# US 2014/0150855 A1 · Porous structure body and method for producing the same

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- Number: US 2014/0150855 A1
- Document ID: US20140150855A1
- Status: Published application
- Kind: A1
- Application number: 14/176,543
- Filed: 2014-02-10
- Published: 2014-06-05
- Earliest claimed: 2011-08-08
- Assignees: Ajinomoto Co., Inc.
- Applicants: Ajinomoto Co., Inc.
- Inventors: Ippei INOUE; Ichiro Yamashita; Bin Zheng; Hisashi Yasueda; Yukiharu Uraoka; Yasuaki Ishikawa
- Web page: https://patentgrep.com/patent/US20140150855A1

## CPC

- H10F 71/138: {Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes}
- B82Y 10/00: Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01B 32/16: Preparation
- C01B 32/174: Derivatisation; Solubilisation; Dispersion in solvents
- C01G 9/02: Oxides; Hydroxides
- C01G 23/047: Titanium dioxide
- C07K 14/195: from bacteria
- H01G 9/2031: {comprising titanium oxide, e.g. TiO2 (H01G9/2036 takes precedence)}
- H10K 85/225: {comprising substituents}
- H10K 85/761: {Biomolecules or bio-macromolecules, e.g. proteins, chlorophyl, lipids or enzymes}
- C07K 2319/00: Fusion polypeptide
- C07K 2319/20: containing a tag with affinity for a non-protein ligand
- C07K 2319/70: containing domain for protein-protein interaction
- H01G 9/204: {comprising zinc oxides, e.g. ZnO (H01G9/2036 takes precedence)}
- H01G 9/2045: {comprising a semiconductor electrode comprising elements of the fourth group of the Periodic Table with or without impurities, e.g. doping materials}
- H01M 4/8605: {Porous electrodes}
- H10K 30/821: {comprising carbon nanotubes}
- Y02E 10/542: Dye sensitized solar cells
- Y02E 10/549: Organic PV cells
- Y02E 60/50: Fuel cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C07K: PEPTIDES (peptides in foodstuffs A23; obtaining protein compositions for foodstuffs, working-up proteins for foodstuffs A23J; preparations for medicinal purposes A61K; peptides containing beta-lactam rings C07D; cyclic dipeptides not having in their molecule any other peptide link than those which form their ring, e.g. piperazine-2,5-diones, C07D; ergot alkaloids of the cyclic peptide type C07D519/02; macromolecular compounds having statistically distributed amino acid units in their molecules, i.e. when the preparation does not provide for a specific; but for a random sequence of the amino acid units, homopolyamides and block copolyamides derived from amino acids C08G69/00; macromolecular products derived from proteins C08H1/00; preparation of glue or gelatine C09H; single cell proteins, enzymes C12N; genetic engineering processes for obtaining peptides C12N15/00; compositions for measuring or testing processes involving enzymes C12Q; investigation or analysis of biological material G01N33/00)
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A functional material having excellent photocatalytic activity, electric characteristics and the like is provided. A porous structure body 10 comprises a first target material 20 and an aggregate body 30 formed by aggregation of the first material. The aggregate body 30 adheres to the first target material and is located so as to surround the first target material. The aggregate body has a plurality of first pores 32 unevenly distributed near the first target material in the aggregate body and a plurality of second pores 34 scattered over the aggregate body.

## Claims

### Claim 1

A porous structure body comprising: a first target material; and an aggregate body formed by aggregation of a second target material, the aggregate body adhering to the first target material and being located so as to surround the first target material, wherein
the aggregate body has a plurality of first pores unevenly distributed near the first target material in the aggregate body and a plurality of second pores scattered over the aggregate body.

### Claim 2 (depends on 1)

The porous structure body according to claim 1, wherein the first target material is a carbon material selected from the group consisting of carbon nanotubes, carbon nanohorns, graphene sheets, fullerenes, and graphite.

### Claim 3 (depends on 1)

The porous structure body according to claim 1, wherein the second target material is titanium oxide or zinc oxide.

### Claim 4 (depends on 1)

The porous structure body according to of claim 1, further comprising a material put in the first pores and different from the second target material.

