JP2022113162A5 - - Google Patents

Description

TECHNICAL FIELD The present invention relates to an electrode and apparatus for splitting water to produce molecular oxygen and hydrogen. More specifically, a conductive thin plate or a conductive non-woven fabric comprising an aromatic amine polymer as an oxidation catalyst for generating oxygen from water (hereinafter referred to as "hydroxylation/oxygen generating catalyst"). A device for producing oxygen by immersing an electrode consisting of an electrode in hydroxide ion-containing water, applying a voltage and / or irradiating with light, and a reduction catalyst for generating hydrogen from water with polyarylene vinylene (hereinafter referred to as "water As a reduction/hydrogen generation catalyst"), an electrode made of a conductive thin plate or conductive nonwoven fabric containing the polyarylene vinylene is immersed in hydrogen ion-containing water, and a device for producing hydrogen by applying voltage, and the above hydroxylation / An electrode equipped with an oxygen generation catalyst and an electrode equipped with a water reduction/hydrogen generation catalyst are combined, immersed in an aqueous electrolyte solution, and oxygen and hydrogen are produced by applying voltage and/or irradiating the hydroxylation/oxygen generation catalyst with light. Regarding the device .

Molecular oxygen is widely used in the oxidative manufacturing process of petrochemicals such as epoxidation, improving combustion efficiency, wastewater treatment with aerobic microorganisms, fisheries such as fish farming, and medical care for respiratory failure.・It is a general-purpose chemical that is used in large amounts. Molecular oxygen is produced by the cryogenic distillation method of air on a large scale, and by the pressure swing separation method and membrane separation method of air on a medium and small scale. On the other hand, molecular hydrogen is not only widely used industrially in ammonia synthesis, petroleum refining, steelmaking, etc., but it is also practically used as a clean energy source and fuel for fuel cells because it emits only water when burned. there is Molecular hydrogen is currently produced mainly in large-scale facilities such as steam reforming of methane and coal gasification, but in the near future , hydrogen production methods that do not rely on fossil resources and do not emit carbon dioxide will be required. . That is, there is a strong demand for a highly efficient method for producing oxygen and hydrogen by splitting water as an environmentally friendly and on - site production method.

One method for producing such oxygen and hydrogen is the electrolysis of water. In particular, there is a high demand for the storage and leveling use of surplus power generated by wind power and solar power generation as hydrogen fuel by water decomposition and the on-site utilization of simultaneously generated oxygen. In the water electrolysis method, acid water electrolysis and alkaline water decomposition using a proton exchange polymer membrane are implemented. There is a strong industrial demand for further development of inexpensive and highly durable electrode catalysts. The catalysts and their electrodes used for water reduction and hydrogen generation include platinum and platinum group catalysts, nickel and transition metal catalysts, and there are many practical and developmental research projects. Electrodes are an extremely important development field together with electrode catalysts for metal-air batteries , which have recently been remarkably developed.

Currently, noble metal oxides such as rutherium oxide and iridium oxide are typical examples of catalysts for generating hydroxide and oxygen for water electrolysis. A metal oxide having a rock salt structure has been developed (Non-Patent Document 1) . In addition to basic research on polynuclear complexes of manganese, which are catalysts for generating oxygen in natural photosynthetic reactions (Non-Patent Document 2), many metal oxides and complexes have been developed and researched. They act as catalysts for the four-electron oxidation of two water molecules to form one oxygen molecule and four protons, but the known catalysts are not always stable in water, especially in acidic or alkaline aqueous solutions.

Moreover, the overvoltage required to electrolyze water by applying a voltage to electrodes made of these catalysts is not low at 0.3 to 0.6 V, and the rate of oxygen generation has been increased per area by devising the shape of the electrodes. The current density of the catalyst itself is 0.1 to several mA/cm ² , and higher catalytic performance is required. Carbon-based materials such as graphene, nitrogen-doped carbon, and carbon nitride have been investigated as catalysts that do not contain metals, but they have not yet achieved high catalytic activity and molding/stability as electrodes (non-metal-containing materials). Patent document 3).

On the other hand, "a method of generating oxygen from water using an organic polymer as an oxidation catalyst" is expected to have an unknown catalytic function, moldability and durability, but there are few reports on it. It has been reported that oxygen is generated at a current density of several mA/cm ² by immersing polyimide formed by impregnating carbon nonwoven fabric in an aqueous solution of pH 13 and applying 1.7 V (vs. reversible hydrogen electrode) as an electrode. , are a few examples (Non-Patent Document 4).

