CN108914148B - Preparation method of photo-anode of photoelectrochemical cell - Google Patents

Preparation method of photo-anode of photoelectrochemical cell Download PDF

Info

Publication number
CN108914148B
CN108914148B CN201810746303.6A CN201810746303A CN108914148B CN 108914148 B CN108914148 B CN 108914148B CN 201810746303 A CN201810746303 A CN 201810746303A CN 108914148 B CN108914148 B CN 108914148B
Authority
CN
China
Prior art keywords
layer
alpha
substrate
photo
anode
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN201810746303.6A
Other languages
Chinese (zh)
Other versions
CN108914148A (en
Inventor
闫小琴
程晓琴
白智明
郇亚欢
李明华
纪箴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
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 University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN201810746303.6A priority Critical patent/CN108914148B/en
Publication of CN108914148A publication Critical patent/CN108914148A/en
Application granted granted Critical
Publication of CN108914148B publication Critical patent/CN108914148B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a preparation method of a photo-anode of a photoelectrochemical cell. The photo-anode is a composite structure and comprises alpha-Fe2O3Layer, intermediate layer, oxygen evolution catalyst layer.When preparing the electrode, firstly heating ferrocene to directly obtain alpha-Fe2O3And sintering the layer by spin-coating a tin precursor solution to obtain an intermediate layer, and finally growing a layer of oxygen evolution catalyst by a water bath method. The preparation steps of the obtained photo-anode are simple and easy to operate, and the photo-anode can be produced in a large area. alpha-Fe prepared by the invention2O3The composite structure electrode maintains alpha-Fe2O3The middle layer well passivates alpha-Fe2O3Surface defects of the layer greatly improve the catalyst and the alpha-Fe2O3Interfacial contact between layers. The intermediate layer and the catalyst layer of the composite structure photoanode enable photocurrent to be respectively improved by 72.6% and 118.4%, and therefore the performance of water photolysis is remarkably improved.