### Claim 5 (depends on 4)

The porous structure body according to claim 4, wherein the material is nanoparticles of a metal selected from the group consisting of iron oxide, nickel, cobalt, manganese, phosphorus, uranium, beryllium, aluminum, cadmium sulfide, palladium, chromium, copper, silver, a gallium complex, platinum cobalt, silicon oxide, cobalt oxide, indium oxide, platinum, gold, gold sulfide, zinc selenide, and cadmium selenide.

### Claim 6 (depends on 5)

The porous structure body according to claim 5, wherein the material is iron oxide nanoparticles.

### Claim 7 (depends on 1)

The porous structure body according to claim 1, wherein the first pores have a diameter within a range of 5 nm to 15 nm.

### Claim 8 (depends on 1)

The porous structure body according to of claim 1, wherein distances to each the first pore from a surface of the first target material are identical and within a range of 1 nm to 500 nm.

### Claim 9 (depends on 1)

An electronic device comprising, as a functional material, the porous structure body according to claim 1.

### Claim 10 (depends on 9)

The electronic device according to claim 9, wherein the electronic device is a solar cell.

### Claim 11 (depends on 10)

The electronic device according to claim 10, wherein the solar cell comprises the porous structure body as a material for an electrode or as a functional material placed on the electrode.

### Claim 12 (depends on 11)

The electronic device according to claim 11, wherein the electronic device is a dye-sensitized solar cell.

### Claim 13

A method for producing a porous structure body, comprising the steps of:
preparing a complex in which a first target material and a second target material or a precursor of the second target material are bound to a multimer of a fusion protein, the complex being prepared by binding the multimer of the fusion protein to the first target material and binding the second target material or the precursor of the second target material to the multimer of the fusion protein, wherein the multimer of the fusion protein has an internal cavity and is formed from the fusion protein that contains a first peptide portion capable of binding to the first target material, a second peptide portion capable of binding to the second target material, and a polypeptide portion capable of forming a multimer having an internal cavity; and
forming an aggregate body by burning the complex to consume the multimer of the fusion protein, the aggregate body adhering to the first target material and being located so as to surround the first target material, the aggregate body having a plurality of first pores unevenly distributed near the first target material and a plurality of second pores scattered over the aggregate body.

### Claim 14 (depends on 13)

The method for producing the porous structure body according to claim 13,
wherein the step of preparing the complex is the step of preparing the complex in which the first target material and the precursor of the second target material are bound to the multimer of the fusion protein, and the step of forming the aggregate body is the step of burning the complex to consume the multimer of the fusion protein and to convert the precursor of the second target material to the second target material, thereby forming the aggregate body.

### Claim 15 (depends on 14)

The method for producing the porous structure body according to claim 14, wherein the step of preparing the complex is the step of binding the precursor of the second target material to the multimer of the fusion protein and depositing the second target material around the first target material.

### Claim 16 (depends on 13)

The method for producing the porous structure body according to claim 13, wherein the first target material is a carbon material selected from the group consisting of carbon nanotubes, carbon nanohorns, graphene sheets, fullerenes, and graphite.

### Claim 17 (depends on 13)

The method for producing the porous structure body according to claim 13, wherein the second target material is titanium oxide or zinc oxide.

### Claim 18 (depends on 13)

The method for producing the porous structure body according to claim 13,
wherein the multimer of the fusion protein further comprises a material different from the first target material, each of the metal particles being encapsulated in the internal cavity thereof, and the aggregate body formed further comprises the material in the first pores.

### Claim 19 (depends on 18)

The method for producing a porous structure body according to claim 18, wherein the material are nanoparticles selected from the group consisting of iron oxide, nickel, cobalt, manganese, phosphorus, uranium, beryllium, aluminum, cadmium sulfide, palladium, chromium, copper, silver, a gallium complex, platinum cobalt, silicon oxide, cobalt oxide, indium oxide, platinum, gold, gold sulfide, zinc selenide, and cadmium selenide.

### Claim 20 (depends on 19)

The method for producing the porous structure body according to claim 19, wherein the metal particles are iron oxide nanoparticles.

### Claim 21 (depends on 1)

A method for producing an electronic device, comprising the step of forming a functional structure using the porous structure body according to claim 1 as a functional material.

### Claim 22

A method for producing a dye-sensitized solar cell, comprising the steps of:
preparing a substrate comprising a transparent electrode;
obtaining a complex by binding a multimer of a fusion protein to a first target material, wherein the multimer of the fusion protein has an internal cavity and is formed from the fusion protein that contains a first peptide portion capable of binding to the first target material, a second peptide portion capable of binding to the second target material, and a polypeptide portion capable of forming a multimer having an internal cavity, thereby forming a combination body and binding the combination body to a second target material or a precursor of the second target material;
placing a material comprising the complex on the transparent electrode;
burning the material on the transparent electrode to consume the multimer of the fusion protein, thereby forming a structure having a porous structure body on the transparent electrode, the porous structure body comprising an aggregate body that comprises the second target material, adheres to the first target material, and is located so as to surround the first target material, the aggregate body having a plurality of first pores unevenly distributed near the first target material and a plurality of second pores scattered over the aggregate body;
supporting a sensitizing dye by the porous structure body, thereby forming a photoelectrode; and
pouring an electrolyte and sealing the photoelectrode and a counter electrode.

### Claim 23 (depends on 22)

The method for producing the dye-sensitized solar cell according to claim 22, wherein the structure comprising the porous structure body is formed such that a final concentration of the complex is less than 1% by weight.

### Claim 24 (depends on 23)

The method for producing the dye-sensitized solar cell according to claim 23, wherein the structure comprising the porous structure body is formed such that the final concentration of the complex is within a range of 0.06% by weight to 0.5% by weight.

### Claim 25

A method for producing a dye-sensitized solar cell, comprising the steps of:
preparing a substrate comprising a transparent electrode;
forming a porous structure body comprising an aggregate body by binding a multimer of a fusion protein, wherein the multimer of the fusion protein has an internal cavity and is formed from the fusion protein that contains a first peptide portion capable of binding to the first target material, a second peptide portion capable of binding to the second target material, and a polypeptide portion capable of forming a multimer having an internal cavity, to a first target material, thereby forming a combination body, binding the combination body to a second target material or a precursor of the second target material, thereby forming a complex body, and burning the complex body to consume the multimer of the fusion protein, the aggregate body comprising the second target material, adhering to the first target material, and being located so as to surround the first target material, the aggregate body having a plurality of first pores unevenly distributed near the first target material and a plurality of second pores scattered over the aggregate body;
placing a material comprising the porous structure body and the second target material or the precursor of the second target material on the transparent electrode;
heating the material on the transparent electrode, thereby forming a structure body comprising the porous structure body by the transparent electrode;
supporting a sensitizing dye by the porous structure body, thereby forming a photoelectrode; and
pouring an electrolyte and sealing the photoelectrode and a counter electrode.

### Claim 26 (depends on 22)

The method for producing the dye-sensitized solar cell according claim 22, wherein the first target material is a carbon material selected from the group consisting of carbon nanotubes, carbon nanohorns, graphene sheets, fullerenes, and graphite.

### Claim 27

A method for producing a dye-sensitized solar cell, comprising the steps of:
preparing a substrate comprising a transparent electrode;
arranging at least one carbon nanotube used as a first target material on the transparent electrode so as to extend in a direction of a thickness of the substrate;
forming a complex by binding a multimer of a fusion protein to the carbon nanotube, wherein the multimer of the fusion protein has an internal cavity and is formed from the fusion protein that contains a first peptide portion capable of binding to the carbon nanotube, a second peptide portion capable of binding to a second target material or a precursor of the second target material, and a polypeptide portion capable of forming a multimer having an internal cavity, thereby forming a combination body and binding the combination body to a second target material or a precursor of the second target material;
burning the combination body to consume the multimer of the fusion protein, whereby a structure body having a porous structure body comprising an aggregate body is formed on the transparent electrode, the aggregate body comprising the second target material, adhering to the carbon nanotube, and being located so as to surround the carbon nanotube, the aggregate body having a plurality of first pores unevenly distributed near the carbon nanotube and a plurality of second pores scattered over the aggregate body;
supporting a sensitizing dye by the porous structure body, thereby forming a photoelectrode; and
pouring an electrolyte and sealing the photoelectrode and a counter electrode.

### Claim 28 (depends on 27)

The method for producing a dye-sensitized solar cell according to claim 27, wherein the step of arranging the at least one carbon nanotube used as the first target material on the transparent electrode so as to extend in the direction of the thickness of the substrate comprises the step of adsorbing an inorganic material on a substrate, the step of growing a carbon nanotube from the inorganic material as a seed, thereby obtaining a carbon nanotube-arranged substrate, and the step of transferring the carbon nanotube on the carbon nanotube-arranged substrate to the transparent electrode.

### Claim 29 (depends on 28)

The method for producing the dye-sensitized solar cell according to claim 28, wherein the step of adsorbing the inorganic material on the substrate is the step of adsorbing and arranging at least two types of inorganic material-encapsulating proteins with different sizes on the substrate.

### Claim 30 (depends on 29)

The method for producing the dye-sensitized solar cell according to claim 29, wherein the step of adsorbing the inorganic material on the substrate is the step of adsorbing and arranging the inorganic material-encapsulating proteins on a silicon oxide film provided on the substrate used.

### Claim 31 (depends on 29, 30)

The method for producing the dye-sensitized solar cell according to claim 29 or 30, wherein the inorganic material-encapsulating proteins comprise at least one type of protein selected from ferritin protein, Dps protein, CDT protein, and modified proteins thereof.

### Claim 32 (depends on 22)

The method for producing the dye-sensitized solar cell according to claim 22, wherein the second target material is titanium oxide or zinc oxide.

### Claim 33 (depends on 22)

A dye-sensitized solar cell obtainable by the method for producing according to claim 22.

### Claim 34

A dye-sensitized solar cell comprising:
a substrate comprising a transparent electrode;
a photoelectric conversion layer provided on the transparent electrode, the photoelectric conversion layer comprising a porous structure body, the porous structure body supporting a sensitizing dye, the porous structure body comprising a first target material and an aggregate body comprising a second target material, the aggregate body adhering to the first target material and being located so as to surround the first target material, the aggregate body having a plurality of first pores unevenly distributed near the first target material and a plurality of second pores scattered over the aggregate body; and
a sealing portion that seals the dye-sensitized solar cell such that the photoelectrode composed of the photoelectric conversion layer and the transparent electrode faces a counter electrode and the photoelectrode and the counter electrode are in contact with an electrolyte.

### Claim 35

A dye-sensitized solar cell comprising:
a substrate comprising a transparent electrode;
a photoelectric conversion layer provided on the transparent electrode, the photoelectric conversion layer comprising a porous structure body, the porous structure body supporting a sensitizing dye, the porous structure body comprising at least one carbon nanotube used as a first target material and an aggregate body comprising a second target material, the at least one carbon nanotube being arranged to extend in a direction of a thickness of the substrate, the aggregate body adhering to the carbon nanotube and being located so as to surround the carbon nanotube, the aggregate body having a plurality of first pores unevenly distributed near the carbon nanotube and a plurality of second pores scattered over the aggregate body; and
a sealing portion that seals the dye-sensitized solar cell such that the photoelectrode composed of the photoelectric conversion layer and the transparent electrode faces a counter electrode and the photoelectrode and the counter electrode are in contact with an electrolyte.

### Claim 36 (depends on 33)

The dye-sensitized solar cell according to claim 33, wherein the first target material is a carbon material selected from the group consisting of carbon nanotubes, carbon nanohorns, graphene sheets, fullerenes, and graphite.

### Claim 37 (depends on 34)

The dye-sensitized solar cell according to claim 34, wherein the second target material is titanium oxide or zinc oxide.

### Claim 38

A method for producing a carbon nanotube-arranged substrate in which at least one carbon nanotube is arranged to extend in a thickness direction, the method comprising the steps of:
adsorbing and arranging at least two types of inorganic material-encapsulating proteins with different sizes on the substrate; and
growing a carbon nanotube from an inorganic material encapsulated in the inorganic material-encapsulating proteins as a seed.

### Claim 39 (depends on 38)

The method for producing a carbon nanotube-arranged substrate according to claim 38, wherein the step of adsorbing and arranging the at least two types of inorganic material-encapsulating proteins with different sizes on the substrate is performed by adsorbing the inorganic material-encapsulating proteins on a silicon oxide film provided on the substrate used.

### Claim 40 (depends on 38)

The method for producing the carbon nanotube-arranged substrate according to claim 38, wherein the inorganic material-encapsulating proteins comprise at least one type of protein selected from ferritin protein, Dps protein, CDT protein, and modified proteins thereof.