KR101782351B1 - Efficient photocatalytic water splitting using porous meta material photo electrode - Google Patents

Efficient photocatalytic water splitting using porous meta material photo electrode Download PDF

Info

Publication number
KR101782351B1
KR101782351B1 KR1020150091074A KR20150091074A KR101782351B1 KR 101782351 B1 KR101782351 B1 KR 101782351B1 KR 1020150091074 A KR1020150091074 A KR 1020150091074A KR 20150091074 A KR20150091074 A KR 20150091074A KR 101782351 B1 KR101782351 B1 KR 101782351B1
Authority
KR
South Korea
Prior art keywords
nano
meta
substrate
rod
porous
Prior art date
Application number
KR1020150091074A
Other languages
Korean (ko)
Other versions
KR20170001299A (en
Inventor
백정민
박준모
Original Assignee
울산과학기술원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 울산과학기술원 filed Critical 울산과학기술원
Priority to KR1020150091074A priority Critical patent/KR101782351B1/en
Publication of KR20170001299A publication Critical patent/KR20170001299A/en
Application granted granted Critical
Publication of KR101782351B1 publication Critical patent/KR101782351B1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/307—Other macromolecular compounds

Abstract

The water decomposition photo-electrode structure using the porous meta-material according to the present invention comprises a first substrate; A nano-rod grown up on the first substrate; A meta structure in which a plurality of holes are formed in a grid structure on one side so that the distal end of the nanorod can be inserted; And a first substrate formed on the other side of the meta structure, wherein the metal / photocatalyst or the metal / dielectric nanostructure-based meta material is formed to increase the light trapping effect due to the plasmon phenomenon, There is an effect that the operation efficiency can be improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a water-decomposing photoelectrode structure using a porous meta-

The present invention relates to a water-decomposing photoelectrode structure using a porous meta-material, and more particularly, to a photo-electrode structure using a porous meta-material using a composite structure of a metal and a photocatalyst, To a water-decomposing photoelectrode structure using a meta-material and a manufacturing method thereof.

Hydrogen can be produced through a variety of energy sources and technologies, which can be produced using conventional fossil fuels, renewable energy, nuclear power, biomass, artificial photosynthetic photocatalysts, and water decomposition without CO2 emissions.

Most of the photocatalysts used for artificial photosynthesis developed on the basis of TiO 2 react with ultraviolet light. In the case of sunlight, ultraviolet light is about 4%. Therefore, the development of high efficiency photocatalyst which reacts to visible light, which accounts for about 43% It is important.

The Fe 2 O 3, BiVO 4, CdSe , etc. of a light chongmae operating in visible light, but upon irradiation with sunlight it is characteristic that the corrosion due to the photoelectric chemistry, has a problem in service life and reliability.

For this reason, water decomposition or high-efficiency activity is realized in visible light, but unfortunately it is not yet in practical use due to the problem of life at the present stage.

Reliable materials include TiO 2 , but it absorbs almost no visible light and has low efficiency in sunlight. Using photocatalysts such as Fe 2 O 3 , BiVO 4 , ZnO 2 , and WO 3 as a composite structure, Research on the production of photoelectrode that is active has been actively conducted, and research results have been attracting attention to the photocatalytic activity by efficiently separating and recombining electron / hole pairs using a composite photocatalyst such as a pn junction type diode structure.

Recently, plasmonic photoelectrodes capable of producing electrons / holes at low photon energy by inducing plasmon effect in the form of metal particles bonded to TiO 2 photocatalyst material are being studied. Experimental results of plasmonic effect are being studied .

However, most studies show that the efficiency of solar-to-hydrogen conversion is low due to low absorption of light in the visible light region, which is generally about 2%.

On the other hand, the approach used as a nanocomposite photocatalyst electrode is effective in increasing the surface area and optimizing the electron hole transport efficiency, and is thus essential for the production of a high efficiency photocatalyst.