On the other hand, as a water reduction/hydrogen generation electrode for water electrolysis, platinum has been used as a representative, but other precious metals such as palladium and iridium, as well as relatively inexpensive nickel or nickel/cobalt/iron alloys, which have inferior performance, have been put to practical use. It is There are many development studies of transition metal catalysts that can be applied to alkaline electrolysis that can avoid corrosion and acidic vapor due to acid electrolysis (Non-Patent Document 5). Carbon-based materials such as nitrogen-doped carbon have been studied as metal-free catalysts, but their catalytic activity is not high (Non-Patent Document 6). Therefore, there is a demand for a less expensive and highly durable catalyst material that is free from resource constraints.

The present inventors have been studying organic aromatic polymers with oxidation-reduction ability and their functions for many years (Non-Patent Documents 7 and 8). Also, recently, it was reported that a thin layer of thiophene polymer formed on a conductive plate acts on photoelectrochemical decomposition of water and hydrogen generation (Non-Patent Documents 9, 10, and Patent Document 1).

Hiroyuki Nishide, et al., "Method for producing hydrogen", Patent application 2020-065878.

Suen, N-T., et al. Chem. Soc. Rev. 46, 337-365(2017). Park, S., et al. Energy Environ. Sci. 13, 2310-2340 (2020). Zhao, Y. et al. Nat. Commun. 4, 2390(2013). Lin, Y. et al. Angew. Chem. 57, 12563-12566(2018). Mahmood, N., et al. Adv. Sci. 5, 1700464(2018). Hu, C., et al. Energy Environ. Sci. (2019). Oyaizu, K., Nishide, H. Handbook of Conjugated Polymers, CRC Press, 587-594(2019). Oka, K., Nishide, H. Redox Polymer for Energy and Nanomedicine, Royal Soc. Chem. 137-165(2020). Oka, K. et al. Energy Environ. Sci. 11, 1335-1342(2018). Oka, K. et al. Adv. Energy Mater. 9, 1803286(2019).

A specific aromatic polymer with high durability, low cost, and various moldability including thin layer coating is used as a catalyst for hydroxylation and water reduction to create an electrode. It is also an object of the present invention to provide a technique capable of producing oxygen or hydrogen, or both, from water at a high production rate by irradiating a hydroxylated catalyst electrode with light.

Based on the knowledge and experimental techniques of organic aromatic polymers with oxidation-reduction ability, photoelectrochemistry, and water-splitting chemistry, which the present inventors have pioneered in Japan and overseas (Non-Patent Documents 8-10), a series of We explored a wide range of aromatic polymers, and conducted intensive research to develop a simple and highly efficient method for producing molecular oxygen and hydrogen from water. As a result, based on the discovery by the present inventors that the aromatic amine polymer acts as an oxidation catalyst for generating oxygen from water, and the polyarylenevinylene acts as a reduction catalyst for generating hydrogen from water, a catalyst was prepared from both catalysts. By using a conductive thin plate or a conductive non-woven fabric as an electrode, applying a slight overvoltage and/or irradiating the hydroxyl/oxygen generating electrode with light, we have completed the present invention that can produce both oxygen and hydrogen at a high production rate. rice field. Aromatic amine polymers and polyarylenevinylenes are organic polymers that (1) can be obtained at low cost without resource constraints, (2) have extremely high chemical durability in water over a wide pH range, and (3) have various properties. It can be coated with a thin layer on the surface of the collector substrate with high adhesion as a catalyst, and is mechanically tough. It also offers unique advantages such as the ability to control reaction termination due to the adhesion of oxygen and hydrogen bubbles by molecular design, such as the hydrophilicity and hydrophobicity of the polymer layer and surface roughness.

Specifically, the present invention uses an electrode comprising an aromatic amine polymer as an oxidation catalyst for generating molecular oxygen from water and/or an electrode comprising polyarylenevinylene as a reduction catalyst for generating hydrogen from water. characterized by combining these electrodes with an existing hydrogen generating electrode or oxygen generating electrode that forms a pair, or combining these electrodes with each other, immersing them in hydroxide ion-containing water, applying voltage and / or oxygen generating catalyst Provided is a method for producing molecular oxygen and hydrogen, which is also characterized by irradiating an electrode with light.

In addition, the present invention provides poly(triphenylamine)s, which are representative examples of aromatic amine polymers, by coating the starting triphenylamines on a conductive thin plate or conductive nonwoven fabric and exposing them to iodine vapor. , or addition of iodine to a solution of triphenylamines, which is an oxidative polymerization reaction.