Description

Preparation method of photo-anode of photoelectrochemical cell
Technical Field
The invention belongs to the field of photoelectrolysis water, and particularly relates to a preparation method of a photo-anode of a photoelectrochemical cell.
Background
Solar energy is used as a clean energy source, the source is rich, the solar energy is not limited by regions, the storage capacity of water on the earth can reach 138.6 billion cubic meters, and therefore, the solar energy is stored in hydrogen by photolysis of water to produce hydrogen, and the solar energy storage device is a potential method for solving the current energy crisis. alpha-Fe2O3As a narrow bandgap semiconductor (Eg 2.1eV), it is very competitive in the choice of anode for photolytic water splitting. However due to alpha-Fe2O3The presence of surface defects and the relatively slow oxidation kinetics, the passivation of surface defects and the growth of a layer of oxygen evolution catalyst on the surface are important.
Disclosure of Invention
Based on solving the problems, the invention provides a preparation method of the composite structure electrode. The electrode can greatly improve the photoelectrolysis performance.
A preparation method of a photo-anode of a photoelectrochemical cell,characterized in that the photo-anode is made of alpha-Fe2O3The catalyst layer consists of a layer, a middle layer and an oxygen evolution catalyst layer, wherein the alpha-Fe 2O3 layer is microscopically vermicular, the size is 50-100nm, the thickness is 150nm, and the middle layer is tin oxide; the oxygen evolution catalyst layer is ferric oxyhydroxide and has a thickness of 15 nm.
The preparation method of the photo-anode of the photoelectrochemical cell is characterized by comprising the following steps of:
(1) firstly, preprocessing the substrate until the surface of the substrate is clean;
(2) reversely buckling the pretreated substrate on a crucible filled with a certain amount of ferrocene, placing the crucible in a muffle furnace for heating at 400 ℃ for 2 hours, cooling along with the furnace to obtain orange-yellow alpha-Fe on the substrate2O3A film;
(3) coating the tin precursor solution on the substrate obtained in the step (2) in a rotating mode for multiple times at 200 ℃ for 10 min;
(4) immersing the substrate obtained in the step (3) in a solution of ferric salt and sodium nitrate, and placing the substrate in a 100-DEG water bath for 10 min.
Further, in the step (1), the substrate is FTO;
in the step (2), the certain amount is 25 mg;
in the step (3), the tin precursor solution is 180mM SnCl4·5H2O solution;
in the step (4), the ferric salt is 0.10M FeCl3·6H2O solution and sodium nitrate solution are 1M.
Has the advantages that:
alpha-Fe prepared by the invention2O3The composite structure electrode maintains alpha-Fe2O3The middle layer well passivates alpha-Fe2O3Surface defects of the layer greatly improve the catalyst and the alpha-Fe2O3The interface contact between the layers, the intermediate layer and the catalyst layer, increases the photocurrent by 72.6% and 118.4%, respectively, thereby significantly improving the performance of photolyzing water.
Drawings
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention provides the following drawings:
FIG. 1 is a view showing α -Fe prepared in example 12O3Scanning electron micrographs of the material.
FIG. 2 is a view showing α -Fe prepared in example 42O3/SnO2And a transmission electron microscope image of the/FeOOH composite structure.
FIG. 3 shows pure α -Fe prepared in examples 1,2,3 and 4, respectively2O3,α-Fe2O3/SnO2,α-Fe2O3FeOOH and alpha-Fe2O3/SnO2Photocurrent density-voltage curve of/FeOOH electrode.
FIG. 4 shows pure α -Fe prepared in examples 1,2,3 and 4, respectively2O3,α-Fe2O3/SnO2。
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, but are not limited thereto.
Example 1
Pure alpha-Fe2O3The preparation method of the photo-anode material comprises the following steps:
(1) ultrasonically cleaning the FTO glass by using water, ethanol and acetone in sequence;
(2) the cleaned FTO glass is reversely buckled on a crucible filled with a certain amount of ferrocene, placed in a muffle furnace for heating at 400 ℃ for 2 hours, cooled along with the furnace, and the orange yellow alpha-Fe is obtained on a substrate2O3A film;
(3) annealing the FTO glass obtained in the step (2) at 750 ℃ for 10min to obtain pure alpha-Fe2O3A photoanode material.
Example 2
α-Fe2O3/SnO2The preparation method of the photo-anode material comprises the following steps:
(1) ultrasonically cleaning the FTO glass by using water, ethanol and acetone in sequence;
(2) putting the cleaned FTO glass on a crucible containing a certain amount of ferrocene, and placing the crucible on a horseHeating at 400 ℃ in a muffle furnace for 2 hours, cooling along with the furnace, and obtaining orange-yellow alpha-Fe on a substrate2O3A film;
(3) adding 180mM SnCl4·5H2Coating the O solution on the FTO glass obtained in the step (2) in a rotating mode for multiple times, and heating for 10min at 200 ℃;
(4) annealing the FTO glass obtained in the step (3) at 750 ℃ for 10min to obtain alpha-Fe2O3/SnO2A photoanode material.
Example 3
α-Fe2O3The preparation method of the/FeOOH photo-anode material comprises the following steps:
(1) ultrasonically cleaning the FTO glass by using water, ethanol and acetone in sequence;
(2) the cleaned FTO glass is reversely buckled on a crucible filled with a certain amount of ferrocene, placed in a muffle furnace for heating at 400 ℃ for 2 hours, cooled along with the furnace, and the orange yellow alpha-Fe is obtained on a substrate2O3A film;
(3) annealing the FTO glass obtained in the step (2) at 750 ℃ for 10 min;
(4) 0.1mol of sodium nitrate was added to 100ml of 0.10M FeCl3·6H2Obtaining an iron precursor solution in the O solution;
(5) immersing the substrate obtained in the step (3) in the solution obtained in the step (4), and placing the substrate in a 100-DEG water bath for 10 min;
(6) annealing the substrate obtained in the step (5) at 300 ℃ for 3 hours in the air atmosphere to obtain alpha-Fe2O3the/FeOOH photo-anode material.
Example 4
α-Fe2O3/SnO2The preparation method of the/FeOOH photo-anode material comprises the following steps:
(1) ultrasonically cleaning the FTO glass by using water, ethanol and acetone in sequence;
(2) the cleaned FTO glass is reversely buckled on a crucible filled with a certain amount of ferrocene, placed in a muffle furnace for heating at 400 ℃ for 2 hours, cooled along with the furnace, and the orange yellow alpha-Fe is obtained on a substrate2O3A film;
(3) adding 180mM SnCl4·5H2Coating the O solution on the FTO glass obtained in the step (2) in a rotating mode for multiple times, and heating for 10min at 200 ℃;
(4) annealing the FTO glass obtained in the step (3) at 750 ℃ for 10 min;
(5) 0.1mol of sodium nitrate was added to 100ml of 0.10M FeCl3·6H2Obtaining an iron precursor solution in the O solution;
(6) immersing the substrate obtained in the step (4) in the solution obtained in the step (5), and placing the substrate in a 100-DEG water bath for 10 min;
(7) annealing the substrate obtained in the step (6) at 300 ℃ for 3 hours in the air atmosphere to obtain alpha-Fe2O3/SnO2the/FeOOH photo-anode material.
Performance testing
Examples 1,2,3 and 4, photoanode materials, were fabricated into electrodes and tested for photoelectrochemical properties in a three-electrode system. The test results are shown in FIGS. 3 and 4.
The above description is only an example of the invention, and it should be noted that: it will be apparent to those skilled in the art that modifications and variations can be made in the structure of the disclosed device without departing from the spirit and scope of the invention.

