CN108914148A - A kind of preparation method of photoelectrochemical cell light anode - Google Patents

A kind of preparation method of photoelectrochemical cell light anode Download PDF

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Publication number
CN108914148A
CN108914148A CN201810746303.6A CN201810746303A CN108914148A CN 108914148 A CN108914148 A CN 108914148A CN 201810746303 A CN201810746303 A CN 201810746303A CN 108914148 A CN108914148 A CN 108914148A
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layer
light anode
substrate
preparation
solution
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CN108914148B (en
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闫小琴
程晓琴
白智明
郇亚欢
李明华
纪箴
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University of Science and Technology Beijing USTB
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    • 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

Abstract

The present invention provides a kind of preparation methods of photoelectrochemical cell light anode.The light anode is a kind of composite construction, including α-Fe2O3Layer, middle layer, oxygen-separating catalyst layer.When preparing electrode, first passes through heating ferrocene and directly obtain α-Fe2O3Layer, then be sintered to obtain middle layer by spin coating tin precursor solution, finally with the long chromatography VPO catalysts of immersion method.Resulting light anode preparation step is simple to operation and can large area production.α-Fe obtained by the present invention2O3Composite construction electrode maintains α-Fe2O3Nanotopography structure, middle layer has been passivated α-Fe well2O3The surface defect of layer, greatly improves catalyst and α-Fe2O3Interfacial contact between layer.The middle layer and catalyst layer of the composite structure light anode make photoelectric current that 72.6% and 118.4% be respectively increased, to significantly improve the performance of photocatalytic water.

Description

A kind of preparation method of photoelectrochemical cell light anode
Technical field
The invention belongs to photoelectrolysis water field, specially a kind of preparation method of photoelectrochemical cell light anode.
Background technique
For solar energy as a kind of clean energy resource, abundance, without geographical restrictions, the reserves of water on earth are reachable 138.6 billion cubic meters, therefore solar energy is stored in hydrogen by photolysis water hydrogen, it is to solve having very much for current energy crisis The method of potentiality.α-Fe2O3As a kind of narrow gap semiconductor (Eg=2.1eV), there is very much competition in the selection of photocatalytic water anode Power.However due to α-Fe2O3The slow oxidation kinetics process of presence and comparison of surface defect, passivated surface defect and It is long extremely important once chromatography VPO catalysts on its surface.
Summary of the invention
Based on solving the above problems, the invention proposes a kind of preparation methods of composite construction electrode.The electrode can Greatly improve the aqueous energy of photoelectrolysis.
A kind of preparation method of photoelectrochemical cell light anode, it is characterised in that the light anode is by α-Fe2O3Layer, in Interbed, oxygen-separating catalyst layer composition, it is above vermiform that-Fe2O3 layers of α microcosmic, and size is in 50-100nm, with a thickness of 150nm, centre Layer is tin oxide；The oxygen-separating catalyst layer is FeOOH, with a thickness of 15nm.
The preparation method of photoelectrochemical cell light anode as described above, it is characterised in that include the following steps：
(1) first carry out substrate pre-process to substrate surface cleaning；
(2) tips upside down on above-mentioned precondition substrate on the crucible equipped with a certain amount of ferrocene, is placed in Muffle furnace 400 ° It heats 2 hours, furnace cooling, obtains orange-yellow α-Fe on substrate2O3Film；
(3) is by tin precursor solution multiple spin coating 200 ° of heating 10min on the substrate obtained by the step (2)；
(4) substrate obtained by step (3) is immersed in the solution of trivalent iron salt and sodium nitrate by, is placed in 100 ° of water-baths Middle 10min.
Further, in step (1), the substrate is FTO；
It is described a certain amount of for 25mg in step (2)；
In step (3), the tin precursor solution is 180mM SnCl4·5H2O solution；
In step (4), the trivalent iron salt is 0.10M FeCl3·6H2O solution, sodium nitrate solution 1M.
Beneficial effect：
α-Fe prepared by the present invention2O3Composite construction electrode maintains α-Fe2O3Nanotopography structure, middle layer is fine Be passivated α-Fe2O3The surface defect of layer, greatly improves catalyst and α-Fe2O3Interfacial contact between layer, middle layer Make photoelectric current that 72.6% and 118.4% be respectively increased with catalyst layer, to significantly improve the performance of photocatalytic water.
Detailed description of the invention
In order to keep the objectives, technical solutions, and advantages of the present invention clearer, the present invention provides following attached drawing：
Fig. 1 is the α-Fe prepared in embodiment 12O3The scanning electron microscope (SEM) photograph of material.
Fig. 2 is the α-Fe prepared in embodiment 42O3/SnO2The transmission electron microscope picture of/FeOOH composite construction.
Fig. 3 is the pure α-Fe prepared respectively in embodiment 1,2,3,42O3,α-Fe2O3/SnO2,α-Fe2O3/ FeOOH and α- Fe2O3/SnO2Density of photocurrent-voltage curve of/FeOOH electrode.
Fig. 4 is the pure α-Fe prepared respectively in embodiment 1,2,3,42O3,α-Fe2O3/SnO2。
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described, But not limited to this.
Embodiment 1
Pure α-Fe2O3The preparation method of optical anode material, includes the following steps：
(1) FTO glass water, ethyl alcohol and acetone are successively cleaned by ultrasonic completely；
(2) above-mentioned clean FTO glass is tipped upside down on the crucible equipped with a certain amount of ferrocene, is placed in Muffle furnace 400 ° are heated 2 hours, furnace cooling, obtain orange-yellow α-Fe on substrate2O3Film；
(3) the FTO glass that above-mentioned (2) obtain is annealed 10min under 750 °, obtains pure α-Fe2O3Optical anode material.
Embodiment 2
α-Fe2O3/SnO2The preparation method of optical anode material, includes the following steps：
(1) FTO glass water, ethyl alcohol and acetone are successively cleaned by ultrasonic completely；
(2) above-mentioned clean FTO glass is tipped upside down on the crucible equipped with a certain amount of ferrocene, is placed in Muffle furnace 400 ° are heated 2 hours, furnace cooling, obtain orange-yellow α-Fe on substrate2O3Film；
(3) by 180mM SnCl4·5H2O solution multiple spin coating is on the FTO glass that (2) obtain, 200 ° of heating 10min；
(4) the FTO glass that above-mentioned (3) obtain is annealed 10min under 750 °, obtains α-Fe2O3/SnO2Optical anode material.
Embodiment 3
α-Fe2O3The preparation method of/FeOOH optical anode material, includes the following steps：
(1) FTO glass water, ethyl alcohol and acetone are successively cleaned by ultrasonic completely；
(2) above-mentioned clean FTO glass is tipped upside down on the crucible equipped with a certain amount of ferrocene, is placed in Muffle furnace 400 ° are heated 2 hours, furnace cooling, obtain orange-yellow α-Fe on substrate2O3Film；
(3) the FTO glass that above-mentioned (2) obtain is annealed 10min under 750 °；
(4) 0.1mol sodium nitrate is added to 100ml, 0.10M FeCl3·6H2In O solution, iron precursor solution is obtained；
(5) substrate obtained by (3) is immersed in (4) solution, is placed in 10min in 100 ° of water-baths；
(6) lower 300 ° of the substrate air atmosphere obtained (5) are annealed 3 hours, and α-Fe is obtained2O3/ FeOOH optical anode material.
Embodiment 4
α-Fe2O3/SnO2The preparation method of/FeOOH optical anode material, includes the following steps：
(1) FTO glass water, ethyl alcohol and acetone are successively cleaned by ultrasonic completely；
(2) above-mentioned clean FTO glass is tipped upside down on the crucible equipped with a certain amount of ferrocene, is placed in Muffle furnace 400 ° are heated 2 hours, furnace cooling, obtain orange-yellow α-Fe on substrate2O3Film；
(3) by 180mM SnCl4·5H2O solution multiple spin coating is on the FTO glass that (2) obtain, 200 ° of heating 10min；
(4) the FTO glass that above-mentioned (3) obtain is annealed 10min under 750 °；
(5) 0.1mol sodium nitrate is added to 100ml, 0.10M FeCl3·6H2In O solution, iron precursor solution is obtained；
(6) substrate obtained by (4) is immersed in (5) solution, is placed in 10min in 100 ° of water-baths；
(7) lower 300 ° of the substrate air atmosphere obtained (6) are annealed 3 hours, and α-Fe is obtained2O3/SnO2/ FeOOH light anode Material.
Performance test
By example 1,2,3 and 4, electrode is made in optical anode material, and photoelectrochemical behaviour survey is carried out under three-electrode system Examination.Test result such as Fig. 3, shown in 4.
The above is only invention example, it should be pointed out that：For a person skilled in the art, the present invention is not being departed from In the case where spirit and scope, device architecture disclosed by the invention is modified or deformed, should be included in guarantor of the invention Within the scope of shield.

Claims (3)

1. a kind of preparation method of photoelectrochemical cell light anode, it is characterised in that the light anode is by α-Fe2O3Layer, centre Layer, oxygen-separating catalyst layer composition, it is above vermiform that-Fe2O3 layers of α microcosmic, and size is in 50-100nm, with a thickness of 150nm, middle layer For tin oxide；The oxygen-separating catalyst layer is FeOOH, with a thickness of 15nm.
2. the preparation method of photoelectrochemical cell light anode described in claim 1, it is characterised in that include the following steps：
(1) first carry out substrate pre-process to substrate surface cleaning；
(2) tips upside down on above-mentioned precondition substrate on the crucible equipped with a certain amount of ferrocene, is placed on 400 ° of heating in Muffle furnace 2 hours, furnace cooling obtained orange-yellow α-Fe on substrate2O3Film；
(3) is by tin precursor solution multiple spin coating 200 ° of heating 10min on the substrate obtained by (2)；
(4) substrate obtained by (3) is immersed in the solution of trivalent iron salt and sodium nitrate by, is placed in 10min in 100 ° of water-baths.
3. the preparation method of photoelectrochemical cell light anode as described in claim 1, it is characterised in that：
In step (1), the substrate is FTO；
It is described a certain amount of for 25mg in step (2)；
In step (3), the tin precursor solution is 180mM SnCl4·5H2O solution；
In step (4), the trivalent iron salt is 0.10M FeCl3·6H2O solution, sodium nitrate solution 1M.
CN201810746303.6A 2018-07-09 2018-07-09 Preparation method of photo-anode of photoelectrochemical cell Active CN108914148B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110791770A (en) * 2019-11-08 2020-02-14 南京大学 Preparation and application of photo-assisted thermoelectric coupling oxygen precipitation electrode

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101889060A (en) * 2007-12-19 2010-11-17 默克专利股份有限公司 Optically variable pigments of high electrical conductivity
CN103043710A (en) * 2011-10-17 2013-04-17 中国科学院福建物质结构研究所 Method for heterogeneously growing nano SnO2 on surface of alpha-Fe2O3 nanocrystalline
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
CN104953103A (en) * 2015-07-09 2015-09-30 山西大学 Method for preparing Fe2O3 and expanded graphite composite material of lithium ion battery
CN106929827A (en) * 2017-04-27 2017-07-07 郑州大学 A kind of few layer MoS2The preparation method of film
CN107326385A (en) * 2017-06-16 2017-11-07 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
CN108190860A (en) * 2018-01-31 2018-06-22 南京大学 A kind of method that microwave prepares single-walled carbon nanotube

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101889060A (en) * 2007-12-19 2010-11-17 默克专利股份有限公司 Optically variable pigments of high electrical conductivity
CN103043710A (en) * 2011-10-17 2013-04-17 中国科学院福建物质结构研究所 Method for heterogeneously growing nano SnO2 on surface of alpha-Fe2O3 nanocrystalline
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
CN104953103A (en) * 2015-07-09 2015-09-30 山西大学 Method for preparing Fe2O3 and expanded graphite composite material of lithium ion battery
CN106929827A (en) * 2017-04-27 2017-07-07 郑州大学 A kind of few layer MoS2The preparation method of film
CN107326385A (en) * 2017-06-16 2017-11-07 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
CN108190860A (en) * 2018-01-31 2018-06-22 南京大学 A kind of method that microwave prepares single-walled carbon nanotube

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ALAGAPPAN ANNAMALAI等: "Fabrication of superior α-Fe2O3 nanorod photoanodes through exsitu Sn-doping for solar water splitting", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 *
ANTON TSYGANOK等: "Different Roles of Fe1−xNixOOH Cocatalyst on Hematite (α-Fe2O3) Photoanodes with Different Dopants", 《ACS CATAL》 *
GAO YUE等: "Efficient growth of aligned SnO2 nanorod arrays on hematite(a-Fe2O3) nanotube arrays for photoelectrochemicaland photocatalytic applications", 《J MATER SCI: MATER ELECTRON》 *
YUFEI YUAN等: "Combining Bulk/Surface Engineering of Hematite To Synergistically", 《ACS APPL. MATER. INTERFACES》 *
王开放等: "α-Fe2O3光电催化分解水制备氢气研究进展", 《化工进展》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110791770A (en) * 2019-11-08 2020-02-14 南京大学 Preparation and application of photo-assisted thermoelectric coupling oxygen precipitation electrode
CN110791770B (en) * 2019-11-08 2022-02-08 南京大学 Preparation and application of photo-assisted thermoelectric coupling oxygen precipitation electrode

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