More specifically, the present invention uses an aromatic amine polymer as a catalyst for generating oxygen by oxidation of water (hereinafter referred to as a "catalyst for hydroxylation/oxygen generation"), and polyarylene vinylene or a derivative thereof as a catalyst for generating oxygen by oxidizing water. As a hydrogen generation catalyst by reduction (hereinafter referred to as "water reduction/hydrogen generation catalyst"), these are immersed in water, and the hydroxylation/oxygen generation catalyst and the water reduction/hydrogen generation catalyst are connected with a conductive wire. , a method for producing oxygen and hydrogen from water by applying a voltage and/or irradiating a hydroxylated/oxygen generating catalyst with light.

（式中、
nは整数を表し、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、無いか、又はフルオレン基を表す）。 In the method , electrode, and apparatus for producing oxygen and hydrogen from water of the present invention, the aromatic amine polymer may produce oxygen and hydrogen represented by the following formula (I):

(In the formula,
n represents an integer,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X is absent or represents a fluorene group).

（式中、
nは、整数を表し、
R1及びR2は、それぞれ同一又は異なって、アルキル基を表す）。 In the method , electrode, and apparatus for producing oxygen and hydrogen from water of the present invention, oxygen and hydrogen may be produced in which the polyarylene vinylene is a poly(phenylene vinylene) represented by the following formula (II):

(In the formula,
n represents an integer,
R1 and R2 are the same or different and represent an alkyl group).

Further, in the present invention, an aromatic amine polymer is immersed in water as a catalyst for generating oxygen by oxidation of water (hereinafter referred to as "oxygen hydroxide generating catalyst"), and by applying voltage and/or light irradiation, oxygen is produced. Provided are methods , electrodes and apparatus for

（式中、
nは整数を表し、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、無いか、又はフルオレン基を表す）。 The present invention also provides the method, electrode and apparatus for producing oxygen and hydrogen, and the catalyst for hydroxylation and oxygen generation used in the method for producing oxygen, wherein the aromatic amine polymer comprises the following Provided is a hydroxylation/oxygen evolution catalyst which is a poly(triphenylamine) represented by formula (III):

(In the formula,
n represents an integer,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X is absent or represents a fluorene group).

（式中、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、-H、又はフルオレン基を表す）。 The present invention also provides a method for producing the above-described catalyst for generating hydroxylation and oxygen, wherein a triphenylamine compound represented by the following formula (IV) is applied to a conductive thin plate or conductive nonwoven fabric, and exposed to iodine vapor. Alternatively, iodine is added to a solution of triphenylamines to provide a production method for obtaining the poly(triphenylamines) by an oxidative polymerization reaction:

(In the formula,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X represents -H or a fluorene group).

In the method for producing a hydroxylation/oxygen generating catalyst of the present invention, a thin layer of an aromatic amine polymer may be formed on a conductive thin plate or conductive nonwoven fabric, or may be formed as a thin plate composed of an aromatic amine polymer and a conductive aid. be.

Furthermore, in the present invention, polyarylene vinylene or a derivative thereof is immersed in water as a hydrogen generation catalyst by water reduction (hereinafter referred to as "water reduction/hydrogen generation catalyst"), and voltage is applied to produce hydrogen. provide a way.

（式中、
nは、整数を表し、
R1及びR2は、それぞれ同一又は異なって、アルキル基を表す）。 The present invention also provides a water reduction/hydrogen generation catalyst used in the method for producing oxygen and hydrogen and the method for producing hydrogen, wherein the polyarylene vinylene is a poly( Provided is a water reduction/hydrogen generation catalyst characterized by being a phenylene vinylene):

(In the formula,
n represents an integer,
R1 and R2 are the same or different and represent an alkyl group).

The present invention also provides a method for producing the water reduction/hydrogen generation catalyst, wherein a thin layer of polyarylene vinylene or a derivative thereof is formed on a conductive thin plate or a conductive nonwoven fabric, or polyarylene vinylene or a derivative thereof and a conductive agent are formed. Provided is a method for producing a water reduction/hydrogen generation catalyst formed as a thin plate comprising an agent.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel technology for producing oxygen and/or hydrogen that is simple, environmentally friendly, and has a high water decomposition rate.

A simple reaction vessel constructed by placing a conductive plate formed from a hydroxylation/oxygen generating catalyst and a conductive plate formed from a water reduction/hydrogen generating catalyst in water and connecting the two with a lead wire ( This includes the case where one side is implemented with a platinum coil, etc.).

1. Method for Producing Oxygen and/or Hydrogen One of the embodiments of the present invention is a method for producing oxygen and/or hydrogen by decomposing water.

More specifically, the method for producing oxygen and hydrogen comprises conducting a hydroxylation/oxygen generation catalyst typified by an aromatic amine polymer and a water reduction catalyst typified by polyarylenevinylene that generates hydrogen from water. It is a method of producing oxygen and hydrogen from water by combining with a wire, applying voltage and/or irradiating a hydroxylated/oxygen generating catalyst with light.

A method , electrodes and apparatus for producing oxygen and hydrogen will be described with reference to FIG. Oxygen gas is generated in the left compartment in which a conductive plate comprising a hydroxylation/oxygen generating catalyst is installed, and hydrogen gas is generated in the right compartment in which a conductive plate comprising a water reduction/hydrogen generating catalyst is installed. Both compartments are open to each other at the bottom, and the provided water is used in common. Both the hydroxylation and water reduction reactions are mutually compensating and voltages are applied as required. In addition, the application of voltage is reduced by irradiating the hydroxylated/oxygen generating catalyst with light.

In addition, a method for producing oxygen uses a hydroxylation/oxygen generating catalyst typified by an aromatic amine polymer, and produces oxygen from water by applying voltage and/or irradiating the hydroxylating/oxygen generating catalyst with light. The method.

Further, the method for producing hydrogen is a method for producing hydrogen from water by applying a voltage using a water reduction catalyst represented by polyarylenevinylene that generates hydrogen from water.

A more detailed description is provided below.

(1) Aromatic amine polymers that act as catalysts for hydroxylation and oxygen generation They are known as polymer materials with hole transport ability, and some of them are practically used as hole transport layers and films in organic EL, organic transistors, and photoelectric conversion elements. The aromatic amine polymer is not applied as a hole transport material in these dry elements and devices, but is in contact with water in a wet process, and works as a catalyst that oxidizes water molecules to generate oxygen gas. The discovery is the starting point of the present invention.

（式中、
nは整数を表し、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、無いか、又はフルオレン基を表す）。 The aromatic amine polymer that serves as a hydroxylation/oxygen generation catalyst is represented by Formula I below.

(In the formula,
n represents an integer,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X is absent or represents a fluorene group).

In formula (I), the "alkyl group" is preferably a C1-C6 alkyl group, more preferably a C1-C3 alkyl group, most preferably methyl.

In this macromolecule composed of aromatic tertiary amines, both the tertiary amine itself and the one-electron oxidized quaternary ammonium cation radical (corresponding to a hole) interact with the three aromatic rings through resonance effects and steric protection. The potential of cation radicals (0.32 V vs. Ag/AgCl electrode) is more positive (noble) than the oxidation potential of water (0.2-0.3 V) under the same conditions. , itself reverts to a tertiary amine and is thought to be capable of repeatedly catalytically oxidizing water. In polymeric amines, many amine/ammonium cation radical catalyst sites are densely present, so four-electron oxidation (Equation 1), which is necessary for water oxidation and oxygen generation reactions, is thought to be possible.
2H2O → _{O2 +} 4H ⁺ + 4e ^- (1)

Furthermore, if the aromatic amine polymer has a high light absorption coefficient, water decomposition assisted by light irradiation becomes possible.

（式中、
nは、整数を表し、
R1及びR2は、それぞれ同一又は異なって、アルキル基を表す）。 (2) Polyarylenevinylene and its Derivatives as Water Reduction/Hydrogen Generation Catalysts Polyarylenevinylene and its derivatives as water reduction/hydrogen generation catalysts include polymers represented by the following formula (II).

(In the formula,
n represents an integer,
R1 and R2 are the same or different and represent an alkyl group).

In formula (II), the alkyl group is preferably a molecular or linear C1-C12 alkyl group, R1 is a substituent represented by the following formula (IIa) or (IIb), and R2 is more preferably a methyl group. .

The discovery by the inventors, which is the second starting point of the present invention, is that the vinylene group of the polyarylene vinylene acts as a catalyst for reducing water molecules or protons to generate hydrogen gas. The vinylene group is dehydrogenated and converted to an ethynylene group, and the conversion between the two is believed to act as a two-electron reduction catalyst.

(3) Manufacturing method of conductive substrate The hydroxylation/oxygen generation catalyst is formed by forming a thin layer of the above aromatic amine polymer on a conductive thin plate or non-woven fabric, or by forming a thin plate consisting of an aromatic amine polymer and a conductive aid. formed as It can also be formed by applying triphenylamines onto a conductive thin plate or non-woven fabric and obtaining a thin layer of poly(triphenylamine)s by an oxidative polymerization reaction in which it is exposed to iodine vapor.

The water reduction/hydrogen generation catalyst is formed by forming a thin layer of polyarylene vinylene or a derivative thereof on a conductive thin plate or non-woven fabric, or forming a thin plate composed of polyarylene vinylene or a derivative thereof and a conductive aid.

Glassy carbon, carbon paper, conductive glass or conductive plastic film can be used as the conductive thin plate, carbon felt can be used as the conductive nonwoven fabric, and carbon fiber, carbon nanotube or the like can be used as the conductive aid.

2. Hydroxygenation/oxygen evolution catalyst and its production method Another embodiment of the present invention is a hydroxylation/oxygen evolution catalyst formed of an aromatic amine polymer and a production method thereof.

（式中、
nは整数を表し、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、無いか、又はフルオレン基を表す）。 More specifically, the aromatic amine polymer is a hydroxylation/oxygen generation catalyst in which poly(triphenylamine)s represented by the following formula (III):

(In the formula,
n represents an integer,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X is absent or represents a fluorene group).

（式中、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、-H、又はフルオレン基を表す）。 A method for producing a hydroxylation/oxygen generating catalyst is to coat a triphenylamine compound represented by the following formula (IV) on a conductive thin plate or conductive nonwoven fabric and expose it to iodine vapor, or add iodine to a solution of triphenylamine compounds. can be prepared by adding the oxidative polymerization reaction to obtain the poly(triphenylamine)s:

(In the formula,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X represents -H or a fluorene group).

In the method for producing a hydroxylation/oxygen generating catalyst of the present invention, a thin layer of an aromatic amine polymer is formed on a conductive thin plate or a conductive non-woven fabric, or a thin plate composed of an aromatic amine polymer and a conductive aid is formed. A hydroxylation/oxygen generation catalyst can be produced by

Glassy carbon, carbon paper, conductive glass or conductive plastic film can be used as the conductive thin plate, carbon felt can be used as the conductive nonwoven fabric, and carbon fiber, carbon nanotube or the like can be used as the conductive aid.

Oxygen can be produced from water by using the catalyst for generating hydroxylation/oxygen of the present invention, immersing it in water, and applying a voltage and/or irradiating the catalyst for generating hydroxylation/oxygen with light.

3. Water Reduction/Hydrogen Generation Catalyst and Manufacturing Method Thereof Another embodiment of the present invention is a water reduction/hydrogen generation catalyst and a manufacturing method thereof.

（式中、
nは、整数を表し、
R1及びR2は、それぞれ同一又は異なって、アルキル基を表す）。 The water reduction/hydrogen generation catalyst of the present invention is a water reduction/hydrogen generation catalyst used in the above method for producing oxygen and/or hydrogen, wherein the polyarylene vinylene is a poly(phenylene) represented by the following formula (V). (Phenylene vinylene) is a water reduction/hydrogen generation catalyst:

(In the formula,
n represents an integer,
R1 and R2 are the same or different and represent an alkyl group).

In the method for producing a water reduction/hydrogen generation catalyst of the present invention, a thin layer of polyarylene vinylene or a derivative thereof is formed on a conductive thin plate or conductive nonwoven fabric, or formed as a thin plate composed of polyarylene vinylene or a derivative thereof and a conductive aid. It can be manufactured by

Glassy carbon, carbon paper, conductive glass or conductive plastic film can be used as the conductive thin plate, carbon felt can be used as the conductive nonwoven fabric, and carbon fiber, carbon nanotube or the like can be used as the conductive aid.

Hydrogen can be produced from water by immersing the water reduction catalyst of the present invention in water and applying a voltage.

Examples will be described in detail below. All documents mentioned herein are hereby incorporated by reference in their entirety. The examples described herein are illustrative of embodiments of the invention and should not be construed as limiting the scope of the invention.

<Production of oxygen gas using 4-nitrotriphenylamine polymer>
(1) Polymerization of 4-nitrotriphenylamine with iodine vapor on a glassy carbon thin plate Dissolve 100 mg of 4-nitrotriphenylamine (Tokyo Chemical Industry Co., Ltd., product code: N0831) in 10 mL of chlorobenzene and 4 mL was spin-coated (3 seconds, 3000 rpm, then 30 seconds, 3 seconds) on a 5 cm square glassy carbon thin plate (manufactured by ALLIANCE Biosystems Inc.). This was placed in a bell jar, sealed with 0.5 g of iodine placed on another petri dish, and heated at 70° C. for 2 hours. The 4-nitrotriphenylamine-coated surface of the thin plate was annealed in a heat dryer at 120°C for 2 hours, and then washed 3 times with 50 mL of chlorobenzene.

The UV-visible-infrared absorption of the coated layer had a strong absorption band in the light wavelength region of 300-60 nm. There was no absorption in the near-infrared region, indicating that it was a pure undoped triphenylamine polymer.

Also, 100 mg of 4-nitrotriphenylamine (Tokyo Chemical Industry Co., Ltd., product code: N0831) and 0.5 g of iodine were dissolved in 10 mL of chlorobenzene, and the mixture was heated and stirred at 70° C. for 2 hours. Mass spectrometric analysis of the solvent-soluble portion of the same polymer synthesized by solution polymerization by gel permeation chromatography revealed a maximum molecular weight of 3,200. Raman spectroscopy (excitation wavelength 785 nm) showed a strong absorption at 852 cm-1, supporting the formation of a linear polymer. Measurements with a general-purpose multifunctional X-ray diffractometer (RINT-Ultima III, manufactured by Rigaku Co., Ltd.) (measurement from 4° with oblique incidence parallel method) show the formation of amorphous polymers with a broad spectrum. rice field.

The level of the highest occupied molecular orbital was calculated to be -5.4 eV from atmospheric photoelectron yield spectroscopy of the thin layer. Furthermore, the level of the lowest unoccupied molecular orbital was calculated to be -3.2 eV from the bandgap calculated from the ultraviolet absorption spectrum.

(2) Oxygen production by light irradiation and voltage application Both were connected with a copper wire, placed in a two-compartment water tank as shown in Fig. 1, filled with 60 mL of an aqueous potassium hydroxide solution of pH 14, and a voltage of +0.80 V vs. Ag/AgCl (using a reference electrode, 0.4 V as overvoltage). was applied, and oxygen was produced by light irradiation (pseudo sunlight, 1000 W/m ² as irradiance, manufactured by Asahi Spectrosco Co., Ltd.).

The amount of oxygen produced was quantified by gas chromatography and an oximeter (PreSens, product number pH-1 SMA LG1).

10.4, 26.0 and 51.5 mL of oxygen gas were generated 2, 5 and 10 hours after the start of voltage application and light irradiation.

<Production of oxygen gas using poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (commercially available)>

100 mg of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (Sigma Aldrich Co., product code: 702471) was dissolved in 10 mL of chlorobenzene, and 2 mL of the solution was applied to a glassy carbon thin plate ( ALLIANCE Biosystems Inc.) was spin coated (3 seconds, 3000 rpm, then 30 seconds, 3 seconds) on a 5 cm square. The thin plate was annealed at 120°C for 2 hours in a heat dryer.

Oxygen was produced in the same manner as in Example 1, and 22.3 mL of oxygen gas was produced 5 hours after the start of voltage application and light irradiation.

<Oxygen production by voltage application only using 4-nitrotriphenylamine polymer>
When 4-nitrotriphenylamine polymer was used in the same manner as in Example 1 and oxygen was produced only by voltage application, 14.5 mL of oxygen gas was produced 5 hours after the start of voltage application.

<Production of hydrogen gas from poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene]>
50 mg of poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (Sigma Aldrich Co., product code: 546461) was dissolved in 10 mL of chlorobenzene, and the solution was A 5 cm square piece of carbon felt (manufactured by EC Frontier) was impregnated and annealed at 120° C. for 2 hours in a heat dryer.

Both the poly(phenylene vinylene) sheet and the platinum coil electrode were connected with a copper wire, placed in a two-compartment water tank as shown in Fig. 1, filled with 60 mL of a pH 1 sulfuric acid aqueous solution, and -0.4 V vs. Ag/AgCl (-0.4 V vs. Ag/AgCl ( Hydrogen was produced by using a reference electrode and applying a voltage of 0.35 V) as an overvoltage. The amount of hydrogen produced was quantified by gas chromatography. One hour after the start of voltage application, 104 mL of hydrogen gas was generated.

<Production of hydrogen gas using poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]>
Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4- Phenylene vinylene] (Sigma Aldrich Co., product code: 541443) was used to produce hydrogen in the same manner as in Example 4. As a result, 97.2 mL of hydrogen gas was generated 5 hours after the start of voltage application.

A glassy carbon 5 cm square thin plate coated with a thin layer of triphenylamine polymer in Example 1 and a poly(phenylene vinylene) sheet in Example 5 were connected with a copper wire, and placed in a two-compartment water tank as shown in FIG. It was installed, filled with 60 mL of an aqueous potassium hydroxide solution of pH 14, and a voltage of 2.1 V was applied to produce oxygen gas and hydrogen gas. The amount of hydrogen gas produced was quantified by gas chromatography. Two hours after the start of voltage application, 9.6 mL of oxygen gas and 18.8 mL of hydrogen gas were generated.