Korean Patent Laid-Open Publication No. 10-2015-0009076 (2015.01.26)

In order to overcome the above-described problems, the present invention provides a photocatalyst that does not operate in a visible light region having a wide bandgap such as TiO 2 , ZnO, and WO 3 to a high absorbance of light at a resonance frequency And a porous meta material capable of producing hydrogen and oxygen through the light in the visible light region by efficiently transferring electrons excited by the absorbed light to the photocatalyst by using a porous meta structure and inducing a plasmonic phenomenon And to provide a water-decomposable photoelectrode structure and a manufacturing method thereof.

In order to accomplish the above object, the present invention provides a water decomposition photoelectrode structure using porous meta-material, comprising: a first substrate; A nano-rod grown up on the first substrate; A meta structure in which a plurality of holes are formed in a grid structure on one side so that the distal end of the nanorod can be inserted; And a first substrate formed on the other side of the meta structure.

According to another aspect of the present invention, there is provided a method for fabricating a water-decomposing photoelectrode structure using porous meta-materials, comprising: (a) growing TiO 2 on a first substrate by hydrothermal synthesis to form a nanorod ; (b) coating the entire TiO 2 nanorods through the PR coating on the nanorods; (c) etching a portion of the nano-rods to a predetermined depth from the surface through RIE; (d) forming a porous structure having a depth of less than 200 nm and a thickness of 100 nm or more through deposition or plating of the nano-rod exposed on the surface with Au metal; (e) removing the PR coated in step (b) using an organic solvent to form a porous meta structure on the Au metal deposited or plated in step (d); And (f) adsorbing a catalyst such as RuO 2 , NiO, Co, Pt to the Au metal formed of the porous meta structure.

The water-decomposing photoelectrode structure and manufacturing method using the porous meta-material according to the present invention can form a porous metal / photocatalyst or a metal / dielectric nanostructure-based meta material to increase the light trapping effect due to plasmon development, It is possible to improve the operation efficiency.

In addition, the water-decomposing photo-electrode structure and the manufacturing method using the porous meta-material according to the present invention have the effect of enabling water-decomposing photo-electrode development beyond the limit of existing materials.

In addition, the water-decomposing photo-electrode structure and the manufacturing method using the porous meta-material according to the present invention can absorb light corresponding to the plasmon resonance frequency of the porous metal structure and can absorb light in a visible light region that can not be absorbed by a conventional dielectric or photocatalyst The photocurrent can be absorbed and the photocurrent generation efficiency in the sunlight can be improved.

In addition, the water-decomposing photo-electrode structure and the manufacturing method using the porous meta-material according to the present invention have an effect of improving the light absorption rate in the resonance frequency region by changing the resonance frequency according to the shape and size of the hole of the porous structure .

In addition, the water-decomposing photoelectrode structure and the manufacturing method using the porous meta-material according to the present invention have an effect of increasing the efficiency even when a metal having poor catalytic properties is adsorbed on the porous metal surface and the photocatalyst surface .

1 is a conceptual view of a photoelectrode using a porous meta-material and a photocatalyst,
FIG. 2 is a process diagram of a method for fabricating a water decomposition photo-electrode structure using the porous meta-material of the present invention,
3 is a view for explaining the operation principle of the porous meta-material photoelectrode according to the present invention,
4 is a view showing a porous meta-material photoelectrode according to another embodiment of the present invention, and Fig.
5 is a SEM cross-sectional photograph of a porous meta structure according to the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concept of the term appropriately in order to describe its own invention in the best way. The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention.

Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.

First, as an embodiment of the present invention, a water decomposition photo-electrode structure using porous meta-material will be described with reference to FIG.

1 is a conceptual view of a photoelectrode using a porous meta-material and a photocatalyst.

1, a water decomposition photoelectrode structure using a porous meta-material according to the present invention includes a first substrate 100, a growth assist layer 200, a nano rod 300, a meta structure 400, And a second substrate 500.

The first substrate 100 may be a metal, a dielectric, a polymer, or a semiconductor. The first substrate 100 may be made of Cu, Fe, Au, Al, or Ag. And may be composed of PET, PDMS, etc. The semiconductor may be composed of Si, GaAs, etc., and the dielectric may be composed of SiO 2 , TiO 2, or the like.

The growth assist layer 200 may be formed of a material that can grow nano-rods directly on a substrate, which is a layer that helps growth of the nano-rods. The growth assist layer 200 may be formed of TiO 2 , Fe 3 O 4 , ZnO, WO 3 , BiVO 4 , SrTiO 3 , it may be composed of ZnS, ZrO 2, SrTiO 3, KTaO 3, CdS, CdSe, MoS 2, ITO, FTO or the like.

The nano-rod 300 may be composed of a semiconductor or a dielectric material. The semiconductor may be composed of GaN, Ge, Si, GaAs, GaP, and the like. Examples of the photocatalyst include TiO 2 , Fe 3 O 4 , ZnO, WO 3 , BiNO 4 , SrTiO 3 , ZnS, ZrO 2 , SrTiO 3 , KTaO 3 , CdS, CdSe, MoS 2 and the like. The size of the nanorods may have a diameter of 200 nm or less and a length of 300 nm or more.

The meta-structure 400 may be made of a metal such as Au, Pt, Ag, Ni, Al, or Cu. The size of the hole may be 200 nm or less and 300 nm or more Structure.

The nano-rod 300 is inserted into the hole of the meta-structure 400 to form a porous meta-structured photo-electrode as shown in FIG.

5 is a SEM cross-sectional photograph of a porous meta structure according to the present invention.

The second substrate 500 may serve as a substrate and may be made of polymer, glass, or semiconductor. The polymer may be made of PET, PDMS, or the like. The semiconductor may be made of Si, GaAs, or the like .

Hereinafter, a method of manufacturing a water decomposition photo-electrode structure using porous meta-materials will be described with reference to FIG. 2 as an embodiment of the present invention.

2 is a process diagram of a method for fabricating a water decomposition photo-electrode structure using the porous meta-material of the present invention.

As shown in FIG. 2 (a), TiO 2 is grown on the first substrate 100 by hydrothermal synthesis to form the nanorod 300 (S 10).

At this time, the nano-rod 300 uses an FTO transparent electrode as a growth layer, and a transparent electrode (TCO) layer is formed through electron beam deposition, sputtering, or spray deposition.

As shown in FIG. 2 (b), on the nano rod 300 on which the TiO 2 is grown, TiO 2 A step of coating the entire nano-rod 300 is performed (S20).

As shown in FIG. 2 (c), a step of exposing a part of the nano-rod 300 to the surface through a RIE process is performed (S30).

2 (d), a step of forming a porous structure having a depth of less than 200 nm and a depth of 100 nm or more is performed by depositing or plating the nano-rod 300 exposed on the surface with Au metal (S40).

As shown in FIG. 2 (e), the PR coated at step S20 is removed using an organic solvent, and a porous meta structure is formed on the Au metal deposited or plated in step S40 (step S50) .

As shown in FIG. 2 (f), a step of adsorbing a catalyst such as RuO 2 , NiO, Co, Pt to the Au metal formed with the porous meta structure is performed (S 60).

In FIG. 2 (f), the shape of the catalyst is in the form of particles but may actually be a thin film or nanowire structure.

 Hereinafter, the principle of operation of the porous meta-material optical electrode according to the present invention will be briefly described with reference to FIG.

3 is a view for explaining the operation principle of the porous meta-material photoelectrode according to the present invention.

3, the inside of the light coming from outside through the nano-rods (300) TiO 2 The photocatalyst is absorbed at the interface between the photocatalyst and the Ag metal constituting the meta structure 400 and is excited to be transformed into a plasmon state and excited by plasmons, and the electrons move to TiO 2 to form a photocurrent.

In another embodiment of the present patent, the meta structure 400 may be made of a material such as Au, Pt, Ag, Ni, Al, Cu, etc., and the nano rod 300 may be formed thereon with a photocatalyst or a semiconductor. The semiconductor may be composed of GaN, Ge, Si, GaAs, GaP, etc. The photocatalyst may be TiO 2 , Fe 3 O 4 , ZnO, WO 3 , BiVO 4 , SrTiO 3 , ZnS, ZrO 2 , SrTiO 3 , KTaO 3 , CdS, CdSe, MoS 2 , and the like.

Meanwhile, the second substrate 500 shown in FIG. 4 serves as a substrate. The second substrate 500 may be made of polymer, glass, or semiconductor. The polymer may be made of PET, PDMS, GaAs, and the like.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It is to be understood that various modifications and changes may be made without departing from the scope of the appended claims.

100: first substrate
200: growth help layer
300: Nano rod
400: Meta Structure
500: second substrate

Claims (10)

A first substrate 100;
A nano-rod 300 tapered and grown on the first substrate 100;
A meta structure 400 having a plurality of holes in a grid structure on one side thereof so that the distal end of the nano-rod 300 can be inserted; And
And a second substrate (500) formed on the other side of the meta structure (400).
The method according to claim 1,
And a growth assist layer (200) interposed between the first substrate (100) and the nanorods (300) to assist growth of the nanorods (300) Decomposition photoelectrode structure.
The method according to claim 1,
The first substrate (100)
Wherein the metal is made of Cu, Fe, Au, Al and Ag, and the polymer is made of PET or PDMS, and the semiconductor is made of Si or GaAs, And SiO 2 and TiO 2 in the case of a dielectric material.
3. The method of claim 2,
The growth assist layer (200)
Porous meta-material, characterized in that consisting of TiO 2, Fe 3 O 4, ZnO, WO 3, BiVO 4, SrTiO 3, ZnS, ZrO 2, SrTiO 3, KTaO 3, CdS, CdSe, MoS 2, ITO, FTO Water - splitting photo - electrode structure using.
The method according to claim 1,
The nano-
Wherein the photocatalyst comprises at least one of TiO 2 , Fe 3 O 4 , ZnO, WO 3 , BiVO 4 , SrTiO 3 , ZnS, ZrO 2 , 2 , SrTiO 3 , KTaO 3 , CdS, CdSe and MoS 2 .
The method according to claim 1,
The meta-structure (400)
Wherein the porous structure is made of a metal material of Au, Pt, Ag, Ni, Al, and Cu.
The method according to claim 1,
The second substrate 500
Wherein the polymer is made of PET or PDMS, and the semiconductor is made of Si or GaAs.
8. The method according to any one of claims 1 to 7,
The size of the nano-
A water-decomposing photo-electrode structure using a porous meta-material having a diameter of 200 nm or less and a length of 300 nm or more.
8. The method according to any one of claims 1 to 7,
Wherein the size of the pores formed in the meta structure (400) has a diameter of 200 nm or less and a depth of 300 nm or more.
(a) growing TiO 2 on the first substrate 100 by hydrothermal synthesis to form a tapered nano-rod 300;
(b) coating the entire TiO 2 nano-rod 300 through the PR coating on the nano-rod 300;
(c) etching the surface of the nano-rod 300 to a predetermined depth through RIE to expose a part of the nano-rod 300 to the surface;
(d) forming a porous structure having a depth of less than 200 nm and a thickness of at least 100 nm by depositing or plating the nano-rod (300) exposed on the surface with Au metal;
(e) removing the PR coated in the step (b) using an organic solvent to form a porous metal structure (not shown) so that the end of the nano-rod 300 can be inserted into the Au metal deposited or plated in the step ; And
(f) adsorbing a catalyst such as RuO 2 , NiO, Co, Pt or the like to the Au metal formed of the porous meta structure.
KR1020150091074A 2015-06-26 2015-06-26 Efficient photocatalytic water splitting using porous meta material photo electrode KR101782351B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020150091074A KR101782351B1 (en) 2015-06-26 2015-06-26 Efficient photocatalytic water splitting using porous meta material photo electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020150091074A KR101782351B1 (en) 2015-06-26 2015-06-26 Efficient photocatalytic water splitting using porous meta material photo electrode

Publications (2)

Publication Number Publication Date
KR20170001299A KR20170001299A (en) 2017-01-04
KR101782351B1 true KR101782351B1 (en) 2017-09-28

Family

ID=57831511

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020150091074A KR101782351B1 (en) 2015-06-26 2015-06-26 Efficient photocatalytic water splitting using porous meta material photo electrode

Country Status (1)

Country Link
KR (1) KR101782351B1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102627668B1 (en) * 2021-09-30 2024-01-23 울산대학교 산학협력단 Core-shell fe2o3@ws2/wox composition, photocatalyst including the composition, and the method of preparing the same
KR102627617B1 (en) * 2021-09-30 2024-01-23 울산대학교 산학협력단 Tungsten doped alpha fe2o3 and mos2 composition, photocatalyst including the composition and the method of preparing the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101596250B1 (en) 2013-07-15 2016-02-24 한국전기연구원 Large Scale Photo-chemical Water Splitting Unit, Scalable Hydrogen Gas Generating Appatratus Comprising The Same, And Photo-chemical Electrode Used Therin

Also Published As

Publication number Publication date
KR20170001299A (en) 2017-01-04

Similar Documents

Publication Publication Date Title
Wang et al. Heterogeneous p–n junction CdS/Cu2O nanorod arrays: synthesis and superior visible-light-driven photoelectrochemical performance for hydrogen evolution
Jiang et al. Construction of an all-solid-state Z-scheme photocatalyst based on graphite carbon nitride and its enhancement to catalytic activity
Lu et al. Electrospun semiconductor‐based nano‐heterostructures for photocatalytic energy conversion and environmental remediation: opportunities and challenges
Chen et al. Hierarchical nanostructures of metal oxides for enhancing charge separation and transport in photoelectrochemical solar energy conversion systems
Cai et al. Large-scale tunable 3D self-supporting WO3 micro-nano architectures as direct photoanodes for efficient photoelectrochemical water splitting
Li et al. In situ synthesis of strongly coupled Co2P-CdS nanohybrids: an effective strategy to regulate photocatalytic hydrogen evolution activity
CN104988533B (en) TiO2/BiVO4Light anode material and preparation method thereof
Shao et al. One-step fabrication of CdS nanoparticle-sensitized TiO2 nanotube arrays via electrodeposition
Yu et al. ZnS/ZnO heteronanostructure as photoanode to enhance the conversion efficiency of dye-sensitized solar cells
Wang et al. Plasmon-enhanced layered double hydroxide composite BiVO4 photoanodes: layering-dependent modulation of the water-oxidation reaction
Wang et al. Simultaneously efficient light absorption and charge transport of CdS/TiO2 nanotube array toward improved photoelectrochemical performance
KR101826413B1 (en) Three dimensional hybrid nanostructures based materials for efficient photochemical or photoelectrochemical reaction and manufacturing method thereof
CN103354283A (en) Gold nanoparticle-modified dendritic titanium dioxide nanorod array electrode, as well as preparation method and application of hydrogen production by photocatalytic water splitting
WO2016136374A1 (en) Photocatalyst structure and photocell
Ranjith et al. Promotional effect of Cu2S–ZnS nanograins as a shell layer on ZnO nanorod arrays for boosting visible light photocatalytic H2 evolution
CN107723777A (en) The preparation method of the TiO 2 nanotubes modified array of electro-deposition molybdenum disulfide quantum dot
CN104383950A (en) Bi2O3-BiOI heterojunction visible-light response photocatalyst and preparation method thereof
Cheng et al. Enhanced visible light catalytic activity of MoS2/TiO2/Ti photocathode by hybrid-junction
Chen et al. A dual-heterojunction Cu2O/CdS/ZnO nanotube array photoanode for highly efficient photoelectrochemical solar-driven hydrogen production with 2.8% efficiency
KR101782351B1 (en) Efficient photocatalytic water splitting using porous meta material photo electrode
Centi et al. Advanced nanostructured titania photoactive materials for sustainable H2 production
Liu et al. Bio‐inspired plasmonic photocatalysts
Seenivasan et al. Multilayer strategy for photoelectrochemical hydrogen generation: new electrode architecture that alleviates multiple bottlenecks
KR101666378B1 (en) POROUS PYRAMID PHOTOELECTRODE BASED GaN AND METHOD
Guo et al. Synthesis of ZnO/Cu 2 S core/shell nanorods and their enhanced photoelectric performance

Legal Events

Date Code Title Description
A201 Request for examination
N231 Notification of change of applicant
E902 Notification of reason for refusal
AMND Amendment
E601 Decision to refuse application
AMND Amendment
X701 Decision to grant (after re-examination)
GRNT Written decision to grant