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WO2021192631A1 - Élément de capteur d'hydrogène - Google Patents

Élément de capteur d'hydrogène Download PDF

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Publication number
WO2021192631A1
WO2021192631A1 PCT/JP2021/003875 JP2021003875W WO2021192631A1 WO 2021192631 A1 WO2021192631 A1 WO 2021192631A1 JP 2021003875 W JP2021003875 W JP 2021003875W WO 2021192631 A1 WO2021192631 A1 WO 2021192631A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
dopant
sensor element
conjugated polymer
hydrogen sensor
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PCT/JP2021/003875
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English (en)
Japanese (ja)
Inventor
めぐみ 早坂
雄一朗 九内
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住友化学株式会社
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Publication of WO2021192631A1 publication Critical patent/WO2021192631A1/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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance

Definitions

  • the contact combustion type hydrogen sensor element uses a noble metal such as platinum or palladium as a combustion catalyst and tin oxide or alumina as a carrier material in the detection unit, and hydrogen is detected by detecting an increase in the element temperature due to catalytic reaction combustion of hydrogen. Is detected.
  • the semiconductor hydrogen sensor element uses a platinum wire coil coated with fine particles such as indium oxide as a detection unit. When a hydrogen oxidation reaction occurs in the detection unit, oxygen adsorbed by negative ionization is consumed on the surface of the fine particles, and free electrons are generated accordingly to reduce the electric resistance value.
  • the semiconductor hydrogen sensor element detects hydrogen by detecting the decrease in the electric resistance value.
  • the hydrogen detection film 103 contains a conjugated polymer and an organic dopant, and preferably contains a conjugated polymer doped with an organic dopant.
  • the hydrogen detection film 103 is preferably made of a conjugated polymer and an organic dopant, and more preferably made of a conjugated polymer doped with an organic dopant.
  • the hydrogen detection film 103 preferably has a shape having a large surface area from the viewpoint of increasing the reactivity with hydrogen gas and improving the sensitivity.
  • the hydrogen detection film having the above shape is, for example, a film composed of nanofibers of a conjugated polymer and doped (adsorbed) by an organic dopant on the nanofibers; Membranes to which an organic dopant is doped (adsorbed); a film containing a porous material and the porous material is impregnated with a conjugated polymer and an organic dopant.
  • the hydrogen detection film 103 is preferably a membrane containing nanofibers of a conjugated polymer and having an organic dopant doped (adsorbed) on the nanofibers, and more preferably the nanofibers of the conjugated polymer and the nanofibers. It is a film made of an organic dopant that is doped with.
  • the hydrogen detection film 103 exposes the conjugated polymer to the surface from the viewpoint of enabling contact between the conjugated polymer and hydrogen, preferably from the viewpoint of enabling contact between the conjugated polymer and hydrogen on the largest possible surface area. It is preferable to do so.
  • conjugated polymer usually has extremely low electrical conductivity of its own, and exhibits almost no electrical conductivity , for example, 1 ⁇ 10-6 S / m or less.
  • the electrical conductivity of the conjugated polymer itself is low because the electrons are saturated in the valence band and the electrons cannot move freely.
  • the electrons of the conjugated polymer are delocalized, the ionization potential of the conjugated polymer is significantly smaller than that of the saturated polymer, and the electron affinity of the conjugated polymer is very large.
  • conjugated polymers are prone to charge transfer with suitable dopants, such as electron acceptors or donors, and the dopant pulls electrons out of the valence band of the conjugated polymer.
  • electrons can be injected into the conduction band. Therefore, in a conjugated polymer doped with a dopant, there are a small number of holes in the valence band or a small number of electrons in the conduction band, and these can move freely, so that the conductivity tends to be dramatically improved. It is in.
  • the value of the linear resistance R of a single product when the distance between the lead rods is set to several mm to several cm and measured with an electric tester is preferably in the range of 0.01 ⁇ or more and 300 M ⁇ or less at a temperature of 25 ° C. Is.
  • a conjugated polymer has a conjugated system structure in the molecule, for example, a molecule having a skeleton in which double bonds and single bonds are alternately connected, and a polymer having a conjugated unshared electron pair. And so on. As described above, such a conjugated polymer can be easily imparted with electrical conductivity by doping.
  • the conjugated polymer is not particularly limited, and for example, polyacetylene; poly (p-phenylene vinylene); polypyrrole; poly (3,4-ethylenedioxythiophene) [PEDOT] or other polythiophene-based polymer; polyaniline-based polymer. And so on.
  • the polythiophene-based polymer is a polymer having a polythiophene skeleton, a polythiophene skeleton, and a substituent introduced into a side chain, a polythiophene derivative, or the like.
  • the term "polymer” means a similar molecule. Only one type of conjugated polymer may be used, or two or more types may be used in combination.
  • the conjugated polymer is preferably a polyaniline-based polymer.
  • organic dopant an organic compound that functions as an electron acceptor (acceptor) for the conjugated polymer and an organic compound that functions as an electron donor (donor) for the conjugated polymer are included.
  • acceptor an organic compound that functions as an electron acceptor
  • donor an organic compound that functions as an electron donor
  • the doping / dedoping behavior of the dopant on the conjugated polymer is a reversible redox reaction.
  • the doping state is an oxidation state and its chemical potential is high.
  • the conjugated polymer in the doped state acts as an oxidant, but its potential differs depending on the type of the conjugated polymer.
  • the doping rate of the dopant on the conjugated polymer varies, and the chemical potential increases as the doping rate increases. If the doping rate is too high, oxidative decomposition of the conjugated polymer itself will occur.
  • the upper limit doping rate that does not cause oxidative decomposition depends on the type of conjugated polymer.
  • H + A is a dopant that functions as an electron acceptor - cited doped polyaniline example
  • hydrogen detecting film containing a conjugated polymer and the dopant is a mechanism for detecting the hydrogen will be described using the following equation.
  • polyaniline becomes conductive only in the emeraldine salt state.
  • the polyaniline doped with the dopant H + A ⁇ is exposed to hydrogen gas, it is further doped with hydrogen, and as a result, the electric resistance value is lowered. Hydrogen gas can be detected by detecting such fluctuations in the electric resistance value.
  • the organic dopant contained in the hydrogen detection film 103 includes a dopant having a molecular volume of 0.20 nm 3 or less (hereinafter, this organic dopant is also referred to as “dopant (A)”). Thereby, the reversibility of the electric resistance value of the hydrogen sensor element can be improved.
  • the organic dopant contained in the hydrogen detection film 103 may contain only one kind of dopant (A), or may contain two or more kinds of dopant (A).
  • the organic dopant contained in the hydrogen detection film 103 contains the dopant (A)
  • the reversibility of the electric resistance value of the hydrogen sensor element is improved. It is presumed that this is partly due to the ease of approaching and moving away. Further, when the molecular volume of the organic dopant is 0.20 nm 3 or less, it is considered that hydrogen gas easily penetrates into the hydrogen detection film 103, which is considered to be advantageous for improving the sensitivity of the hydrogen sensor element. Be done.
  • the molecular volume of the dopant (A) is preferably not 0.18 nm 3 or less, more preferably 0.16 nm 3 or less, more preferably 0.15 nm 3 or less Is.
  • the molecular volume of the dopant (A) is usually 0.05 nm 3 or more, and is preferably 0.06 nm 3 or more from the viewpoint of improving the long-term stability of the hydrogen detection film 103.
  • the polymer tends to embrace moisture and the influence of humidity on the electric resistance value detected by the hydrogen detection film 103 becomes large, and the reliability of the hydrogen sensor element tends to decrease.
  • the hydrogen detection film 103 may further contain an organic dopant other than the dopant (A) together with the dopant (A), but preferably contains only the dopant (A).
  • the dopant (A) may be a compound that functions as an acceptor for the conjugated polymer, or may be a compound that functions as a donor for the conjugated polymer.
  • Examples of the organic dopant having a molecular volume of 0.20 nm 3 or less and being an acceptor include organic acids (excluding phenolic compounds), organic cyano compounds, phenolic compounds, and organic metal compounds.
  • an organic acid such as an organic carboxylic acid, an organic sulfonic acid, or an organic phosphonic acid is preferably used as the organic dopant having a molecular volume of 0.20 nm 3 or less and being an acceptor.
  • Organic sulfonic acid is more preferably used.
  • the organic acid has a low proton donating property, so that the polyaniline-based polymer is less likely to be oxidatively decomposed, and the long-term stability of the hydrogen detection film 103 tends to be improved.
  • organic acid examples include ethanesulfonic acid, hydroxypropanesulfonic acid, 2-fluorobenzenesulfonic acid, 3-fluorobenzenesulfonic acid, 4-fluorobenzenesulfonic acid, pyridine-2-sulfonic acid, and pyridine-3-sulfonic acid.
  • Pyridine-4-sulfonic acid ethanedisulfonic acid, 3-amino-1-propanesulfonic acid, aminoethylsulfonic acid, malonic acid, succinic acid and the like.
  • Examples of the organic dopant having a molecular volume of 0.20 nm 3 or less and being a donor include alkylamine and alkylammonium salt, and specifically, methylamine, ethylamine, butylamine, ethylenediamine, tetramethylammonium salt and dimethyl. Examples thereof include diethylammonium salt.
  • a preferable example of the hydrogen detection membrane 103 is that the conjugated polymer is a polyaniline-based polymer, the organic dopant is the dopant (A), and the dopant (A) is the acceptor.
  • Another preferred example of the hydrogen detection film 103 is that the conjugated polymer is a polyaniline-based polymer, the organic dopant is the dopant (A), and the dopant (A) is an organic acid as an acceptor.
  • the dopant (A) preferably does not contain a fluorine atom from the viewpoint of improving the sensitivity of the hydrogen sensor element.
  • the dopant (A) contained in the hydrogen detection film 103 is a dipole moment. ) Is preferably 6D (Debye) or less.
  • the humidity dependence of the electric resistance value indicated by the hydrogen sensor element can be reduced (the electric resistance value can be less affected by the humidity of the measurement environment), and thus the function and / or the function of the hydrogen sensor element and / or The reliability can be further improved.
  • the dipole moment of the dopant (A) is 6D or less, the humidity dependence of the electric resistance value can be reduced because the dopant has a low affinity with water, which is a polar molecule. It is presumed that one of the reasons is that it is difficult to attract water.
  • the dipole moment of an organic dopant changes depending on the electronegativity and three-dimensional structure of the atoms that make up the dopant.
  • the water insolubility of the dopant (A) can be increased, so that the humidity dependence can be further reduced.
  • it tends to be difficult to attract water when the dipole moment is small and the degree of uneven distribution of electric charges is small rather than being water-insoluble. It is presumed that the humidity dependence can be further reduced by satisfying the above (b) because the packing property of the dopant (A) with the conjugated polymer is improved.
  • the molecular structure of the organic dopant and the type of functional group it has can affect the humidity dependence.
  • having a hydrophilic group tends to increase the humidity dependence.
  • the dopant (A) contained in the hydrogen detection film 103 is an atom having an acid group and having an absolute value of negative charge of 0.55 or more (hereinafter, this atom is also referred to as “atom a”). It is preferably contained in a molecular structure other than the acid group. Thereby, the sensitivity of the hydrogen sensor element can be improved. As the atom a, usually, among the atoms contained in the molecular structure other than the acid group, the atom having the largest absolute value of the negative charge is selected.
  • the positive charge of the conjugated polymer In order to increase the sensitivity (reactivity to hydrogen) of the hydrogen sensor element, it is important to reduce the positive charge of the conjugated polymer. Reducing the positive charge in the conjugated polymer means reducing the attraction of electrons from the conjugated polymer by the dopant, which leaves room in the conjugated polymer for electrons to be attracted by doping with hydrogen gas. Can be done. In the dopant (A) containing the atom a in the molecular structure other than the acid group, the charge of the atom around the atom a is positively large, and the positive charge of the acid group is small accordingly.
  • organic dopants having a molecular volume of 0.20 nm 3 or less and having an acid group and containing the atom a in a molecular structure other than the acid group include pyridine-3-sulfonic acid and hydroxypropanesulfonic acid. , 3-Amino-1-propanesulfonic acid, aminoethylsulfonic acid and the like.
  • the energy of LUMO of the dopant and the energy of HOMO of the conjugated polymer are based on their molecular structure, and DFT (Density Functional Theory) using general calculation software is used. It can be calculated by APFD / 6-31G + g (d)) calculation. Examples of the calculation software include a quantum chemistry calculation program "Gaussian series" manufactured by HULINKS.
  • of 4.5 eV or more and the dopant (A) include polyaniline and ethanesulfonic acid, polyaniline and hydroxypropanesulfonic acid, and polyaniline and 3-amino-1-propanesulfonic acid. , Polyaniline and aminoethyl sulfonic acid, polyaniline and malonic acid, polyaniline and succinic acid and the like.
  • the thickness of the hydrogen detection film 103 is not particularly limited, but is, for example, 0.3 ⁇ m or more and 50 ⁇ m or less. From the viewpoint of the flexibility of the hydrogen sensor element, the thickness of the hydrogen detection film 103 is preferably 0.3 ⁇ m or more and 40 ⁇ m or less.
  • Hydrogen sensor element for the hydrogen sensor element, for example, a substrate 104 on which a pair of electrodes composed of a first electrode 101 and a second electrode 102 is formed is prepared, and is in contact with both the first electrode 101 and the second electrode 102. It can be manufactured by forming the hydrogen detection film 103 so as to be arranged.
  • the hydrogen detection film 103 can be produced, for example, by subjecting a substrate 104 to a polymerization reaction to form a film (layer) of a conjugated polymer and then impregnating it with an organic dopant.
  • a polymerization reaction on the substrate 104 include a method in which a liquid containing a monomer forming a conjugated polymer and a liquid containing a polymerization initiator are placed on the substrate 104 in an overlapping manner. The substrate may be heated as needed to accelerate the polymerization reaction.
  • the hydrogen sensor element can include other components other than those described above.
  • Other components include, for example, antioxidants, metal microparticles, metal oxide microparticles, graphite and the like.
  • the antioxidant may contribute to the antioxidant of the hydrogen detection film 103.
  • Metal fine particles, metal oxide fine particles, and graphite can contribute to improving the sensitivity of the hydrogen sensor element.
  • a test is conducted in which gas is flowed into the container 402 in the order of the following [1] to [4] for the following time.
  • the following test is carried out in an environment with a temperature of 23 ° C.
  • the electric resistance value H2 indicates that the gas introduced into the container 402 has a hydrogen concentration of 2 vol. It is the average value of the electric resistance values from 3 minutes to 10 minutes after switching to the mixed gas of%.
  • the electric resistance value H0 is the average value of the electric resistance values from 3 minutes to 10 minutes after introducing only the dry air into the container 402 or after switching the gas to be introduced into the container 402 to only the dry air. Is.
  • the electric resistance value change rate Z is an index (sensitivity index) indicating the sensitivity of the hydrogen sensor element, and for example, the electric resistance value change rate Z1 can be used as an index of the sensitivity of the hydrogen sensor element. From the viewpoint of enhancing the function and / or reliability as a hydrogen sensor element, it is preferable that the electric resistance value change rate Z is high.
  • the electrical resistance value change rate Z1 can be 1% or more at 23 ° C., preferably 4% or more, more preferably 6% or more, and further preferably 8% or more.
  • the rate of change in electrical resistance Z1 may be 25% or less at 23 ° C. According to the present invention, it is possible to provide a hydrogen sensor element having good sensitivity for various purposes and usage environments.
  • the index value (%) of the reversibility of the electrical resistance value is obtained based on the following formula.
  • the humidity dependence of the electric resistance value of the hydrogen sensor element can be evaluated by, for example, the following method. After manufacturing the hydrogen sensor element, the hydrogen sensor element is exposed to dry air overnight, and a pair of Au electrodes of the hydrogen sensor element and a commercially available digital multimeter are connected by a lead wire. Next, the hydrogen sensor element is allowed to stand for 30 minutes in an atmosphere of a temperature of 30 ° C. and a relative humidity of 30% RH while monitoring the electric resistance value with a digital multimeter. Next, the hydrogen sensor element is allowed to stand for 30 minutes in an atmosphere of a temperature of 30 ° C. and a relative humidity of 80% RH while monitoring the electric resistance value with a digital multimeter. From the electric resistance value under each atmosphere, the humidity dependence index value (%) of the electric resistance value is obtained based on the following formula.
  • the electric resistance value RH30 is an electric resistance value when the product is allowed to stand in an atmosphere having a temperature of 30 ° C. and a relative humidity of 30% RH. Is the average value of.
  • the electric resistance value RH80 is an electric resistance value when left standing in an atmosphere of a temperature of 30 ° C. and a relative humidity of 80% RH. Specifically, it is an average value of electric resistance values from a standing time of 15 minutes to 30 minutes. be.
  • the humidity dependence index value is preferably less than 30%, more preferably 25% or less, still more preferably 20% or less, still more preferably 15% or less, and particularly preferably 10% or less. Is.
  • the index value of humidity dependence may be 1% or more.
  • Example 1 With reference to FIG. 2, by sputtering using an ion coater (“IB-3” manufactured by Eiko Co., Ltd.) on one surface of a square glass substrate (“Eagle XG” manufactured by Corning Inc.) having a side of 5 cm. , A pair of rectangular Au electrodes having a length of 2 cm and a width of 3 mm were formed. The thickness of the Au electrode by cross-sectional observation using a scanning electron microscope (SEM) was 200 nm.
  • IB-3 ion coater
  • Eagle XG manufactured by Corning Inc.
  • Solution A in which 0.029 g of ammonium persulfate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was dissolved in 1.55 mL of 1M hydrochloric acid, and 0.48 g of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) were xylene (Tokyo Chemical Industry Co., Ltd.).
  • Example 2 Examples except that as the dopant solution for immersing the polyaniline nanofiber film, a dopant solution 2 in which 1 g of hydroxypropanesulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 19 g of distilled water was used instead of the dopant solution 1.
  • a hydrogen sensor element was produced in the same manner as in 1. When the thickness of the hydrogen detection film was measured in the same manner as in Example 1, it was 30 ⁇ m.
  • Example 4 As the dopant solution for immersing the polyaniline nanofiber film, a dopant solution 4 in which 1 g of pyridine-3-sulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 19 g of distilled water was used instead of the dopant solution 1.
  • a hydrogen sensor element was produced in the same manner as in Example 1. When the thickness of the hydrogen detection film was measured in the same manner as in Example 1, it was 30 ⁇ m.
  • Table 1 shows the types of organic dopants used in Examples and Comparative Examples and their molecular volumes.
  • the molecular volume of the organic dopant was determined by DFT (Density Functional Theory; B3LYP / 6-31G + g (d)) calculation using the quantum chemistry calculation program "Gaussian 16" manufactured by HULINKS based on its molecular structure.

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Abstract

L'invention concerne un élément de capteur d'hydrogène contenant une paire d'électrodes et un film sensible à l'hydrogène disposé de manière à être en contact avec la paire d'électrodes, le film sensible à l'hydrogène contenant un polymère conjugué et un dopant organique, et le dopant organique comprenant des dopants ayant un volume moléculaire de 0,20 nm3 ou moins.
PCT/JP2021/003875 2020-03-26 2021-02-03 Élément de capteur d'hydrogène WO2021192631A1 (fr)

Applications Claiming Priority (2)

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JP2020-055634 2020-03-26
JP2020055634A JP2021156675A (ja) 2020-03-26 2020-03-26 水素センサ素子

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WO2021192631A1 true WO2021192631A1 (fr) 2021-09-30

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0389156A (ja) * 1989-08-31 1991-04-15 Sumitomo Chem Co Ltd ガスセンサ素子
US20080101994A1 (en) * 2006-10-28 2008-05-01 Shabnam Virji Polyaniline Nanofiber Hydrogen Sensors
US20100089772A1 (en) * 2006-11-10 2010-04-15 Deshusses Marc A Nanomaterial-based gas sensors
US20160161433A1 (en) * 2014-05-16 2016-06-09 Massachusetts Institute Of Technology Electrospun Polymer Fibers for Gas Sensing

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0389156A (ja) * 1989-08-31 1991-04-15 Sumitomo Chem Co Ltd ガスセンサ素子
US20080101994A1 (en) * 2006-10-28 2008-05-01 Shabnam Virji Polyaniline Nanofiber Hydrogen Sensors
US20100089772A1 (en) * 2006-11-10 2010-04-15 Deshusses Marc A Nanomaterial-based gas sensors
US20160161433A1 (en) * 2014-05-16 2016-06-09 Massachusetts Institute Of Technology Electrospun Polymer Fibers for Gas Sensing

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JP2021156675A (ja) 2021-10-07

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