（式中、
nは整数を表し、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、無いか、又はフルオレン基を表す）。
（態様３）
前記ポリアリーレンビニレンが下記式(II)で表わされるポリ（フェニレンビニレン）類であることを特徴とする、態様１又は２に記載の酸素と水素を製造する装置：

（式中、
nは、整数を表し、
R1及びR2は、それぞれ同一又は異なって、アルキル基を表す）。
（態様４）
芳香族アミン高分子を水の酸化による酸素発生触媒（以下、「水酸化酸素発生触媒」と記載）を備えた電極を水に浸漬し、前記電極に電圧印加及び／又は光照射により、酸素を製造する装置。
(態様５）
態様１～３に記載の酸素と水素を製造する装置及び態様４に記載の酸素を製造する装置で使用される水酸化・酸素発生触媒を備えた電極であって、前記芳香族アミン高分子が、下記式(III)で表されるポリ（トリフェニルアミン）類であることを特徴とする電極：

（式中、
nは整数を表し、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、無いか、又はフルオレン基を表す）。
（態様６）
態様５に記載の電極であって、下記式(IV)で表されるトリフェニルアミン類を導電薄板や導電不織布上に塗布して、ヨウ素蒸気に曝す、又はトリフェニルアミン類の溶液にヨウ素を加える、酸化重合反応で前記ポリ（トリフェニルアミン）類を得ることを特徴とする電極：

（式中、
R1は、-H、アルキル基、フェニル基、ハロゲン基、エーテル基、カルバゾール基、トリフェニルアミン基、ニトロ基、アセチレニル基、チエニル基、アミノ基、ホルミル基又はボロン基を表し、
R2及びR3は、それぞれ同一又は異なって、-H又はアルキル基を表し、
Xは、-H、又はフルオレン基を表す）。
（態様７）
芳香族アミン高分子の薄層を導電薄板や導電不織布上に形成、又は、芳香族アミン高分子と導電助剤から成る薄板として形成することを特徴とする、態様６に記載の電極。
（態様８）
ポリアリーレンビニレン又はその誘導体を、水の還元による水素発生触媒（以下、「水還元・水素発生触媒」と記載）として、水に浸漬し、電圧印加により、水素を製造する装置。
(態様９）
態様１～３に記載の酸素と水素を製造する装置及び態様８に記載の水素を製造する装置で使用される水還元・水素発生触媒を備えた電極であって、前記ポリアリーレンビニレンが下記式(V)で表わされるポリ（フェニレンビニレン）類であることを特徴とする電極：

（式中、
nは、整数を表し、
R1及びR2は、それぞれ同一又は異なって、アルキル基を表す）。
（態様１０)
態様９に記載の電極であって、ポリアリーレンビニレン若しくはその誘導体の薄層を導電薄板や導電不織布上に形成、又は、ポリアリーレンビニレン若しくはその誘導体と導電助剤から成る薄板として形成することを特徴とする電極。 In addition, the present disclosure includes the following aspects 1 to 10.
(Aspect 1)
An aromatic amine polymer is used as a catalyst for generating oxygen by oxidizing water (hereinafter referred to as a "catalyst for hydroxylation/oxygen generation"), and a polyarylene vinylene or a derivative thereof is used as a catalyst for generating hydrogen by reducing water (hereinafter referred to as a "water These are immersed in water, the hydroxylation/oxygen generation catalyst and the water reduction/hydrogen generation catalyst are connected with a conductive wire, voltage is applied and / or hydroxylation/oxygen A device that produces oxygen and hydrogen from water by irradiating light to the generation catalyst.
(Aspect 2)
The apparatus for producing oxygen and hydrogen according to aspect 1, wherein the aromatic amine polymer is represented by the following formula (I):

(In the formula,
n represents an integer,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X is absent or represents a fluorene group).
(Aspect 3)
The apparatus for producing oxygen and hydrogen according to aspect 1 or 2, wherein the polyarylene vinylene is a poly(phenylene vinylene) represented by the following formula (II):

(In the formula,
n represents an integer,
R1 and R2 are the same or different and represent an alkyl group).
(Aspect 4)
An electrode equipped with an oxygen generating catalyst (hereinafter referred to as a "hydroxyl oxygen generating catalyst") by oxidation of an aromatic amine polymer with water is immersed in water, and oxygen is generated by applying a voltage and/or light irradiation to the electrode. Equipment to manufacture.
(Aspect 5)
An electrode equipped with a hydroxylation/oxygen generation catalyst used in the apparatus for producing oxygen and hydrogen according to aspects 1 to 3 and the apparatus for producing oxygen according to aspect 4, wherein the aromatic amine polymer is , an electrode characterized by being poly(triphenylamine)s represented by the following formula (III):

(In the formula,
n represents an integer,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X is absent or represents a fluorene group).
(Aspect 6)
In the electrode according to aspect 5, a triphenylamine represented by the following formula (IV) is applied on a conductive thin plate or conductive nonwoven fabric and exposed to iodine vapor, or iodine is added to a solution of triphenylamine. In addition, an electrode characterized by obtaining the poly(triphenylamine)s by an oxidative polymerization reaction:

(In the formula,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X represents -H or a fluorene group).
(Aspect 7)
7. The electrode according to aspect 6, wherein the thin layer of the aromatic amine polymer is formed on a conductive thin plate or conductive non-woven fabric, or formed as a thin plate comprising the aromatic amine polymer and a conductive aid.
(Aspect 8)
An apparatus for producing hydrogen by immersing polyarylenevinylene or a derivative thereof in water as a catalyst for hydrogen generation by water reduction (hereinafter referred to as "water reduction/hydrogen generation catalyst") and applying voltage.
(Aspect 9)
An electrode provided with a water reduction/hydrogen generation catalyst used in the apparatus for producing oxygen and hydrogen according to aspects 1 to 3 and the apparatus for producing hydrogen according to aspect 8, wherein the polyarylene vinylene is represented by the following formula: Electrodes characterized in that they are poly(phenylene vinylene)s represented by (V):

(In the formula,
n represents an integer,
R1 and R2 are the same or different and represent an alkyl group).
(Aspect 10)
The electrode according to mode 9, characterized in that a thin layer of polyarylene vinylene or a derivative thereof is formed on a conductive thin plate or conductive nonwoven fabric, or formed as a thin plate composed of polyarylene vinylene or a derivative thereof and a conductive aid. electrode.

Claims (10)

An aromatic amine polymer is used as a catalyst for generating oxygen by oxidizing water (hereinafter referred to as a "catalyst for hydroxylation/oxygen generation"), and a polyarylene vinylene or a derivative thereof is used as a catalyst for generating hydrogen by reducing water (hereinafter referred to as a "water These are immersed in water, the hydroxylation/oxygen generation catalyst and the water reduction/hydrogen generation catalyst are connected with a conductive wire, voltage is applied and / or hydroxylation/oxygen A device that produces oxygen and hydrogen from water by irradiating light to the generation catalyst. The apparatus for producing oxygen and hydrogen according to claim 1, wherein the aromatic amine polymer is represented by the following formula (I):

(In the formula,
n represents an integer,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X is absent or represents a fluorene group). The apparatus for producing oxygen and hydrogen according to claim 1 , wherein the polyarylene vinylene is a poly(phenylene vinylene) represented by the following formula (II):

(In the formula,
n represents an integer,
R1 and R2 are the same or different and represent an alkyl group). An electrode equipped with an oxygen generating catalyst (hereinafter referred to as a "hydroxyl oxygen generating catalyst") by oxidation of an aromatic amine polymer with water is immersed in water, and oxygen is generated by applying a voltage and/or light irradiation to the electrode. Equipment to manufacture. An electrode equipped with a hydroxylation/oxygen generation catalyst used in the apparatus for producing oxygen and hydrogen according to any one of claims 1 to 3 and the apparatus for producing oxygen according to claim 4, wherein An electrode characterized in that the molecules are poly(triphenylamine)s represented by the following formula (III):

(In the formula,
n represents an integer,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X is absent or represents a fluorene group). 6. The electrode according to claim 5, wherein a triphenylamine represented by the following formula (IV) is coated on a conductive thin plate or conductive nonwoven fabric and exposed to iodine vapor, or iodine is added to a triphenylamine solution. and an electrode characterized in that the poly(triphenylamine)s are obtained by an oxidative polymerization reaction:

(In the formula,
R represents -H, an alkyl group, a phenyl group, a halogen group, an ether group, a carbazole group, a triphenylamine group, a nitro group, an acetylenyl group, a thienyl group, an amino group, a formyl group or a boron group;
R2 and R3 are each the same or different and represent -H or an alkyl group;
X represents -H or a fluorene group). 7. The electrode according to claim 6, wherein a thin layer of aromatic amine polymer is formed on a conductive thin plate or conductive non-woven fabric, or formed as a thin plate composed of aromatic amine polymer and conductive aid. An apparatus for producing hydrogen by immersing polyarylenevinylene or a derivative thereof in water as a catalyst for hydrogen generation by water reduction (hereinafter referred to as "water reduction/hydrogen generation catalyst") and applying voltage. An electrode equipped with a water reduction/hydrogen generation catalyst used in the apparatus for producing oxygen and hydrogen according to any one of claims 1 to 3 and the apparatus for producing hydrogen according to claim 8, wherein the polyarylenevinylene is Electrodes characterized by being poly(phenylene vinylene)s represented by the following formula (V):

(In the formula,
n represents an integer,
R1 and R2 are the same or different and represent an alkyl group). 10. The electrode according to claim 9, wherein a thin layer of polyarylene vinylene or a derivative thereof is formed on a conductive thin plate or conductive nonwoven fabric, or formed as a thin plate composed of polyarylene vinylene or a derivative thereof and a conductive aid. An electrode characterized by: