JP2010086923A - Electrolyte material for fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolyte material for a fuel cell, having sufficiently high proton conductivity under a low humidity condition and sufficiently improving high power generation efficiency under a low humidity condition. <P>SOLUTION: The electrolyte material for the fuel cell contains a bottleneck type silica meso porous body having bottleneck type pores satisfying such conditions that the pore inlet diameter and the pore inside diameter have the conditions (A) and (B): [condition (A)] pore inside diameter is 1.5-30 mm, [condition (B)] the ratio of the pore inlet diameter to the pore inside diameter ([pore inlet diameter]/[pore inside diameter]) is 0.05-0.95, wherein an organic group having an ion exchangeable functional group is introduced in the pores. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrolyte material for a fuel cell.

Conventionally, various electrolyte materials have been studied. Such an electrolyte material is considered to exhibit ionic conductivity by movement of ions in a solid. As such an electrolyte material, for example, in WO2002 / 37506 pamphlet (Patent Document 1), a metal atom having a central pore diameter of 1 to 30 nm and bonded to the metal atom, An electrolyte comprising an organic-inorganic composite material having a skeleton composed of an organic group having one or more carbon atoms bonded to a metal atom or the oxygen atom, and a functional group having an ion exchange ability bonded to the organic group in the pores A material is disclosed. Further, in Japanese Patent 2006-117873 (Patent Document 2), the _{formula: (HO 3 S-CH 2} -CH 2 -CH 2 -SiO 3/2) n (HS-CH 2 -CH 2 -CH 2 -SiO _3/2 ) _m (SiO ₂ ) _{1- nm} (where n = 0.30 to 0.63, m = 0.03 to 0.40, n + m = 0.33 to 0.70) is there. An electrolyte material composed of a silica-based mesoporous material represented by the following formula is disclosed. Furthermore, in Japanese Patent Application Laid-Open No. 2003-263999 (Patent Document 3), an aryl group such as a phenyl group is bonded to a silicon atom in a silicate skeleton, and a functional group having ion exchange ability such as a sulfonic acid is bonded to the aryl group. An electrolyte material composed of a silica-based mesoporous material to which groups are bonded is disclosed. Japanese Patent Application Laid-Open No. 2006-196290 (Patent Document 4) is composed of a mesoporous thin film mainly composed of a crosslinked structure having a metal-oxygen skeleton to which an acid group is bonded at least partially. An electrolyte material in which the inner walls of the pores are coated with a modifying group is disclosed. However, such conventional electrolyte materials as described in Patent Documents 1 to 4 do not always have sufficient proton conductivity under low humidity conditions.
WO2002 / 37506 pamphlet JP 2006-117873 A JP 2003-263999 A JP 2006-196290 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and has an electrolyte material for fuel cells that has sufficiently high proton conductivity under low humidity conditions and sufficiently improved power generation efficiency under low humidity conditions. The purpose is to provide.

As a result of intensive studies to achieve the above object, the present inventors have determined that the pore inlet diameter and the pore internal diameter are the following conditions (A) to (B):
[Condition (A)] The pore internal diameter is 1.5 to 30 nm.
[Condition (B)] The ratio of the pore inlet diameter to the pore inner diameter ([pore inlet diameter] / [pore inner diameter]) is 0.05 to 0.95.
A bottleneck type silica-based mesoporous material having a bottleneck type pore satisfying the above and having an organic group having an ion-exchange functional group introduced therein. It has been found that the proton conductivity of the electrolyte material under low humidity conditions is sufficiently improved, and that the power generation efficiency of the electrolyte material for fuel cells is sufficiently improved under low humidity conditions, and the present invention has been completed. .

That is, in the electrolyte material for fuel cells of the present invention, the pore inlet diameter and the pore internal diameter satisfy the following conditions (A) to (B):
[Condition (A)] The pore internal diameter is 1.5 to 30 nm.
[Condition (B)] The ratio of the pore inlet diameter to the pore inner diameter ([pore inlet diameter] / [pore inner diameter]) is 0.05 to 0.95.
A bottleneck type silica-based mesoporous material having a bottleneck type pore satisfying the above and having an organic group having an ion exchange functional group introduced therein is contained. It is.

  In the fuel cell electrolyte material of the present invention, the ion exchange functional group is at least one functional group selected from the group consisting of a sulfonic acid group, a sulfonimide group, a phosphoric acid group, and a carboxylic acid group. Is preferred.

  In the fuel cell electrolyte material of the present invention, the organic group having an ion exchange functional group is composed of a chain hydrocarbon group having 6 or less carbon atoms and a cyclic hydrocarbon group having 10 or less carbon atoms. It is preferable to contain a group having the ion exchange functional group bonded to at least one hydrocarbon group selected from the group consisting of

  The reason why the fuel cell electrolyte material of the present invention sufficiently increases proton conductivity under low humidity conditions and sufficiently improves the power generation efficiency under low humidity conditions is not necessarily clear. Guess as follows. That is, it is presumed that the electrolyte material containing the silica-based mesoporous material fills the pores of the silica-based mesoporous material with water using the water capillary condensation phenomenon, thereby expressing proton conduction. In the fuel cell electrolyte material of the present invention, such a silica-based mesoporous material has a pore diameter inside the pore of 1.5 to 30 nm and a pore diameter on the inlet side of the pore and a fine pore inside the pore. A silica-based mesoporous material having bottleneck-type pores whose ratio to the pore diameter is reduced to 0.05 to 0.95 is used. In a silica-based mesoporous material having pores satisfying such conditions, a sufficient amount of water is present in the pores even under low humidity conditions as compared with conventional silica-based mesoporous materials. This is because the capillary condensation of water in the bottleneck type pores, the adsorption of water depends on the pore diameter inside the pores, and the desorption of water depends on the pore diameter of the pore inlet. In the present invention, an organic group having an ion exchange functional group is introduced into the pore. Such an ion-exchange-functional functional group can exchange ions, so that proton conduction can be efficiently expressed in water. In the present invention, as described above, water is sufficiently present in the pores due to the capillary condensation phenomenon even under low humidity conditions, so that the ion-exchange capacity functional group introduced into the pores reduces the low humidity conditions. Underlying proton conductivity is sufficient. In other words, in the present invention, proton conductivity under low humidity conditions is sufficiently improved by the bottleneck shape of the pores and the ion exchange capability functional group introduced into the pores. Therefore, the present inventors speculate that the power generation efficiency under low humidity conditions is sufficiently improved in the fuel cell electrolyte material of the present invention.

  According to the present invention, it is possible to provide a fuel cell electrolyte material having sufficiently high proton conductivity under low humidity conditions and sufficiently improved power generation efficiency under low humidity conditions.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

In the fuel cell electrolyte material of the present invention, the pore inlet diameter and the pore internal diameter satisfy the following conditions (A) to (B):
[Condition (A)] The pore internal diameter is 1.5 to 30 nm.
[Condition (B)] The ratio of the pore inlet diameter to the pore inner diameter ([pore inlet diameter] / [pore inner diameter]) is 0.05 to 0.95.
A bottleneck type silica-based mesoporous material having a bottleneck type pore satisfying the above and having an organic group having an ion exchange functional group introduced therein is contained. It is.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and duplicate descriptions are omitted.

  FIG. 1 shows a schematic diagram of a longitudinal section of the pores of such a bottleneck type silica-based mesoporous material. Reference numeral 1 in FIG. 1 indicates the pore wall of the pore, reference numeral d1 indicates the pore diameter inside the bottleneck-type pore (pore internal diameter), and reference numeral d2 indicates the inlet of the bottleneck-type pore. The pore diameter (pore inlet diameter) is shown.

  The pores of such a bottleneck type silica-based mesoporous material have a pore internal diameter d1 of 1.5 to 30 nm (condition (A)). Such pore internal diameter d1 is more preferably 1.5 to 30 nm, and particularly preferably 1.6 to 5.0 nm. When the pore internal diameter d1 is less than the lower limit, it becomes difficult to take water into and out of the pores, and sufficient proton conduction is not exhibited. On the other hand, when the pore internal diameter d1 exceeds the upper limit, high proton conductivity is not exhibited at low humidity (for example, relative humidity of 40% or less).

  Further, the pores of the bottleneck type silica-based mesoporous material have a ratio (d2 / d1) of the pore inlet diameter d2 to the pore internal diameter d1 of 0.05 to 0.95 (condition (B)). . Such a ratio (d2 / d1) is more preferably 0.05 to 0.95, and particularly preferably 0.5 to 0.95. When the ratio is less than the lower limit, high conductivity is not exhibited during water adsorption at low humidity.

  Furthermore, the pore entrance diameter d2 is preferably 1.5 to 4.5 nm, and more preferably 1.5 to 4.0 nm. When the pore entrance diameter is less than the lower limit, it tends to be difficult to take water into and out of the pores. On the other hand, when the upper limit is exceeded, there is a tendency not to show high conductivity at low humidity during water desorption. It is in.

  Further, such “pore internal diameter (d1)” and “pore entrance diameter (d2)” are measured as follows. That is, first, the silica-based mesoporous material is cooled to a liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is determined by a constant volume method or a gravimetric method, and then the pressure of the nitrogen gas to be introduced is determined. Gradually increase the amount of nitrogen gas adsorbed against each equilibrium pressure to obtain an adsorption isotherm. Next, using this adsorption isotherm, a pore size distribution curve (a value (unit: cc / g) obtained by multiplying the total pore volume (V) by the logarithm of pore diameter (logD)) is calculated by the BJH method. The curve plotted against the pore diameter (D) is determined.

  Further, in such a bottleneck type silica-based mesoporous material, an organic group having an ion exchange functional group is introduced into the pores. The organic group introduced into the pores is bonded to silicon atoms on the pore wall surface. Further, the “ion exchange functional group” of such an organic group is a functional group having ion exchange ability, and it is possible to impart higher ion conductivity by such an ion exchange ability functional group. . Such an ion exchange functional group is not particularly limited as long as it is a functional group having ion exchange ability, and examples thereof include a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a sulfonimide group. Among these, at least one functional group selected from the group consisting of a sulfonic acid group, a sulfonimide group, a phosphoric acid group, and a carboxylic acid group is more preferable, and a sulfonic acid group and a sulfonimide group are particularly preferable.

  In addition, the organic group having such an ion exchange functional group includes at least one hydrocarbon group selected from the group consisting of a chain hydrocarbon group (i) and a cyclic hydrocarbon group (ii). Those containing a group having an exchangeable functional group bonded thereto are preferred, a chain hydrocarbon group (i) having 6 or less (more preferably 1 to 3) carbon atoms and 10 or less (more preferably 6 to 10) carbon atoms. It is more preferable to contain a group in which the ion exchange functional group is bonded to at least one hydrocarbon group selected from the group consisting of cyclic hydrocarbon groups (ii). When the number of carbon atoms of the chain hydrocarbon group (i) or the cyclic hydrocarbon group (ii) exceeds the upper limit, the pore volume is reduced or a regular pore structure is not formed during production. There is a tendency. In the present invention, a group in which the ion exchange functional group is bonded to the chain hydrocarbon group (i) or the cyclic hydrocarbon group (ii) may be directly used as the organic group having the ion exchange functional group. Or a group in which the ion-exchangeable functional group is bonded to the chain hydrocarbon group (i) or the cyclic hydrocarbon group (ii) and another divalent hydrocarbon group or the like. It may be an organic group having an exchangeable functional group. Further, when the organic group having the ion exchange functional group contains the other divalent hydrocarbon group, it is bonded to the silicon atom on the surface of the pore wall through the other divalent hydrocarbon group. Bonding is preferred.

  Such a chain hydrocarbon group (i) may be linear or branched, and may be a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched group. Linear butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched Linear nonyl group, linear or branched decyl group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched tetradecyl group, linear or branched Examples include a chain hexadecyl group, a linear or branched octadecyl group, and the like, among which a methyl group, an ethyl group, and a linear or branched propyl group are preferable.

  Further, the cyclic hydrocarbon group (ii) is not particularly limited, but is a cycloalkyl group (ii-1) such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, anthryl. An aromatic ring-containing group containing at least one aromatic ring such as a group, tetracenyl group, biphenyl group, terphenyl group, quadrophenyl group, phenalenyl group, phenanthrenyl group, chrysenyl group, tetraphenyl group, pyrenyl group, and triphenylenyl group (ii -2) and the like, and among them, the aromatic ring-containing group (ii-2) is more preferable. Further, such a chain hydrocarbon group (i) and a cyclic hydrocarbon group (ii) may have other substituents, such as a sulfo group, a phospho group, A carboxyl group etc. are mentioned.

Moreover, as an organic group introduced into such pores, from the viewpoint of obtaining higher proton conductivity, an aromatic ring-containing group (ii-2) to which the ion exchange functional group is bonded, And an organic group containing at least one divalent hydrocarbon group selected from the group consisting of an alkylene group, an alkenylene group and an alkynylene group. That is, the silica-based mesoporous material according to the present invention includes an aromatic ring-containing group having an ion-exchange-functional functional group on the silicon atom on the pore wall surface of the pore via the divalent hydrocarbon group ( What ii-2) couple | bonded is preferable. In addition, a silica-based mesoporous material in which an aromatic ring-containing group (ii-2) having an ion exchange functional group is bonded to a silicon atom on the surface of the pore wall of such a pore via the divalent hydrocarbon group. The reason why higher proton conductivity can be obtained is not always clear, but the present inventors presume as follows. That is, first, in the silica-based mesoporous material, due to the bulkiness of the organic groups introduced into the pores, the silanol groups (Si—OH) on the surface of the pore walls and the ion-exchange ability function under low humidity conditions. A group (for example, —SO ₃ H) may be hydrogen-bonded. However, when the aromatic ring-containing group (ii-2) having an ion exchange functional group is bonded to a silicon atom in the pore wall via the divalent hydrocarbon group, a silanol group (Si The bulky aromatic ring-containing group (ii-2) is present between the —OH) and the ion-exchange-functional functional group in the pore, and the silanol group (Si—OH) and the ion-exchange-functional functional group The hydrogen bond between them can be suppressed sufficiently efficiently. Further, when a hydrocarbon group is present between the aromatic ring-containing group (ii-2) and the silicon atom, a decrease in the π electron density of the aromatic ring-containing group (ii-2) is sufficiently suppressed during production, and the aromatic group Since it becomes possible to easily introduce an ion exchange functional group into the ring-containing group (ii-2), it becomes easy to introduce a sufficient amount of the ion exchange functional group. Therefore, in the silica-based mesoporous material in which the aromatic ring-containing group (ii-2) having an ion exchange functional group is introduced through the divalent hydrocarbon group, higher proton conductivity is obtained. The present inventors speculate that

The divalent hydrocarbon group is at least one selected from the group consisting of an alkylene group, an alkenylene group, and an alkynylene group. As such an alkylene group, a C1-C6 thing is preferable and a 1-3 thing is more preferable. Such an alkylene group may be linear or branched, and examples thereof include a methylene group, an ethylene group, a propylene group, and a trimethylene group. An ethylene group (—CH ₂ —CH ₂ —) and a trimethylene group are particularly preferable from the viewpoint of sufficiently suppressing the decrease in π electron density. Moreover, as said alkenylene group, a C2-C6 thing is preferable and a 2-4 thing is more preferable. Such alkenylene groups may be linear or branched, and particularly preferred are ethenylene, propenylene, butenylene, and butadienylene. Furthermore, as said alkynylene group, a C2-C6 thing is preferable and a C2-C4 thing is more preferable. Such an alkynylene group may be linear or branched, and for example, an ethynylene group, a propynylene group, and a butynylene group are particularly preferable.

  The aromatic ring-containing group (ii-2) is not particularly limited as long as it is a group having at least one aromatic ring as described above, but preferably has 1 to 4 aromatic rings. A number of 1 to 3 is more preferable. When the number of such aromatic rings exceeds the upper limit, regular mesopores tend not to be formed.

Further, as the aromatic ring-containing group (ii-2), in low humidity conditions, that the silanol groups (Si-OH) and sulfo group (-SO 3 _H) in the surface of the pore walls are attached From the viewpoint that it can be sufficiently suppressed and that regular pores can be efficiently formed, phenyl group, naphthyl group, anthryl group, tetracenyl group, biphenyl group, terphenyl group, quadrophenyl group, phenalenyl group, phenanthrenyl group, chrysenyl At least one selected from the group consisting of a group, a tetraphenyl group, a pyrenyl group, and a triphenylenyl group is preferable, and among them, a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a terphenyl group, a phenalenyl group, and a phenanthrenyl group are more preferable. From the viewpoint of production efficiency and the like, a phenyl group is particularly preferable.

Further, as such a bottleneck type silica-based mesoporous material, the content ratio of silicon atoms on the surface of the pore wall of the pore to which the organic group is bonded is such that the silicon atom in the silica-based mesoporous material is It is preferably in the range of 2 mol% or more and less than 30 mol%, more preferably in the range of 10 mol% or more and less than 30 mol% with respect to the total amount. When the content ratio of silicon atoms to which such an organic group is bonded is in the above range, the ratio of silicon atoms contributing to the formation of three-dimensional crosslinks in the silica-based mesoporous material is increased. Mesoporous materials tend to exhibit a higher degree of water resistance. On the other hand, when the content ratio of the silicon atom is less than the lower limit, proton conductivity tends to be insufficient. In addition, the content ratio of such a silicon atom is a composition formula when it is assumed that the monomer has reacted without excess or deficiency from the charged amount of the silica raw material (monomer) at the time of producing the silica-based mesoporous material:
[A-SiO _3/2 ] _m [SiO ₂ ] _n
[Wherein, A represents the organic group, and m and n each represent a numerical value such that m + n = 1. ]
Can be determined by calculating the formula: {m / (m + n)} × 100 (mol%) from the numerical values of m and n in the composition formula.

Further, in such a bottleneck type silica-based mesoporous material, the amount of H ⁺ in the ion exchange capacity functional group introduced into the pores is 0.1 mmol / g or more and less than 1.5 mmol / g. It is preferably 1.0 mmol / g or more and less than 1.5 mmol / g. When the amount of H ⁺ is less than the lower limit, the proton conductivity of the obtained fuel cell electrolyte material tends to be insufficient. On the other hand, when the amount exceeds the upper limit, the resulting fuel cell electrolyte material Hydrophilicity increases and tends to dissolve in water. Such an amount of H ⁺ can be measured by an acid-base titration method.

Furthermore, the No particular limitation is imposed on the specific surface area of the bottleneck-type mesoporous silica material, it is preferable 100~1000m ² / g (more preferably 300~1000m ² / g) is in the range of. The “specific surface area” can be calculated as a BET specific surface area from an adsorption isotherm using a BET isotherm adsorption formula.

  Further, such a bottleneck type silica-based mesoporous material preferably has one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more in the X-ray diffraction pattern. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. Therefore, having one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more means that the pores are regularly arranged at intervals of 1 nm or more.

  Further, the pores of such a bottleneck type silica-based mesoporous material are formed not only on the surface of the porous material but also on the inside. The arrangement state (pore arrangement structure or structure) of the pores in such a porous body is not particularly limited, but is preferably a 2d-hexagonal structure, a 3d-hexagonal structure, or a cubic structure. Such a pore arrangement structure may have a disordered pore arrangement structure.

  Here, that the porous body has a hexagonal pore arrangement structure means that the arrangement of the pores is a hexagonal structure (S. Inagaki, et al., J. Chem. Soc., Chem. Commun., 680, 1993; see S. Inagaki, et al., Bull. Chem. Soc. Jpn., 69, 1449, 1996, Q. Huo, et al., Science, 268, 1324, 1995). Moreover, the porous body having a cubic pore arrangement structure means that the arrangement of the pores is a cubic structure (JC Vartuli, et al., Chem. Mater., 6, 2317, 1994). Q. Huo, et al., Nature, 368, 317, 1994). Further, that the porous body has a disordered pore arrangement structure means that the arrangement of the pores is irregular (PT Tanev, et al., Science, 267, 865, 1995; S; A. Bagshaw, et al., Science, 269, 1242, 1995; R. Ryoo, et al., J. Phys. Chem., 100, 17718, 1996). The cubic structure is preferably Pm-3n, Im-3m or Fm-3m symmetric. The symmetry is determined based on a space group notation.

  Further, the shape of such a bottleneck type silica-based mesoporous material is not particularly limited, but it is preferably in the form of a thin film or particles, and from the viewpoint that it can be used as an electrolyte membrane for a fuel cell as it is. More preferably. The “particulate” referred to here may be in the form of a cylinder, needle or the like in addition to a sphere.

  Furthermore, the fuel cell electrolyte material of the present invention only needs to contain the bottleneck type silica-based mesoporous material as described above, and may contain other electrolytes and the like. As such other electrolytes, known electrolyte materials can be used as appropriate.

  Moreover, in such an electrolyte material for fuel cells, when the shape of the bottleneck type silica-based mesoporous material is a thin film, it can be used as it is as an electrolyte membrane for a fuel cell. In addition, when the shape of the bottleneck type silica-based mesoporous material is a powder, it can be used alone or as a mixture with the other electrolytes, and molded into a film to form an electrolyte membrane for a fuel cell. It can also be used.

Next, a method for producing the bottleneck type silica mesoporous material as described above will be described. As a method for producing such a bottleneck type silica-based mesoporous material, silica having pores that satisfies the above conditions (A) and (B) and into which an organic group having the ion exchange functional group is introduced The method is not particularly limited as long as it is a method capable of producing a porous mesoporous material, but a method including the following steps (A) to (E) can be suitably employed. That is, in a solvent, a surfactant and the following general formula (1):
(R ¹ ) ₃ Si—Y (1)
(In the formula, R ¹ may be the same or different and each represents a lower alkoxy group, a hydroxyl group (—OH), an allyl group (CH ₂ ═CH—CH ₂ —), an ester group (preferably having 1 to 5 carbon atoms). An ester group (RCOO-)) and a halogen atom (chlorine atom, fluorine atom, bromine atom, iodine atom), and Y has a precursor of an ion-exchange functional group Indicates an organic group.)
A step of precipitating the first porous body precursor in which the surfactant is introduced into the silica (A). )When,
Removing the surfactant in the vicinity of the inlet of the pores of the first porous precursor to obtain a second porous precursor; and subjecting the second porous precursor to a CVD treatment And (C) a step of obtaining a third porous body precursor by laminating an inorganic oxide in the vicinity of the pore inlet and reducing the pore inlet diameter.
Removing the surfactant introduced into the third porous body precursor to obtain a porous body (D);
The process of converting the precursor of the ion exchange capability functional group in the organic group introduce | transduced into the silica in the said porous body into an ion exchange capability functional group, and obtaining the bottleneck-type silica mesoporous body (E )When,
It is possible to suitably employ a method including: Hereinafter, steps (A) to (E) will be described separately.

  In the step (A), in the solvent, the surfactant is mixed with a mixture of a silica raw material including the first silica raw material and the second silica raw material represented by the general formula (1), and the interface This is a step of precipitating the first porous body precursor into which the activator has been introduced. As used herein, the term “precipitation” refers to the time when the diffraction peak of pores begins to appear by X-ray diffraction measurement of the reaction solution, and the diffraction peak gradually increases to a constant value. Is defined as the end time of precipitation.

R ¹ in the general formula (1) is a lower alkoxy group, a hydroxyl group (—OH), an allyl group (CH ₂ ═CH—CH ₂ —), an ester group (preferably an ester group having 1 to 5 carbon atoms ( RCOO-)) and a halogen atom (chlorine atom, fluorine atom, bromine atom, iodine atom). Such R ¹ is preferably a lower alkoxy group, and more preferably an alkoxy group having about 1 to 4 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) from the viewpoint of reactivity.

Y in the general formula (1) is an organic group having a precursor of an ion exchange capacity functional group, and ion exchange with the chain hydrocarbon group (i) or the cyclic hydrocarbon group (ii). A group containing a functional functional group precursor is preferred. As such Y (organic group), the following general formula (2):
-R ² -X-Q ⁽²⁾
Wherein R ² represents at least one divalent hydrocarbon group selected from the group consisting of an alkylene group, an alkenylene group and an alkynylene group, and X represents the aromatic ring-containing group (ii-2). , Q represents a precursor of an ion exchange capacity functional group.)
When the organic group represented by the formula (1) is used, the ion exchange capacity functional group is preferably bonded to the silicon atom on the pore wall surface of the pore, which is suitable as the silica-based mesoporous material, via the divalent hydrocarbon group. It becomes possible to produce a silica-based mesoporous material to which an aromatic ring-containing group (ii-2) having a group is bonded.

  Further, as a precursor of such an ion exchange functional group, it is only necessary to have a group that can be converted into the ion exchange functional group. For example, chlorosulfonyl group, mercapto group, cyano Group, fluorosulfonyl group and the like.

  Examples of the first silica raw material represented by the general formula (1) include 3-mercaptopropyltrimethoxysilane, 3-cyanopropyltrimethoxysilane, 3-cyanoethyltrimethoxysilane, 2- ( 4-chlorosulfonylphenyl) -ethyltriethoxysilane, 2- (4-chlorosulfonylphenyl) -ethyltrimethoxysilane, 2- (4-mercaptophenyl) ethyltriethoxysilane, 2- (4-mercaptophenyl) ethyltri Examples include methoxysilane and 2- (4-fluorosulfonylphenyl) -ethyltriethoxysilane.

  The second silica raw material may be tetraalkoxysilane having 4 alkoxy groups, trialkoxysilane having 3 alkoxy groups, dialkoxysilane having 2 alkoxy groups, or the like. When such an alkoxysilane has 3 or 2 alkoxy groups, a hydroxyl group or the like may be bonded to the silicon atom in the alkoxysilane. Although it does not restrict | limit especially as such a 2nd silica raw material, For example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane etc. are mentioned. Such a second silica raw material may be used alone or in combination of two or more.

  In addition, when the first silica raw material and the second silica raw material are hydrolyzed, silanol groups are generated, and the generated silanol groups are condensed to form a silicon oxide. Here, when silicon silane is formed, if an alkoxysilane having a large number of alkoxy groups in the molecule is used, bonds generated by hydrolysis and condensation tend to increase. Therefore, it is preferable to use tetraalkoxysilane having many alkoxy groups as the second silica raw material. As such a tetraalkoxysilane, it is particularly preferable to use tetramethoxysilane or tetraethoxysilane from the viewpoint of reaction rate.

  Moreover, as a mixture of the silica raw material containing the first silica raw material and the second silica raw material, the content ratio of the first silica raw material in the mixture is 2 mol% or more and 30 mol with respect to the total amount of the mixture. %, Preferably 10 mol% or more and less than 30 mol%. When the content ratio of the first silica raw material is less than the lower limit, a sufficient amount of ion-exchange capacity functional groups cannot be arranged in the obtained porous body, and sufficient ion conductivity tends not to be obtained. On the other hand, when the above upper limit is exceeded, not only regular pores tend to be formed, but also the proportion of silica atoms that contribute to the formation of three-dimensional crosslinks in the mesoporous material tends to decrease and water resistance tends to decrease. is there. In addition, by setting the content ratio of the first silica raw material in the mixture within the above range, the content ratio of the silicon atom bonded to the organic group having an ion exchange functional group in the obtained silica-based mesoporous material is Since it becomes possible to set it as the range of 2 mol% or more and less than 30 mol% with respect to the total amount of the silicon atom in a porous body, it becomes possible to exhibit high water resistance by the silica type mesoporous material obtained. Moreover, the manufacturing method in particular of such a mixture is not restrict | limited, For example, the method of mixing a 1st silica raw material and a 2nd silica raw material in dry nitrogen stream is employable.

In addition, the surfactant used in the step (A) is not particularly limited, and a known surfactant that can be used for producing a porous body having pores having a pore diameter of 1.5 to 30 nm is appropriately selected. For example, the following general formula (3):
C _n H _{2n + 1} N (CH ₃ ) ₃ · Z (3)
(In the formula, n represents an integer of 2 or more, and Z represents a halide ion such as chloride ion or bromide ion, or an organic anion such as HSO ₄ or acetate ion.)
And alkyltrimethylammonium halides, alkyl alcohols, fatty acids and the like. Further, as such a surfactant, an alkyltrimethylammonium halide having a long-chain alkyl group having 10 to 26 carbon atoms is preferable, among which decyltrimethylammonium halide, dodecyltrimethylammonium halide, tetradecyltrimethylammonium halide, hexa Decyltrimethylammonium halide, octadecyltrimethylammonium halide, eicosyltrimethylammonium halide, and docosyltrimethylammonium halide are more preferable.

  Such a surfactant forms a complex in a solvent together with the mixture of silica raw materials. The silica raw material in the composite is changed to silicon oxide by the reaction, but silicon oxide is not generated in the part where the surfactant is present, so pores are formed in the part where the surfactant is present. Will be. That is, such a surfactant is introduced into the silica raw material and functions as a template for pore formation. Further, such surfactants can be used alone or in combination of two or more, but as described above, the surfactant functions as a template for forming pores in the reaction product of the silica raw material. Since the type greatly affects the pore shape of the porous body, it is preferable to use only one type of surfactant from the viewpoint of obtaining a porous body having a more uniform pore diameter. The surfactant may be added as a powder, or may be added after being dissolved in a small amount of water.

  Moreover, as said solvent, the well-known solvent which can be used when manufacturing a silica type mesoporous material can be used suitably. As such a solvent, an aqueous solvent having an alcohol content of 80% by volume or less is preferably used. Further, when the first porous body precursor is formed into a thin film, the aqueous solvent is added to the silica raw material, and the surfactant is added after stirring at room temperature for several minutes to 3 hours. preferable. Moreover, when making a 1st porous body precursor into thin film form, it is preferable to add a small amount of acids as a pH adjuster to a solvent, and it is preferable to adjust pH value to the range of 1-4. Thus, by adding an acid, each component melt | dissolves and it exists in the tendency which can prepare a uniform solution. In addition, examples of the acid include dilute hydrochloric acid (for example, 2 N), nitric acid, sulfuric acid, and the like, and dilute hydrochloric acid (for example, 2 N) can be preferably used.

  Further, when the first porous body precursor is in the form of particles, the ratio of water and alcohol in the aqueous solvent is changed to obtain a particle size while maintaining a high level of uniformity. The particle size of the silica-based mesoporous material obtained can be easily controlled. For example, when the water ratio is high, the porous body is likely to precipitate, so the particle size is small. Conversely, when the alcohol ratio is high, a porous body having a large particle size can be obtained. In addition, when forming a particulate porous body, it is preferable to mix a silica raw material etc. on basic conditions. When the reaction is carried out under such basic conditions, the reaction point of the silicon atom is increased compared with the case where the reaction is carried out under an acidic condition, and a silicon oxide having excellent physical properties such as moisture resistance and heat resistance is obtained. Tend to be able to get. As such basic conditions, the pH value of the solvent is preferably 7.5 to 13.

  Furthermore, when the first porous body precursor is obtained by mixing the mixture of the silica raw material and the surfactant in the solvent, the content of the surfactant is changed to 1 mol of the silica raw material in the mixture. On the other hand, it is preferable to set it as 0.1-3 mol. If the surfactant content exceeds the above upper limit, surplus surfactant that does not contribute to the formation of the mesoporous material tends to be mixed in the sample, while if it is less than the lower limit, it does not contribute to the formation of the mesoporous material. Excess Si is mixed, and the silica layer becomes thick and the pore volume tends to decrease.

  Moreover, the reaction conditions (reaction temperature, reaction time, etc.) in the step (A) are not particularly limited, and the reaction temperature is preferably, for example, −20 ° C. to 90 ° C. Moreover, when making the said porous body precursor into thin film form, it is preferable to set it as 10 to 40 degreeC, and when making into a particulate form, it is 0 to 80 degreeC (more preferably 10 to 40 degreeC). More preferably. In addition, it is preferable to determine suitably specific reaction conditions based on the kind of silica raw material to be used, the shape of the target porous body, etc.

  When the first porous body precursor is formed into a thin film, a solution obtained by mixing the mixture of the silica raw material and the surfactant in the solvent is coated on the substrate and reacted. As a result, the whole can be solidified while being uniform, and a thin-film porous precursor can be obtained. The method for coating the substrate with such a solution is not particularly limited, and a known method can be appropriately employed, and a spin coating method, a casting method, a dip coating method, or the like can be employed.

  On the other hand, when the first porous body precursor is in the form of particles, the silica raw material is used as it is by using a solution obtained by mixing the mixture of the silica raw material and the surfactant in the solvent. What is necessary is just to make it react. Moreover, when making said 1st porous body precursor into a particulate form, it is preferable to advance reaction in the stirring state.

  The first porous body precursor thus obtained is preferably subjected to a drying treatment. As conditions for such a drying process, it is preferable to set it as about 1 to 24 hours at 30-200 degreeC under atmospheric pressure.

  Next, the step (B) will be described. Step (B) is a step of removing the surfactant in the vicinity of the entrance of the pores of the first porous precursor to obtain a second porous precursor. In FIG. 2, the schematic diagram of the longitudinal cross-section of the pore of such a 2nd porous body precursor is shown. In FIG. 2, reference numeral 1 denotes a pore wall, reference numeral 2 denotes a surfactant, and reference numeral 3 conceptually denotes an inlet of the pore.

  Examples of the method for removing the surfactant near the pore inlet of the first porous body precursor include a method of treating with an organic solvent and a method of using an ion exchange method. . In the case of adopting such a method of treating with an organic solvent, the surfactant is appropriately changed according to the design of the target pore so as to remove only the surfactant near the pore inlet, The surfactant is extracted by immersing the first porous body precursor in a good solvent having a high solubility in. Examples of such an organic solvent include ethanol, methanol, acetone, hexane and the like.

  In addition, as conditions for immersing the first porous body precursor in an organic solvent to remove the surfactant near the pore inlet, depending on the design of the intended pore, the type of surfactant, etc. Although it can change suitably, it is preferable to set it as the conditions of 30-100 degreeC (more preferably 40-80 degreeC) and immersion time 30-360 minutes (more preferably 30-180 minutes) under atmospheric pressure.

  In addition, when the ion exchange method is adopted as a method of removing the surfactant near the pore inlet of the first porous body precursor, the object is to remove only the surfactant near the pore inlet. The surfactant is extracted by immersing the porous precursor in an acidic solution (such as ethanol containing a small amount of acetic acid) while appropriately changing the conditions according to the design of the pores. As a result, the surfactant present in the vicinity of the pore entrance of the porous precursor is ion-exchanged with hydrogen ions. As such an acidic solution, ethanol, methanol or the like is used as a solvent, and a solution containing a small amount of acid in the solvent is preferable. Further, as such an acid, acetic acid, hydrochloric acid, sulfuric acid and the like are preferable. Moreover, it is preferable that it is about 0.5-20 mass% as content of the acid in an acidic solution.

  The conditions for removing the surfactant in the vicinity of the pore inlet by immersing the first porous body precursor in the acidic solution depend on the design of the intended pore, the type of surfactant, etc. However, it is preferable that the temperature is 30 to 100 ° C. (more preferably 40 to 80 ° C.) and the immersion time is 30 to 360 minutes (more preferably 30 to 180 minutes) under atmospheric pressure. .

  Next, process (C) is demonstrated. In step (C), the second porous body precursor is subjected to a CVD treatment, and an inorganic oxide is laminated in the vicinity of the pore entrance to reduce the pore entrance diameter. It is the process of obtaining. In FIG. 3, the schematic diagram of the longitudinal cross-section of the pore of such a 3rd porous body precursor is shown. In FIG. 3, reference numeral 1 denotes a pore wall, reference numeral 2 denotes a surfactant, and reference numeral 4 conceptually denotes an inorganic oxide layer laminated in the vicinity of the pore inlet.

  Such a CVD method (Chemical Vapor Deposition) is not particularly limited as long as it is a method capable of laminating the inorganic oxide, and is well-known such as thermal CVD, photo CVD, plasma CVD method and the like. The CVD method is mentioned. An apparatus used when performing such a CVD method is not particularly limited, and a known CVD apparatus can be appropriately used.

  The reaction atmosphere employed in such a CVD method may cause combustion of the surfactant and organic groups introduced into the pores of the second porous body precursor depending on the temperature conditions employed when the oxidation atmosphere is employed. An inert atmosphere such as nitrogen or argon is preferable.

  The temperature condition employed in such a CVD method is not particularly limited, but the temperature of the second porous body precursor is preferably 250 ° C. or lower (more preferably 100 to 200 ° C.). When such a temperature condition is less than the lower limit, the lamination speed of the inorganic oxide tends to be slow, and the reaction time and energy consumption tend to increase. On the other hand, if the upper limit is exceeded, the second porous body The surfactant and organic group introduced into the pores of the precursor tend to be decomposed.

The inorganic oxide laminated by such a CVD method is not particularly limited, and examples thereof include silica, zirconia, titania, alumina, P ₂ O _{5 and the} like. Among such inorganic oxides, silica is more preferable from the viewpoint of hydrophilicity.

  The raw material compound used for laminating the inorganic oxide is not particularly limited as long as it can form the inorganic oxide by a CVD method, and examples thereof include trimethoxysilane and tetraethoxysilane. , Tetramethoxysilane, triethoxysilane and the like. Among such raw material compounds, trimethoxysilane and triethoxysilane are more preferable from the viewpoint of being an industrial raw material and capable of reducing cost.

  In addition, in such a step (C), an inorganic oxide is laminated in the vicinity of the pore inlet, whereby the ratio of the pore inlet diameter d2 to the pore inner diameter d1 ([pore inlet diameter] / [fine pore diameter] The pore diameter at the inlet of the pore is reduced so that the pore internal diameter]) is 0.05 to 0.95. In this way, the pore inlet diameter d2 is set so that the ratio of the pore inlet diameter d2 to the pore inner diameter d1 ([pore inlet diameter] / [pore inner diameter]) is 0.05 to 0.95. By reducing the size, the resulting porous body can efficiently utilize capillary condensation of water. For example, a fuel cell having sufficiently high proton conductivity even under a low relative humidity condition where the relative humidity is 40% or less. It is possible to obtain an electrolyte material for use. Conditions for reducing the pore inlet diameter d2 so as to achieve such a ratio are not particularly limited, and may vary depending on the CVD reaction temperature, the type of raw material compound used, the flow rate when introducing the raw material compound, and the like. Therefore, it is necessary to adjust the conditions appropriately according to the CVD method employed. When the thermal CVD method is employed as the CVD method, the thickness of the inorganic oxide layer 4 is particularly correlated with the CVD reaction time, and therefore the thickness can be controlled to some extent by adjusting the CVD reaction time. Thus, the pore inlet diameter d2 can be controlled to a desired size. Thus, by appropriately adjusting the conditions, the ratio of the pore inlet diameter d2 to the pore inner diameter d1 ([pore inlet diameter] / [pore inner diameter]) is 0.05 to 0.95. In this way, the pore inlet diameter d2 can be reduced. In step (C), since the surfactant remains inside the pores of the second porous body precursor, the inorganic oxide layer 4 is formed only near the entrance of the pores by the CVD process. Thus, it is possible to reduce only the pore inlet diameter without changing the regular structure of the pores of the obtained third porous body precursor or the pore diameter inside the pores.

  Next, process (D) is demonstrated. Step (D) is a step of removing the surfactant introduced into the third porous body precursor to obtain a porous body.

  The method for removing the surfactant introduced into the third porous body precursor is not particularly limited, and the surfactant is removed from the silica-based mesoporous material into which the surfactant has been introduced. A known method capable of performing the above can be employed as appropriate, and examples thereof include a method of treating with an organic solvent and an ion exchange method. In the case of employing such a method of treating with an organic solvent, the surfactant is extracted by immersing the third porous body precursor in a good solvent having high solubility in the surfactant. In the case of employing the ion exchange method, the third porous body precursor is immersed in an acidic solution (such as ethanol containing a small amount of hydrochloric acid) and heated at, for example, 50 to 70 ° C. to extract the surfactant. In addition, as an acid used for this acidic solution, hydrochloric acid and a sulfuric acid are preferable. Thereby, the surfactant existing in the pores of the third porous body precursor is ion-exchanged with hydrogen ions. In addition, although hydrogen ions remain in the hole by ion exchange, the problem of blockage of the hole does not occur because the ion radius of the hydrogen ion is sufficiently small.

  Next, process (E) is demonstrated. In the step (E), a bottleneck type silica-based mesoporous material is subjected to a treatment for converting an ion-exchangeable functional group precursor in an organic group introduced into silica in the porous material into an ion-exchangeable functional group. It is the process of obtaining.

  As a method of converting the precursor of such an ion exchange functional group into an ion exchange functional group, any method can be used as long as the precursor of the ion exchange functional group can be converted into an ion exchange functional group. Well, not particularly limited, various methods can be adopted depending on the type of ion-exchange capacity functional group precursor and the type of ion-exchange capacity functional group to be converted. A known method that can be converted into an ion-exchange functional group such as an acid group can be appropriately employed.

  As the treatment for converting into such an ion exchange functional group, for example, when the functional group of the precursor of the ion exchange functional group is a mercapto group, and this is converted into a sulfonic acid group, an oxidizing agent is used. It is possible to employ a method of oxidizing. The method of oxidizing using such an oxidizing agent is not particularly limited as long as it is a method capable of oxidizing a mercapto group and converting it into a sulfonic acid group using an oxidizing agent. The oxidizing agent is not particularly limited as long as it can oxidize a mercapto group and convert it into a sulfonic acid group, and examples thereof include hydrogen peroxide, nitric acid, sulfuric acid, and crown ether. It is done. Among these oxidizing agents, hydrogen peroxide is preferable from the viewpoints of high reactivity and pore retention. In addition, conditions such as reaction temperature and reaction time in the method of oxidizing using such an oxidizing agent are not particularly limited, but the reaction temperature is 100 ° C. or less (more preferably 10 to 80 ° C.). The reaction time is preferably within 30 minutes to 6 hours. When the reaction temperature and reaction time are less than the lower limit, the mercapto group is hardly oxidized, and it tends to be difficult to oxidize the mercapto group and convert it to a sulfonic acid group. In addition, the pores of the silica-based mesoporous material tend to collapse partially.

  In addition, as a treatment for converting into such an ion exchange functional group, the functional group of the precursor of the ion exchange functional group is a cyano group, and when this is converted into a carboxylic acid group, an oxidizing agent is used. It is possible to employ a method of oxidizing. Such an oxidizing agent is not particularly limited as long as it can oxidize a cyano group to be converted into a carboxylic acid group. For example, an acid such as sulfuric acid, hydrochloric acid, acetic acid, formic acid, or a peroxidic acid can be used. Examples thereof include hydrogen and crown ether. Among such oxidizing agents, sulfuric acid is preferable from the viewpoints of high reactivity and pore retention. In addition, conditions such as reaction temperature and reaction time in the method of oxidizing using such an oxidizing agent are not particularly limited. However, when sulfuric acid having a concentration of 1 mol / L or more is used, it is 25 to 150 ° C. ( More preferably, the mixture is refluxed for about 1 to 24 hours under a temperature condition of 50 to 130 ° C.

  In addition, when the functional group of the precursor of the ion-exchange-functional functional group is a chlorosulfonyl group, and this is converted into a sulfonic acid group, the acid used when extracting the surfactant in the step (D) described above. You may employ | adopt the method of exchanging a chlorosulfonyl group into a sulfonic acid group collectively with a solution. Thus, in the method for producing a silica-based mesoporous material including the steps (A) to (E), the step (D) and the step (E) may be performed simultaneously with the acidic solution.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

Example 1
First, the following general formula (4):

It was obtained by previously mixing 0.68 g of 2- (4-chlorosulfonylphenyl) ethyltrimethoxysilane (CSPETMS) and 0.60 g of tetramethoxysilane (TMOS) expressed in a dry nitrogen stream. Ethanol (5.0 ml) was added to the silica raw material (molar ratio of TMOS and CSPETMS: TMOS / CSPETMS = 0.53), and then H ₂ O (993 μl) and 2N HCl (7 μl) were mixed. The mixture was stirred at room temperature (25 ° C.) and 200 rpm for 1 hour to obtain a TMOS / CSPETMS sol solution. Next, 0.81 g of octadecyltrimethylammonium chloride (C ₁₈ TMA ⁺ Cl ⁻ ) as a surfactant, ethanol (10 ml), and H ₂ O (0.1 ml) were added to the obtained TMOS / CSPETMS sol solution. ) And 2N HCl (10 μl) were added and stirred for 2 hours at 300 rpm to obtain a mixed solution.

Next, a four-terminal electrode substrate shown in FIG. 4 (vertical 40 mm, horizontal 20 mm, electrode type: platinum electrode, distance X between electrode 12 (c) and electrode 12 (d): 5 mm, electrode 12 (a) and electrode The distance Y between the electrode 12 (b) and the electrode 12 (d) is 2 mm, the distance between the electrode 12 (a) and the electrode 12 (d) is 1 mm, the distance between the electrode 12 (b) and the electrode 12 (c) is 1 mm, and the electrode 12 ( c) width V: 5 mm and electrode 12 (d) width U: 5 mm) are coated with the mixed solution so as to have a film thickness of 300 nm by a dip coating method to obtain a coated film laminated substrate. It was. Next, after the coated film laminated substrate was placed in an autoclave, TMOS (150 μl) was added to the coated film and treated at a temperature of 120 ° C. for 2 hours. Next, 28% by volume of NH ₃ aqueous solution (100 μl) was added to the coated film, treated at 100 ° C. for 2 hours, and then the thin film was dried at 100 ° C. for 1 hour to obtain a surfactant. A thin film comprising the introduced first porous body precursor was obtained. Thereafter, using a 1% by mass acetic acid solution diluted with ethanol, the surfactant present in the vicinity of the pore inlet of the pores of the first porous body precursor is removed under room temperature (25 ° C.) conditions. A thin film made of the second porous body precursor in which the surfactant remains inside the pores was obtained. FIG. 4 is a schematic diagram showing a four-terminal electrode substrate on which a thin film is formed.

  Next, the thin film of the second porous body precursor thus obtained is subjected to a CVD treatment, and silica is laminated in the vicinity of the pore inlet of the second porous body precursor, so that the third porous body A precursor was obtained. In such a CVD process, a CVD apparatus schematically shown in FIG. 5 was used. The CVD apparatus shown in FIG. 5 basically includes a rotary pump 20, a container R1 for introducing a trap solution 21, a container R2 for introducing water 22, and a thin film of a second porous precursor. A container R3 for introducing the formed substrate 23, a container R4 for introducing the inorganic oxide raw material compound 24, a pressure gauge 25, and a pipe 26 are provided. In such a CVD apparatus, the inflow and release of gas into each container can be controlled by opening and closing valves provided in pipes connected to the containers R1 to R4. Furthermore, in this example, water is introduced into the container R2, a substrate on which the thin film of the second porous precursor obtained as described above is formed is introduced into the container R3, and the inorganic material is introduced into the container R4. Trimethoxysilane (TMOS) was introduced as the oxide raw material compound 24, the trap solution 21 was not used, and the container R1 for introducing the trap solution 21 was emptied.

Moreover, the silica lamination process (CVD process) using such a CVD apparatus was a process in which the following first to fourth processes were repeated 30 times.
<First Step> The system is depressurized by the rotary pump 20 and the thin film 23 is heated at 200 ° C. for 2 hours under reduced pressure conditions (about 10 ⁻³ Pa).
<Second Step> The raw material compound 24 (trimethoxysilane) is evaporated at room temperature, and the thin film 23 is exposed to a trimethoxysilane gas phase for 3 minutes under reduced pressure (about 10 ⁻³ Pa) and 200 ° C.
<Third Step> Water 22 is evaporated at room temperature, and the thin film 23 is exposed to a steam atmosphere for 3 minutes under reduced pressure (about 10 ⁻³ Pa) and 200 ° C.
<Fourth Step> The thin film 23 is heated at a temperature of 200 ° C. for 2 hours under reduced pressure (about 10 ⁻³ Pa).

Subsequently, the substrate on which the thin film of the third porous body precursor was formed was taken out from the CVD apparatus. And the board | substrate with which the thin film of the 3rd porous body precursor was formed was immersed in 1 mass% hydrochloric acid solution (ethanol dilution), and the said 3rd porous body precursor was carried out on 60 degreeC temperature conditions. A thin-film bolt neck type silica in which an organic group having a sulfonic acid group is introduced by removing the surfactant from the thin film and converting the chlorosulfonyl group introduced into the pores into a sulfonic acid group An electrolyte material for a fuel cell comprising a porous mesoporous material was obtained. Incidentally, the H ⁺ amount of sulfonic in groups such bolt neck mold mesoporous silica material, acid - was measured by base titration, H ⁺ amount in the introduced sulfonic acid group in the pores It was confirmed to be 1.3 mmol / g.

(Comparative Example 1)
First, a method similar to the method employed in Example 1 was employed to obtain a substrate on which a thin film made of the second porous body precursor was formed. Next, the substrate on which the thin film made of the second porous body precursor is formed is immersed in a 1% by mass hydrochloric acid solution (ethanol diluted), and the third porous body is formed under a temperature condition of 60 ° C. The surfactant was removed from the precursor film. In this way, the chlorosulfonyl group introduced into the pores is converted into a sulfonic acid group, and a thin-film silica-based mesoporous material into which an organic group having a sulfonic acid group is introduced is used for comparison. A fuel cell electrode material was obtained.

[Evaluation of Fuel Cell Electrode Material Obtained in Example 1 and Comparative Example 1]
<Characteristic evaluation of silica-based mesoporous material>
The pore distribution curves of the thin-film silica-based mesoporous materials obtained in Example 1 and Comparative Example 1 were determined. That is, each silica-based mesoporous material is cooled to a liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is determined by a gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased. The amount of nitrogen gas adsorbed with respect to each equilibrium pressure was plotted, and a nitrogen adsorption isotherm was obtained. Thereafter, the BJH method was used to calculate the pore diameter distribution curve based on the nitrogen adsorption isotherm. The obtained pore size distribution curve is shown in FIG. For reference, a pore size distribution curve was also obtained for a silica mesoporous material (Reference Example 1) obtained in the same manner as in Example 1 except that the number of CVD treatments was 15. The obtained pore size distribution curve is shown in FIG. Further, the pore diameter of each silica mesoporous material obtained from such a pore distribution curve is shown in Table 1, and the specific surface area (BET) of each silica mesoporous material calculated based on the nitrogen adsorption isotherm described above. Method) and pore volume are shown in Table 1, respectively.

  As is apparent from the results shown in Table 1 and FIG. 6, in the silica-based mesoporous material subjected to the CVD treatment (Example 1 and Reference Example 1), peaks were confirmed at two locations in the pore distribution curve, It can be seen that the inlet diameter of the pore is reduced. On the other hand, in the silica-based mesoporous material (Comparative Example 1) obtained without performing the CVD treatment, only one peak was observed in the pore distribution curve. From these results, it can be seen that in Example 1 and Reference Example 1 in which the production method as described above was employed, a silica-based mesoporous material in which only the pore inlet diameter was reduced was obtained. Further, in the silica-based mesoporous material obtained in Example 1, the ratio of the pore inlet diameter to the pore internal diameter of the pore was 0.9 (2.6 / 2.9). On the other hand, the ratio of the pore inlet diameter to the pore internal diameter of the silica-based mesoporous material (Reference Example 1) subjected to 15 CVD treatments ([pore inlet diameter] / [pore internal diameter]) Was 0.93 (2.7 nm / 2.9 nm). From these results, it has been found that, under the CVD process conditions employed in this example, it is necessary to perform about 30 or more CVD processes when the ratio is 0.9 or less.

<Measurement of proton conductivity>
The proton conductivity of the fuel cell electrode material (thin film) obtained in Example 1 and Comparative Example 1 was measured by a four-terminal DC method. FIG. 7 shows a schematic diagram of an apparatus used for measurement of such proton conductivity. In measuring the proton conductivity, the four-terminal electrode substrates 11 on which the fuel cell electrode materials (thin films) obtained in Example 1 and Comparative Example 1 were laminated, respectively, were used. The picoammeter 30 was attached to (c) and the electrode 12 (d), and the current value when 0.5 V was applied was measured. Moreover, the voltmeter 31 was attached to two center electrode 12 (a) and electrode 12 (b), and the voltage was measured. And resistance value was computed from the measured electric current and voltage, and proton conductivity was calculated | required. Such proton conductivity is measured by placing a four-terminal electrode substrate in the gas flow pipe 32 and flowing a gas containing 1% by volume of H ₂ (nitrogen dilution) under a temperature condition of 25 ° C. The relative humidity was changed in the range of 10 to 90%. In such measurement, the relative humidity is first increased to 10 to 90%, and 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%. Proton conductivity was measured under each relative humidity condition (adsorption). Next, the relative humidity is lowered to 90 to 10%, and the proton conductivity is adjusted under the relative humidity conditions of 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, and 10%. Measured (desorption). Further, when measuring the proton conductivity at each relative humidity, the proton conductivity was measured after 5 minutes had passed after the humidity was stabilized at each set relative humidity. A graph showing the relationship between relative humidity (unit:%) and proton conductivity (unit: S / cm) obtained by such measurement is shown in FIG.

  As is clear from the results shown in FIG. 8, the electrode material for a fuel cell of the present invention (Example 1) composed of a bottlenecked silica-based mesoporous material subjected to CVD treatment was obtained without performing CVD treatment. Compared with the fuel cell electrode material (Comparative Example 1) for comparison made of the silica-based mesoporous material, the proton conductivity at the time of adsorption and desorption under a low humidity condition is sufficiently high Was confirmed. It can be seen that such a result is due to the reduction of the inlet diameter of the pores. In addition, in the fuel cell electrode material for comparison (Comparative Example 1), the proton conductivity shows the same behavior at the time of adsorption and desorption, whereas the present invention comprising a bottleneck type silica-based mesoporous material. It was confirmed that the fuel cell electrode material (Example 1) had higher conductivity during desorption and exhibited hysteresis. From these results, it can be seen that the fuel cell electrode material of the present invention (Example 1) has a bottleneck structure in which silica is laminated at the pore inlet and the pore diameter in the vicinity of the inlet is reduced. It was. In addition, as described above, the fuel cell electrode material of the present invention (Example 1) has sufficiently high proton conductivity even under low humidity conditions. Therefore, the use of the fuel cell electrode material of the present invention reduces the humidity. It was found that the power generation efficiency under the conditions was sufficiently improved.

  As described above, according to the present invention, it is possible to provide a fuel cell electrolyte material having sufficiently high proton conductivity under low humidity conditions and sufficiently improved power generation efficiency under low humidity conditions. Become. Therefore, the fuel cell electrolyte material of the present invention is particularly useful as a material for an electrolyte membrane of a fuel cell.

It is a schematic diagram which shows the longitudinal cross-section of the pore of a bottleneck type | system | group silica type mesoporous material. It is a schematic diagram which shows the longitudinal cross-section of the pore of a 2nd porous body precursor. It is a schematic diagram which shows the longitudinal cross-section of the pore of a 3rd porous body precursor. 1 is a schematic diagram of a four-terminal electrode substrate on which thin films of fuel cell electrolyte materials obtained in Example 1 are stacked. FIG. 1 is a schematic longitudinal sectional view schematically showing a CVD apparatus used in Example 1. FIG. 2 is a graph of pore distribution curves of silica-based mesoporous materials obtained in Example 1, Comparative Example 1 and Reference Example 1. It is a schematic diagram of the apparatus used for the measurement of proton conductivity. It is a graph which shows the relationship between the proton conductivity (unit: S / cm) and relative humidity (unit:%) of the electrolyte material for fuel cells obtained in Example 1 and Comparative Example 1.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Pore wall, 2 ... Surfactant, 3 ... Line which shows pore entrance | concept conceptually, 4 ... Inorganic oxide layer, 11 ... 4 terminal electrode board | substrate, 12 (a)-(d) ... Platinum electrode, DESCRIPTION OF SYMBOLS 13 ... Thin film of electrolyte material for fuel cells, 20 ... Rotary pump, 21 ... Trap solution, 22 ... Water, 23 ... Silica mesoporous material, 24 ... Raw material compound of inorganic oxide, 25 ... Pressure gauge, 26 ... Pipe, DESCRIPTION OF SYMBOLS 30 ... Picoammeter, 31 ... Voltmeter, 32 ... Gas flow pipe, d1 ... Pore inside diameter, d2 ... Pore inlet diameter, R1-4 ... Container, A ... Gas flow direction, X ... Electrode 12 (c) , The distance between the electrode 12 (d), Y: the distance between the electrode 12 (a) and the electrode 12 (b), Z: the distance between the electrode 12 (a) and the electrode 12 (d), W: the electrode 12 (b) ) And the electrode 12 (c), V: the width of the electrode 12 (c), U: the width of the electrode 12 (d).

Claims (3)

The pore inlet diameter and pore internal diameter are the following conditions (A) to (B):
[Condition (A)] The pore internal diameter is 1.5 to 30 nm.
[Condition (B)] The ratio of the pore inlet diameter to the pore inner diameter ([pore inlet diameter] / [pore inner diameter]) is 0.05 to 0.95.
And a bottleneck type silica-based mesoporous material in which an organic group having an ion-exchange functional group is introduced into the pores. Battery electrolyte material.   2. The fuel according to claim 1, wherein the ion-exchange capacity functional group is at least one functional group selected from the group consisting of a sulfonic acid group, a sulfonimide group, a phosphoric acid group, and a carboxylic acid group. Battery electrolyte material.   The organic group having an ion-exchange-functional functional group includes at least one hydrocarbon group selected from the group consisting of a chain hydrocarbon group having 6 or less carbon atoms and a cyclic hydrocarbon group having 10 or less carbon atoms. 3. The fuel cell electrolyte material according to claim 1, comprising a group to which an ion exchange function functional group is bonded.

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