Claims (2)

1. A method for preparing photo-anode of photoelectrochemical cell is characterized in that the photo-anode is made of alpha-Fe2O3Layer, intermediate layer, oxygen evolution catalyst layer, alpha-Fe2O3The layer is vermicular in microcosmic, 50-100nm in size and 150nm in thickness, and the middle layer is tin oxide; the oxygen evolution catalyst layer is ferric hydroxide and has the thickness of 15 nm; the preparation method of the photoelectrochemical cell photoanode comprises the following steps:
(1) firstly, preprocessing the substrate until the surface of the substrate is clean;
(2) reversely buckling the pretreated substrate on a crucible filled with a certain amount of ferrocene, placing the crucible in a muffle furnace, heating the crucible for 2 hours at 400 ℃, cooling the crucible along with the furnace to obtain orange-yellow alpha-Fe on the substrate2O3A film;
(3) coating the tin precursor solution on the substrate obtained in the step (2) in a rotating mode for multiple times, and heating for 10min at 200 ℃;
(4) immersing the substrate obtained in the step (3) in a solution of ferric salt and sodium nitrate, and placing the substrate in a water bath kettle at the temperature of 100 ℃ for 10 min.
2. The method of preparing a photoanode of a photoelectrochemical cell of claim 1, wherein the method comprises the steps of:
in the step (1), the substrate is FTO;
in step (2), the amount is 25 mg;
in the step (3), the tin precursor solution is 180mM SnCl4·5H2O solution;
in the step (4), the trivalent iron salt is 0.10M FeCl3·6H2O solution and sodium nitrate solution are 1M.
CN201810746303.6A 2018-07-09 2018-07-09 Preparation method of photo-anode of photoelectrochemical cell Active CN108914148B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810746303.6A CN108914148B (en) 2018-07-09 2018-07-09 Preparation method of photo-anode of photoelectrochemical cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810746303.6A CN108914148B (en) 2018-07-09 2018-07-09 Preparation method of photo-anode of photoelectrochemical cell

Publications (2)

Publication Number Publication Date
CN108914148A CN108914148A (en) 2018-11-30
CN108914148B true CN108914148B (en) 2020-01-21

Family

ID=64425679

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810746303.6A Active CN108914148B (en) 2018-07-09 2018-07-09 Preparation method of photo-anode of photoelectrochemical cell

Country Status (1)

Country Link
CN (1) CN108914148B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110791770B (en) * 2019-11-08 2022-02-08 南京大学 Preparation and application of photo-assisted thermoelectric coupling oxygen precipitation electrode

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009077122A2 (en) * 2007-12-19 2009-06-25 Merck Patent Gmbh Optically variable pigments of high electrical conductivity
CN103043710B (en) * 2011-10-17 2015-09-16 中国科学院福建物质结构研究所 A kind of at α-Fe 2o 3nanocrystal surface Heteroepitaxy nano SnO 2method
CN103726090A (en) * 2012-10-11 2014-04-16 中国科学院大连化学物理研究所 Preparation method for alpha-Fe2O3 photoanode applied to photoelectrolysis
CN104953103B (en) * 2015-07-09 2017-10-17 山西大学 Fe for lithium ion battery2O3The preparation method of/exfoliated-graphite composite
CN106929827A (en) * 2017-04-27 2017-07-07 郑州大学 A kind of few layer MoS2The preparation method of film
CN107326385B (en) * 2017-06-16 2019-01-22 中国科学院化学研究所 A kind of preparation method of boron doping di-iron trioxide optoelectronic pole
CN107497431A (en) * 2017-08-09 2017-12-22 西安交通大学 Heterogeneous fenton catalyst of high-specific surface area FeOOH/ carbon cloths and preparation method thereof
CN108163887A (en) * 2018-01-05 2018-06-15 宁波工程学院 Water-soluble SnO2The preparation method of inorganic semiconductor nanometer material and application
CN108190860B (en) * 2018-01-31 2021-06-15 南京大学 Method for preparing single-walled carbon nanotube by microwave

Also Published As

Publication number Publication date
CN108914148A (en) 2018-11-30

Similar Documents

Publication Publication Date Title
Kang et al. Interface engineering for modulation of charge carrier behavior in ZnO photoelectrochemical water splitting
Ahn et al. Boron doping of metal-doped hematite for reduced surface recombination in water splitting
Jang et al. Photoelectrochemical water splitting with p‐type metal oxide semiconductor photocathodes
Long et al. Bamboo shoots shaped FeVO4 passivated ZnO nanorods photoanode for improved charge separation/transfer process towards efficient solar water splitting
Tang et al. Metal–organic framework derived Co3O4/TiO2/Si heterostructured nanorod array photoanodes for efficient photoelectrochemical water oxidation
Liu et al. Enhanced photoelectrochemical water-splitting performance of semiconductors by surface passivation layers
Zhang et al. Recent Advances in Photoelectrochemical Applications of Silicon Materials for Solar‐to‐Chemicals Conversion
Dubale et al. Heterostructured Cu 2 O/CuO decorated with nickel as a highly efficient photocathode for photoelectrochemical water reduction
Wang et al. Single‐crystal semiconductors with narrow band gaps for solar water splitting
Shi et al. Recent progress in photoelectrochemical water splitting for solar hydrogen production
Xiao et al. Recent advances of metal‐oxide photoanodes: engineering of charge separation and transportation toward efficient solar water splitting
Fang et al. Mo-doping induced crystal orientation reconstruction and oxygen vacancy on BiVO4 homojunction for enhanced solar-driven water splitting
Xie et al. Self-improvement of Ti: Fe2O3 photoanodes: photoelectrocatalysis improvement after long-term stability testing in alkaline electrolyte
Minguez-Bacho et al. Conformal Cu2S-coated Cu2O nanostructures grown by ion exchange reaction and their photoelectrochemical properties
Qin et al. Sn-doped hematite films as photoanodes for efficient photoelectrochemical water oxidation
Wu et al. Enhancing photoelectrochemical activity with three-dimensional p-CuO/n-ZnO junction photocathodes
Wei et al. Rationally designed heterojunction on a CuBi2O4 photocathode for improved activity and stability during photoelectrochemical water reduction
Kim et al. Enhanced photoelectrochemical stability of GaN photoelectrodes by Al 2 O 3 surface passivation layer
CN105039938A (en) Method for preparing photoelectrode of alpha-iron oxide film by single-source precursor
Tolod et al. Visible light-driven catalysts for water oxidation: towards solar fuel biorefineries
Wei et al. Room temperature surface modification of ultrathin FeOOH cocatalysts on Fe2O3 photoanodes for high photoelectrochemical water splitting
Kim et al. Toward high-performance hematite nanotube photoanodes: charge-transfer engineering at heterointerfaces
Selvaraj et al. Synthesis and photo-electrochemical properties of spinel-ferrite-coated hematite for solar water splitting
Chen et al. Solution–processed Cu2O/ZnO/TiO2/Pt nanowire photocathode for efficient photoelectrochemical water splitting
Zhao et al. The influence of Ti doping on morphology and photoelectrochemical properties of hematite grown from aqueous solution for water splitting

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant