticles can be supported on the carrier carbon in a dispersed state.
  • the degree of dispersion of the gold nanoparticles can be made substantially uniform. Therefore, if such a gold-supporting carbon is used as a noble metal catalyst in a gas sensor, for example, it is possible to prevent the gas detection performance from varying.
  • attaching gold nanoparticles having an average particle size equal to or less than the average particle size of carbon powder is referred to as “supporting”, and gold nanoparticles having an average particle size larger than the average particle size of carbon powder. It is distinguished from the conventional gold-attached carbon to which is attached.
  • the second characteristic configuration of the noble metal catalyst according to the present invention is that the gold nanoparticles are supported at 5 to 50% by weight of 5 to 50 nm particles.
  • a gold nanoparticle can be carry
  • the content of gold nanoparticles was variously changed from 5 to 50% by weight, and a potentiostatic gas sensor was prepared for each.
  • stable gas sensitivity can be obtained if the added amount of the gold nanoparticles is 5% by weight or more, and the added amount of the gold nanoparticles in the gold-supported carbon is 50% by weight in view of the production cost of the gold-supported carbon. It was recognized that it should be suppressed by
  • the third characteristic configuration of the noble metal catalyst according to the present invention is that the particle size of the carbon powder is in the range of 5 to 300 nm.
  • the particle size of the carbon powder can be set to an arbitrary particle size in the range of 5 to 300 nm, and the particle size of the gold nanoparticle can be set to be equal to or less than the arbitrary particle size.
  • the particle size of carbon black can be adjusted to have such a particle size range.
  • the first characteristic configuration of the constant potential electrolytic gas sensor according to the present invention includes a working electrode that chemically reacts a gas to be detected as a gas electrode that detects gas, a counter electrode with respect to the working electrode, and a reference electrode that controls the potential of the working electrode.
  • the noble metal catalyst according to any one of the first to three characteristic configurations is provided as each electrode. is there.
  • the noble metal catalyst of this configuration can be supported on carbon as a carrier in a state where gold nanoparticles are dispersed, the degree of dispersion of the gold nanoparticles can be made almost uniform. Therefore, if such a gold-supported carbon is used as a noble metal catalyst, it is possible to prevent the gas detection performance from varying in the constant potential electrolytic gas sensor.
  • the second characteristic configuration of the controlled potential electrolysis gas sensor according to the present invention is that the noble metal catalyst includes a carbon powder addition step in which carbon powder is added to a solvent and stirred, and a gold powder in which a colloidal solution in which gold nanoparticles are dispersed is added.
  • a nanoparticle addition step a drying step of drying in a state maintained below the boiling point of the solvent, a firing step of firing carbon powder carrying gold nanoparticles obtained by drying at 250 to 450 ° C., It is in the point produced by performing.
  • gold-supported carbon supported in a state where gold nanoparticles are dispersed can be used as a noble metal catalyst. Since the gold-supporting carbon uses a colloidal solution in the production process, it can be supported on carbon as a carrier in a state in which the gold nanoparticles are dispersed, so the degree of dispersion of the gold nanoparticles is almost uniform. It can be in a state. Therefore, if such a gold-supported carbon is used as a noble metal catalyst, it is possible to prevent the gas detection performance from varying in the constant potential electrolytic gas sensor.
  • the gold-supporting carbon according to the present configuration can suppress the firing temperature to 250 to 450 ° C. during the production process, so there is no possibility that the carbon as the carrier will burn.
  • the third characteristic configuration of the potentiostatic gas sensor according to the present invention is that a surfactant is added in the carbon powder addition step.
  • the dispersibility of carbon in the solvent can be improved by adding a surfactant.
  • the noble metal catalyst of the present invention is used as a noble metal catalyst for each electrode in a potentiostatic gas sensor.
  • gold nanoparticles having an average particle size equal to or less than the average particle size of the carbon powder are supported on carbon powder as a carrier.
  • the constant potential electrolysis gas sensor X is a gas electrode for detecting a gas.
  • the electrode 13 is provided so as to face the electrolytic solution storage part 31 of the electrolytic bath 30 in which the electrolytic solution 20 is stored.
  • the working electrode 11, the counter electrode 12, and the reference electrode 13 are formed by applying and baking a paste made of a known electrode material on the surface of a porous gas-permeable film 14 having water repellency.
  • the working electrode 11, the counter electrode 12 and the reference electrode 13 are disposed to face each other.
  • the electrolytic cell 30 has an opening 32 that opens laterally to form a gas conduction portion 33.
  • Two gas permeable membranes 14 are provided.
  • One gas permeable membrane 14 is provided with a working electrode 11, and the other gas permeable membrane 14 is provided with a counter electrode 12 and a reference electrode 13.
  • the gas permeable membrane 14 disposed on the working electrode 11 side is attached to the electrolytic cell 30 so as to face the opening 32.
  • the gas to be detected is introduced from the gas conduction part 33 and reacts on the working electrode 11.
  • Each gas permeable membrane 14 and O-ring 15 are fixed by a lid member 16.
  • An electrolytic solution inlet 34 for performing maintenance such as injection of the electrolytic solution 20 is formed on the bottom surface of the electrolytic bath 30.
  • Such a constant potential electrolytic gas sensor X includes a current measuring unit capable of detecting a current based on electrons generated on the working electrode 11 by a reaction of the gas to be detected, and a potential control unit capable of controlling the potential of the working electrode 11. It is used as a gas detection device by connecting to a gas detection circuit (not shown).
  • the constant potential electrolytic gas sensor X of the present invention is used for detection of hydride gas such as silane, phosphine, germane, arsine, diborane.
  • each electrode 10 in the controlled potential electrolytic gas sensor X of the present invention includes a noble metal catalyst, and the noble metal catalyst includes a carbon powder addition step A in which carbon powder is added to a solvent and stirred.
  • the carbon powder is produced by performing a firing step D in which the carbon powder is fired at 250 to 450 ° C.
  • the carbon powder addition step A a predetermined amount of carbon powder is weighed, and water as a solvent is added and sufficiently stirred.
  • a known carbon powder for example, carbon black (particle size of about 5 to 300 nm) can be used, and in particular, acetylene black obtained by thermally decomposing acetylene gas is preferably used, but is not limited thereto. It is not something.
  • This step may be performed by adding a surfactant.
  • a surfactant By adding the surfactant, the dispersibility of carbon in the solvent can be improved.
  • the surfactant any of anionic, cationic, nonionic, and betaine surfactants can be used.
  • a surface treatment such as adding a hydroxyl group to the surface of carbon to increase hydrophilicity may be performed, Alternatively, ultrasonic treatment may be performed as pretreatment.
  • a colloidal solution in which gold nanoparticles are dispersed in the solution obtained in the carbon powder addition step A is added.
  • the colloidal solution in which the gold nanoparticles are dispersed is in a state in which the gold nanoparticles having the above-described particle size are dispersed in the solution.
  • the colloidal gold solution uses an in-solution reduction reaction in which metal ions are reduced to a colloid by adding a citrate solution as a reducing agent to a chloroauric acid solution such as tetrachloroauric acid (III) and heating. However, it is not limited to such a method.
  • the size of colloidal gold particles can be changed by increasing or decreasing the amount of reducing agent added to chloroauric acid.
  • the gold nanoparticles may be particles having a particle size of about 5 to 50 nm, but are not limited to this range. In this case, the particle size distribution is preferably such that the proportion of 5 to 50 nm particles is 90% by weight or more.
  • the solution obtained in the gold nanoparticle addition step B is dried while being maintained at a boiling point or lower of the solvent (water).
  • the temperature set to be equal to or lower than the boiling point of the solvent is not particularly limited, but when the solvent is water, it is preferably about 80 to 100 ° C.
  • a drying method a known method such as reduced-pressure drying, vacuum drying, suction drying, or hot air drying can be applied. Known conditions may be applied as drying conditions in these drying methods.
  • the firing temperature in the present embodiment is a temperature (250 to 450 ° C.) at which the organic substance such as the used surfactant evaporates at a temperature at which carbon oxidation does not proceed under an air atmosphere and atmospheric pressure.
  • the firing time may be set as appropriate until the surfactant, colloid protective agent, and the like are completely eliminated by evaporation, sublimation, and thermal decomposition. Therefore, the firing time can be shortened or extended each time depending on the amount of powder to be fired. However, in consideration of grain growth of gold nanoparticles, a decrease in activity due to sintering, etc., the upper limit of the firing time may be set to about 3 hours, for example. Moreover, you may set so that the baking process D may be complete
  • the controlled potential electrolytic gas sensor X of the present invention can use gold-supported carbon supported in a state where gold nanoparticles are dispersed as a noble metal catalyst. Since the gold-supporting carbon uses a colloidal solution in the production process, it can be supported on carbon as a carrier in a state in which the gold nanoparticles are dispersed, so the degree of dispersion of the gold nanoparticles is almost uniform. It can be in a state. Therefore, if such gold-supported carbon is used as a noble metal catalyst, it is possible to prevent the gas detection performance from varying in the constant potential electrolytic gas sensor X.
  • the gold-supporting carbon according to the present configuration can suppress the firing temperature to 250 to 450 ° C. during the production process, so there is no possibility that the carbon as the carrier will burn.
  • the gold nanoparticles can be dispersed with a particle size of about 5 to 50 nm.
  • the amount of added gold fine particles in the gold-supported carbon prepared by the conventional method is more than 50% by weight, whereas the amount of gold nanoparticles added in the gold-supported carbon prepared by the above method is 5 to 50% by weight.
  • Example 1 A gold-supporting carbon used as a noble metal catalyst in the electrode of the controlled potential electrolysis gas sensor X of the present invention was produced as follows. Each reagent was adjusted so that the content of the gold nanoparticles with respect to the gold-supported carbon was 25% by weight.
  • FIG. 3 shows the particle size distribution (measured by the X-ray small angle scattering method) of the gold nanoparticle powder of Invention Example 1
  • FIG. 4 shows an electron micrograph of the gold-supporting carbon
  • FIG. 5 shows an electron micrograph of a conventional gold-supporting carbon (comparative example) for comparison.
  • the gold nanoparticle powder had a particle size of about 5 to 50 nm.
  • the gold-supported carbon of Invention Example 1 it was recognized that the gold nanoparticles were dispersed and supported on the carbon (FIG. 4).
  • the gold-supporting carbon of the comparative example it was recognized that the gold fine particles were aggregated (FIG. 5).
  • each electrode of the potentiostatic gas sensor X was produced as follows. In the gold-supporting carbon used in each electrode, the content of gold nanoparticles was variously changed from 5 to 50% by weight, and a constant potential electrolytic gas sensor X was produced in each.
  • 0.1 g of gold-supported carbon powder 0.1 mL of surfactant (sodium dodecylbenzenesulfonate), PTFE (polytetrafluoroethylene: Teflon) dispersion (a colloidal solution containing fine particles of PTFE, specific gravity 1.5). 35 mL of each was added and kneaded to prepare an electrode material paste. The obtained electrode material paste was printed on a PTFE sheet, dried, and baked at 280 ° C. for 8 hours to obtain each electrode 10. Each of the obtained electrodes 10 was used as a working electrode 11, a counter electrode 12, and a reference electrode 13, and a potentiostatic gas sensor X was prepared in which the electrolytic solution 20 was a 42% by weight sulfuric acid aqueous solution.
  • surfactant sodium dodecylbenzenesulfonate
  • PTFE polytetrafluoroethylene: Teflon
  • gas sensitivity was measured for phosphine gas 1 ppm and 0.5 ppm in an environment of 20 ° C. and 50% RH (FIG. 6). Similarly, gas sensitivity measurement was performed for 1 ppm of each gas of silane, phosphine, germane, arsine, and diborane (FIG. 7). The gas sensitivity was defined by the magnitude of the current value flowing from the working electrode 11 to the gas detection circuit 40 in the target gas atmosphere.
  • the potentiostatic gas sensor X in which the amount of added gold nanoparticles in the gold-supported carbon is 5% by weight or more, particularly 20% by weight or more is recognized as a working electrode having a sufficiently high reactivity to gas. It was.
  • the amount of gold nanoparticles added to the gold-supported carbon should be suppressed to 50% by weight, preferably 30% by weight. Therefore, in consideration of gas sensitivity and production cost, the amount of gold nanoparticles added to the gold-supported carbon is preferably about 5 to 50% by weight.
  • the present invention provides a working electrode for electrochemically reacting a gas to be detected as a gas electrode for detecting a gas, a counter electrode for the working electrode, and a reference electrode for controlling the potential of the working electrode.
  • the present invention can be used for the noble metal catalyst used in the constant potential electrolytic gas sensor provided facing the housing portion and the constant potential electrolytic gas sensor.

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Abstract

L'invention concerne un catalyseur en métal noble faisant en sorte que des nanoparticules de métal sont supportées sur des particules de carbone servant de support, lesdites nanoparticules de métal possédant un diamètre particulaire moyen ne dépassant pas le diamètre particulaire moyen des particules de carbone. Le catalyseur en métal noble est utilisé pour chaque électrode dans un capteur d'électrolyte gazeux à potentiel constant (X) comprenant : une électrode de travail (11), en tant qu'électrode à gaz qui détecte un gaz, qui fait en sorte que le gaz détecté réagisse chimiquement ; une contre-électrode (12) pour l'électrode de travail (11) ; et une électrode de référence (13) commandant le potentiel de l'électrode de travail. Lesdites électrodes font face à une section de logement d'électrolyte (31) d'une cellule électrolytique (30) logeant un électrolyte (20).
PCT/JP2014/066129 2013-06-18 2014-06-18 Catalyseur en métal noble et capteur d'électrolyte gazeux à potentiel constant WO2014203923A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2013127648A JP6326670B2 (ja) 2013-06-18 2013-06-18 定電位電解式ガスセンサ
JP2013-127650 2013-06-18
JP2013-127648 2013-06-18
JP2013127650A JP6233562B2 (ja) 2013-06-18 2013-06-18 貴金属触媒

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WO2014203923A1 true WO2014203923A1 (fr) 2014-12-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019159015A3 (fr) * 2018-02-07 2019-10-10 Stratuscent Inc. Éléments de détection comprenant du noir de carbone sur lequel sont greffées des nanoparticules d'or

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08313480A (ja) * 1995-05-23 1996-11-29 Gastec:Kk 定電位電解式ガスセンサの電極
JP2004146223A (ja) * 2002-10-25 2004-05-20 National Institute Of Advanced Industrial & Technology 燃料電池用負極触媒
JP2012081469A (ja) * 2003-02-13 2012-04-26 E I Du Pont De Nemours & Co 電極触媒および製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08313480A (ja) * 1995-05-23 1996-11-29 Gastec:Kk 定電位電解式ガスセンサの電極
JP2004146223A (ja) * 2002-10-25 2004-05-20 National Institute Of Advanced Industrial & Technology 燃料電池用負極触媒
JP2012081469A (ja) * 2003-02-13 2012-04-26 E I Du Pont De Nemours & Co 電極触媒および製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019159015A3 (fr) * 2018-02-07 2019-10-10 Stratuscent Inc. Éléments de détection comprenant du noir de carbone sur lequel sont greffées des nanoparticules d'or
US11788985B2 (en) 2018-02-07 2023-10-17 Stratuscent Inc. Sensing elements comprising gold nanoparticle-grafted carbon black

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