CN113174610B - Alpha/gamma-ferric oxide film electrode and preparation method and application thereof - Google Patents
Alpha/gamma-ferric oxide film electrode and preparation method and application thereof Download PDFInfo
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- CN113174610B CN113174610B CN202110459133.5A CN202110459133A CN113174610B CN 113174610 B CN113174610 B CN 113174610B CN 202110459133 A CN202110459133 A CN 202110459133A CN 113174610 B CN113174610 B CN 113174610B
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 56
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 98
- 239000000243 solution Substances 0.000 claims description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 60
- 239000007864 aqueous solution Substances 0.000 claims description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 36
- 235000010344 sodium nitrate Nutrition 0.000 claims description 30
- 239000004317 sodium nitrate Substances 0.000 claims description 30
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 23
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 36
- 229940032296 ferric chloride Drugs 0.000 description 21
- 238000001035 drying Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 229910001566 austenite Inorganic materials 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910000859 α-Fe Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- UKDYPJBSLOCNRU-UHFFFAOYSA-J ethanol tetrachlorotitanium Chemical compound CCO.Cl[Ti](Cl)(Cl)Cl UKDYPJBSLOCNRU-UHFFFAOYSA-J 0.000 description 10
- 238000007664 blowing Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention provides an alpha/gamma-ferric oxide film electrode, a preparation method and application thereof, belonging to the technical field of photocatalytic materials, comprising the following steps: pouring the precursor solution on the surface of a matrix for first hydrothermal calcination to obtain an alpha-ferric oxide film electrode; and then carrying out secondary hydrothermal calcination to obtain the alpha/gamma-ferric oxide film electrode. The invention prepares the first layer of alpha-ferric oxide film through one-time hydrothermal calcination, then prepares the second layer of alpha-ferric oxide film through the two-time hydrothermal calcination, simultaneously the alpha-ferric oxide in the first layer of film is converted into gamma-ferric oxide, the newly generated alpha-ferric oxide film is covered on the surface of the gamma-ferric oxide, the alpha/gamma-ferric oxide film electrode is obtained, the photoelectrocatalysis activity of the photo-anode is fully improved, and the photocurrent of the prepared alpha/gamma-ferric oxide film electrode is more than or equal to 0.5mA/cm 2 。
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to an alpha/gamma-ferric oxide film electrode, a preparation method and application thereof.
Background
With the development of economy and the consumption of energy, the utilization of inexhaustible solar energy is an effective method for solving the problem that fossil fuels are not renewable. At present, the solar energy utilization modes are mainly divided into three types: photo-thermal conversion, photoelectric conversion, and photochemical conversion. Photo-thermal conversion is to convert solar energy into heat, and the generated heat can be directly utilized (such as a solar water heater) and indirectly utilized to drive certain endothermic reactions. Such as using solar energy converted heat to drive CO and H 2 The reaction produces fuel, a technology that has been used on a large scale in the united states and morocco, among other countries. The photoelectric conversion is to convert solar energy into electric energy, and the first time in 1883 U.S. scientists Charles fritts realize the conversion of solar energy into electric energy by using germanium semiconductorsAlthough the photoelectric conversion efficiency is only 1%, a method is provided for the realization of solar energy to electric energy, and then various electrode materials are found and used in solar cells. Compared with the two solar energy utilization modes, the photochemical conversion is to convert solar energy into chemical energy, and the problems of efficiency, cost and the like are still in a research stage at present. Ways of investigating the conversion of relatively large amounts of solar energy into chemical energy in the laboratory include decomposing hydrogen from water using solar energy, reducing CO using solar energy 2 And degrading organic pollutants by utilizing solar energy, synthesizing ammonia by utilizing solar energy, and the like. Among them, the decomposition of hydrogen from water by solar energy is attracting attention. It is well known that hydrogen energy is a clean energy source, and with the continuous consumption of fossil fuels, the utilization of solar energy to produce hydrogen is the most promising means for solving the energy shortage. Because four electrons are needed for the photocatalytic water oxidation, the photocatalytic water oxidation becomes a speed control step of the overall efficiency of the photocatalytic water, and therefore, the construction of a high-efficiency photo-anode material is a key for improving the overall efficiency of the photocatalytic water.
An ideal photoanode should have three conditions: (1) the electrode itself has excellent electrical conductivity; (2) The electrode has relatively high catalytic activity on the oxidation reaction of the electrolyte; (3) the electrode can exist stably in the electrolyte. The single-component photo-anode can not well meet the three requirements, so the research and development of the composite photo-anode become the hot spot of the current research. It is known that a composite photo-anode can combine the unique advantages of two materials, reduce the bulk recombination of a single semiconductor, promote the effective transmission of interface charges, thereby realizing 1+1>2. Such as: composite heterojunction photo-anode Co 3 O 4 /Ti:Fe 2 O 3 Is constructed to reduce Fe 2 O 3 Is capable of enabling holes to rapidly migrate to Co 3 O 4 The surface participates in the oxidation reaction of water. Therefore, the construction of the composite photo-anode is an effective way for improving the water photolysis performance.
However, for the heterojunction, due to lattice mismatch of different materials at two sides, the transmission of interface charges is not smooth enough, so that the optimal effect cannot be achieved. Thus, fe is constructed 2 O 3 The homojunction becomes the killer for solving the interface transmission problem, and Fe 2 O 3 Exhibit different photocatalytic activities. Such as reported in the literature for alpha/beta Fe 2 O 3 Rutile/anatase TiO 2 Exhibit excellent photocatalytic performance. Thus, a/gamma-Fe containing different crystal phases was constructed 2 O 3 Is to promote Fe 2 O 3 An efficient way of fast charge transport. However, the current research has the defects of the ex-situ preparation of the composite electrode material, and is easy to cause Fe 2 O 3 Between the metal oxide and the FTO substrate and Fe 2 O 3 The contact between different crystal phases is not compact enough, thereby influencing the photocatalytic activity of the composite electrode material and failing to achieve the expected effect. Accordingly, it is desirable to provide a catalyst capable of increasing α/γ -Fe 2 O 3 A method for preparing film catalytic activity.
Disclosure of Invention
The invention aims to provide an alpha/gamma-ferric oxide thin film electrode, a preparation method and application thereof, and the alpha/gamma-ferric oxide thin film electrode prepared by the preparation method provided by the invention has higher catalytic activity under the potential of 1.23Vvs.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an alpha/gamma-ferric oxide film electrode, which comprises the following steps:
(1) Pouring the precursor solution on the surface of a matrix, performing first hydrothermal reaction, and then performing first calcination treatment to obtain an alpha-ferric oxide film electrode;
(2) Pouring the precursor solution on the surface of the alpha-ferric oxide film electrode obtained in the step (1), performing a second hydrothermal reaction, and then performing a second calcination treatment to obtain an alpha/gamma-ferric oxide film electrode;
the precursor solution in the step (1) and the step (2) is formed by mixing a mixed aqueous solution of ferric chloride and sodium nitrate with an ethanol solution of titanium tetrachloride.
Preferably, the concentration of ferric chloride in the mixed aqueous solution used for preparing the precursor solutions in the step (1) and the step (2) is independently 0.0187 to 0.075mol/L, and the concentration of sodium nitrate is independently 0.125 to 0.5mol/L.
Preferably, the volume percentage of titanium tetrachloride in the ethanol solution used for preparing the precursor solutions in the step (1) and the step (2) is independently 0.5-1.5%.
Preferably, the volume ratio of the mixed aqueous solution to the ethanol solution used for preparing the precursor solutions in the step (1) and the step (2) is 100000: (75-175).
Preferably, the temperature of the first hydrothermal reaction in the step (1) is 80-120 ℃, and the time of the first hydrothermal reaction is 10-15 h.
Preferably, the temperature of the first calcination treatment in the step (1) is 500-600 ℃, and the time of the first calcination treatment is 1-4 hours.
Preferably, the temperature of the second hydrothermal reaction in the step (2) is 80-120 ℃, and the time of the second hydrothermal reaction is 10-15 h.
Preferably, the temperature of the second calcination treatment in the step (2) is 500-600 ℃, and the time of the second calcination treatment is 1-4 hours.
The invention provides an alpha/gamma-ferric oxide film electrode prepared by the preparation method, which comprises a substrate, a gamma-ferric oxide film attached to the surface of the substrate and an alpha-ferric oxide film covered on the surface of the gamma-ferric oxide film, wherein Ti is doped in the alpha-ferric oxide film and the gamma-ferric oxide film 4 + 。
The invention also provides application of the alpha/gamma-ferric oxide film electrode in photoelectrochemical decomposition water as a photo-anode.
The invention provides a preparation method of an alpha/gamma-ferric oxide film electrode, which comprises the following steps: (1) Pouring the precursor solution on the surface of a matrix, performing first hydrothermal reaction, and then performing first calcination treatment to obtain an alpha-ferric oxide film electrode; (2) Pouring the precursor solution into the alpha-ferric oxide film electrode obtained in the step (1)Carrying out a second hydrothermal reaction on the surface, and then carrying out a second calcination treatment to obtain an alpha/gamma-ferric oxide film electrode; the precursor solution in the step (1) and the step (2) is formed by mixing a mixed aqueous solution of ferric chloride and sodium nitrate with an ethanol solution of titanium tetrachloride. The invention prepares alpha/gamma-Fe by a two-step hydrothermal calcination method 2 O 3 The film electrode is prepared into a first layer of alpha-Fe through one-time hydrothermal calcination treatment 2 O 3 Film, then at the first layer of alpha-Fe 2 O 3 Preparing a second layer of alpha-Fe by performing secondary hydrothermal calcination on the surface of the film 2 O 3 Film, while alpha-Fe in the first film 2 O 3 Gradually converted into gamma-Fe during calcination 2 O 3 Forming gamma-Fe 2 O 3 Film, newly formed alpha-Fe 2 O 3 The film will cover the generated gamma-Fe 2 O 3 Surface, thereby obtaining alpha/gamma-Fe 2 O 3 Film electrode, fe is improved 2 O 3 Between the Fe and the matrix, and Fe 2 O 3 Contact performance between different crystal phases; the preparation process is simple, the operation is easy, the production cost is greatly reduced, the photoelectrocatalysis activity of the photo-anode can be fully improved, the photoelectric conversion efficiency is improved, and the preparation process is suitable for the photocatalytic electrode material of the oxidation type. The results of the examples show that alpha/gamma-Fe prepared by the preparation method of the present invention 2 O 3 The photocurrent of the thin film electrode serving as the photo-anode under the potential of 1.23V vs. RHE is more than or equal to 0.5mA/cm 2 。
Drawings
FIG. 1 is a schematic diagram of the structure of an α/γ -iron oxide thin film electrode provided by the present invention;
FIG. 2 is an XRD pattern of an alpha-iron sesquioxide film and an alpha/gamma-iron sesquioxide film prepared in example 2 of the present invention;
FIG. 3 is a graph showing photocurrent density-voltage (J-V) curves of the thin film electrodes prepared in examples 1 to 3 and comparative example 1 according to the present invention.
Detailed Description
The invention provides a preparation method of an alpha/gamma-ferric oxide film electrode, which comprises the following steps:
(1) Pouring the precursor solution on the surface of a matrix, performing first hydrothermal reaction, and then performing first calcination treatment to obtain an alpha-ferric oxide film electrode;
(2) Pouring the precursor solution on the surface of the alpha-ferric oxide film electrode obtained in the step (1), performing a second hydrothermal reaction, and then performing a second calcination treatment to obtain an alpha/gamma-ferric oxide film electrode;
the precursor solution in the step (1) and the step (2) is formed by mixing a mixed aqueous solution of ferric chloride and sodium nitrate with an ethanol solution of titanium tetrachloride.
The sources of the components are not particularly limited, and the products are commercially available or prepared by conventional methods known to those skilled in the art.
The precursor solution is poured on the surface of a matrix, and is subjected to first hydrothermal reaction and then first calcination treatment to obtain the alpha-ferric oxide film electrode.
In the invention, the precursor solution is formed by mixing a mixed aqueous solution of ferric chloride and sodium nitrate with an ethanol solution of titanium tetrachloride.
In the present invention, the concentration of ferric chloride in the mixed aqueous solution used for preparing the precursor solution is preferably 0.0187 to 0.075mol/L, more preferably 0.025 to 0.05mol/L, and still more preferably 0.035 to 0.04mol/L. The concentration of ferric chloride in the mixed aqueous solution is limited in the range, so that the film has proper thickness, and the photoelectrocatalysis performance of the film electrode is further improved.
In the present invention, the concentration of sodium nitrate in the mixed aqueous solution used for preparing the precursor solution is preferably 0.125 to 0.5mol/L, more preferably 0.15 to 0.4mol/L, and still more preferably 0.2 to 0.3mol/L. The invention limits the concentration of sodium nitrate in the mixed aqueous solution within the above range, and can regulate and control the crystal form of ferric oxide to obtain alpha-ferric oxide.
The method for preparing the mixed aqueous solution of ferric chloride and sodium nitrate is not particularly limited, and the technical scheme for preparing the mixed aqueous solution, which is well known to the person skilled in the art, can be adopted. In the present invention, the method for preparing the mixed aqueous solution of ferric chloride and sodium nitrate is preferably to mix ferric chloride hexahydrate and sodium nitrate with water. In the present invention, the mixing is preferably performed under ultrasonic conditions; the time of the ultrasound is preferably 20min.
In the present invention, the volume percentage of titanium tetrachloride in the ethanol solution used for preparing the precursor solution is preferably 0.5 to 1.5%, more preferably 0.7 to 1.2%, and most preferably 0.9 to 1.0%. The invention limits the volume percentage of titanium tetrachloride in the ethanol solution to the above range, and can regulate and control Ti in alpha-ferric oxide 4+ The doping amount of the alpha-ferric oxide is improved, and the photoelectrocatalysis performance of the film electrode is further improved.
In the present invention, the volume ratio of the mixed aqueous solution to the ethanol solution used for preparing the precursor solution is preferably 100000: (75 to 175), more preferably 100000: (100 to 155), more preferably 100000: (115-145), most preferably 100000: (125-130). The invention limits the volume ratio of the mixed aqueous solution and the ethanol solution in the above range, and can adjust the thickness of the alpha-ferric oxide film and Ti 4+ Further improves the performance of the photocatalytic reaction and improves the photoelectrocatalysis performance.
The operation of mixing the aqueous solution of ferric chloride and sodium nitrate with the ethanol solution of titanium tetrachloride is not particularly limited, and a technical scheme of mixing materials well known to those skilled in the art can be adopted. In the present invention, the mixing is preferably performed under stirring conditions; the stirring time is preferably 10 to 30 minutes. In embodiments of the invention, the mixing is preferably performed in a beaker.
In the present invention, the substrate is preferably FTO conductive glass. In the present invention, the substrate is preferably pretreated prior to use; the pretreatment preferably comprises washing with dilute hydrochloric acid, analytical ethanol, acetone, ethyl acetate and high-grade ethanol in sequence; the washing is preferably carried out under ultrasonic conditions; the time for each washing is preferably 20 minutes. In the present invention, the concentration of the dilute hydrochloric acid is preferably 0.2mol/L. In the present invention, the amount of the detergent is preferably 30mL. In the present invention, the size of the substrate is preferably 1cm×2.5cm.
In the present invention, the temperature of the first hydrothermal reaction is preferably 80 to 120 ℃, more preferably 90 to 110 ℃, and most preferably 100 ℃; the time of the first hydrothermal reaction is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours. In the present invention, fe during the first hydrothermal reaction 3+ The reaction is carried out to generate FeOOH nano-rods, and titanium tetrachloride is hydrolyzed to generate titanium dioxide.
The apparatus for the first hydrothermal reaction is not particularly limited, and a reaction apparatus known to those skilled in the art may be used. In the present invention, the first hydrothermal reaction is preferably performed in an electrothermal blowing dry oven. The present invention preferably places the substrate in an autoclave liner for a first hydrothermal reaction.
After the first hydrothermal reaction is finished, the product of the first hydrothermal reaction is preferably subjected to cooling, washing and drying in sequence and then subjected to first calcination treatment to obtain the alpha-ferric oxide film electrode. In the present invention, the cooling is preferably furnace-mounted cooling, and the end point of the cooling is preferably room temperature; the drying is preferably blow-drying under nitrogen atmosphere.
In the present invention, the temperature of the first calcination treatment is preferably 500 to 600 ℃, more preferably 520 to 580 ℃, most preferably 540 to 560 ℃, and the time of the first calcination treatment is preferably 1 to 4 hours, more preferably 2 to 3 hours. In the invention, feOOH reacts to produce alpha-ferric oxide, ti in the first calcination process 4+ Ions are doped into the alpha-ferric oxide. In the present invention, the first calcination treatment is preferably performed in air.
In the present invention, the temperature rising rate of the temperature to the first calcination treatment temperature is preferably 1 to 3 ℃/min, more preferably 2 ℃/min.
The invention limits the temperature and time of the first hydrothermal reaction and the first calcination treatment in the above range, so that the alpha-ferric oxide has better crystallinity and further improves the photoelectrocatalysis performance.
In the present invention, the thickness of the α -ferric oxide film obtained after the first calcination treatment is preferably 220 to 300nm.
After the alpha-ferric oxide film electrode is obtained, the precursor solution is poured on the surface of the alpha-ferric oxide film electrode, and the alpha/gamma-ferric oxide film electrode is obtained after the second hydrothermal reaction and the second calcination treatment.
In the invention, the precursor solution is formed by mixing a mixed aqueous solution of ferric chloride and sodium nitrate with an ethanol solution of titanium tetrachloride.
In the present invention, the concentration of ferric chloride in the mixed aqueous solution used for preparing the precursor solution is preferably 0.0187 to 0.075mol/L, more preferably 0.025 to 0.05mol/L, and still more preferably 0.035 to 0.04mol/L. The concentration of ferric chloride in the mixed aqueous solution is limited in the range, so that the film has proper thickness, and the photoelectrocatalysis performance of the film electrode is further improved.
In the present invention, the concentration of sodium nitrate in the mixed aqueous solution used for preparing the precursor solution is preferably 0.125 to 0.5mol/L, more preferably 0.15 to 0.4mol/L, and still more preferably 0.2 to 0.3mol/L. The invention limits the concentration of sodium nitrate in the mixed aqueous solution within the above range, and can regulate and control the crystal form of ferric oxide to obtain alpha-ferric oxide.
The method for preparing the mixed aqueous solution of ferric chloride and sodium nitrate is not particularly limited, and the technical scheme for preparing the mixed aqueous solution, which is well known to the person skilled in the art, can be adopted. In the present invention, the method for preparing the mixed aqueous solution of ferric chloride and sodium nitrate is preferably to mix ferric chloride hexahydrate and sodium nitrate with water. In the present invention, the mixing is preferably performed under ultrasonic conditions; the time of the ultrasound is preferably 20min.
In the present invention, the volume percentage of titanium tetrachloride in the ethanol solution used for preparing the precursor solution is preferably 0.5 to 1.5%, more preferably 0.7 to 1.2%, and most preferably 0.9 to 1.0%. The book is provided withThe invention limits the volume percentage of titanium tetrachloride in the ethanol solution to the above range, and can regulate and control Ti in alpha-ferric oxide 4+ The doping amount of the alpha-ferric oxide is improved, and the photoelectrocatalysis performance of the film electrode is further improved.
In the present invention, the volume ratio of the mixed aqueous solution to the ethanol solution used for preparing the precursor solution is preferably 100000: (75 to 175), more preferably 100000: (100 to 155), more preferably 100000: (115-145), most preferably 100000: (125-130). The invention limits the volume ratio of the mixed aqueous solution and the ethanol solution in the above range, and can adjust the thickness of the alpha-ferric oxide film and Ti 4+ Further improves the performance of the photocatalytic reaction and improves the photoelectrocatalysis performance.
The operation of mixing the aqueous solution of ferric chloride and sodium nitrate with the ethanol solution of titanium tetrachloride is not particularly limited, and a technical scheme of mixing materials well known to those skilled in the art can be adopted. In the present invention, the mixing is preferably performed under stirring conditions; the stirring time is preferably 10 to 30 minutes. In embodiments of the invention, the mixing is preferably performed in a beaker.
In the present invention, the temperature of the second hydrothermal reaction is preferably 80 to 120 ℃, more preferably 90 to 110 ℃, and most preferably 100 ℃, and the time of the second hydrothermal reaction is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours. In the present invention, fe during the second hydrothermal reaction 3+ The reaction is carried out to generate FeOOH nano-rods, and titanium tetrachloride is hydrolyzed to generate titanium dioxide.
The apparatus for the second hydrothermal reaction is not particularly limited, and a reaction apparatus known to those skilled in the art may be used. In the present invention, the second hydrothermal reaction is preferably performed in an electrothermal blowing dry oven. The invention preferably places the film surface of the alpha-ferric oxide film electrode in the liner of the high-pressure reaction kettle in a downward inclined 45 DEG for carrying out the second hydrothermal reaction.
After the second hydrothermal reaction is finished, the product of the second hydrothermal reaction is preferably subjected to cooling, water washing and drying in sequence and then is subjected to a second calcination treatment to obtain the alpha/gamma-ferric oxide film electrode. In the present invention, the cooling is preferably furnace-mounted cooling, and the end point of the cooling is preferably room temperature; the drying is preferably blow-drying under nitrogen atmosphere.
In the present invention, the temperature of the second calcination treatment is preferably 500 to 600 ℃, more preferably 520 to 580 ℃, most preferably 540 to 560 ℃, and the time of the second calcination treatment is preferably 1 to 4 hours, more preferably 2 to 3 hours. In the invention, a layer of alpha-ferric oxide film is newly generated in the second calcination process, and meanwhile, the first layer of alpha-ferric oxide is gradually converted into gamma-ferric oxide, and the newly generated alpha-ferric oxide film covers the surface of the gamma-ferric oxide film to form an alpha/gamma-ferric oxide film. In the present invention, the second calcination treatment is preferably performed in air.
In the present invention, the rate of heating to the second calcination treatment temperature is preferably 1 to 3℃per minute, more preferably 2℃per minute.
The invention limits the temperature and time of the second hydrothermal reaction and the second calcination treatment in the above range, so that the ferric oxide has better crystallinity and further improves the photoelectrocatalysis performance.
In the present invention, the thickness of the α/γ -iron sesquioxide film obtained after the second calcination treatment is preferably 230 to 310nm.
The invention prepares alpha/gamma-Fe by a two-step hydrothermal calcination method 2 O 3 The film electrode is prepared into a first layer of alpha-Fe through one-time hydrothermal calcination treatment 2 O 3 Film, then at the first layer of alpha-Fe 2 O 3 Preparing a second layer of alpha-Fe by performing secondary hydrothermal calcination on the surface of the film 2 O 3 Film, while alpha-Fe in the first film 2 O 3 Gradually converted into gamma-Fe during calcination 2 O 3 Forming gamma-Fe 2 O 3 Film, newly formed alpha-Fe 2 O 3 The film will cover the generated gamma-Fe 2 O 3 Surface, thereby obtaining alpha/gamma-Fe 2 O 3 Film electrode, fe is improved 2 O 3 Between the Fe and the matrix, and Fe 2 O 3 Contact performance between different crystal phases; the concentration of each component and the preparation process parameters are controlled, so that the film has proper thickness and Ti 4+ The doping amount further improves the photoelectrocatalysis performance, the preparation process is simple, the operation is easy, the production cost is greatly reduced, and the preparation method is suitable for the oxidation type photoelectrocatalysis electrode material.
The invention provides an alpha/gamma-ferric oxide film electrode prepared by the preparation method, which comprises a substrate, a gamma-ferric oxide film attached to the surface of the substrate and an alpha-ferric oxide film covered on the surface of the gamma-ferric oxide film, wherein Ti is doped in the alpha-ferric oxide film and the gamma-ferric oxide film 4 + . In the present invention, the thickness of the α/γ -iron sesquioxide thin film in the α/γ -iron sesquioxide thin film electrode is preferably 230 to 310nm.
The alpha/gamma-ferric oxide film electrode prepared by the invention comprises ferric oxide with different crystal phases to form a homojunction structure, the different crystal phases have good contact performance, the rapid transmission of charges in the ferric oxide can be promoted, the film has proper thickness, the photocatalysis reaction is facilitated, and simultaneously the doped Ti 4+ The conductivity of the thin film can be improved, so that the thin film electrode has excellent photoelectrocatalysis performance.
The invention also provides application of the alpha/gamma-ferric oxide film electrode in photoelectrochemical decomposition water as a photo-anode. The application of the alpha/gamma-ferric oxide film electrode as a photo-anode in photoelectrochemical decomposition water is not particularly limited, and the technical scheme of the application of the photo-anode in photoelectrochemical decomposition water, which is well known to the person skilled in the art, is adopted.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the alpha/gamma-ferric oxide film electrode comprises the following specific steps:
(1) Ultrasonically washing 1cm multiplied by 2.5cm FTO conductive glass sequentially with dilute hydrochloric acid, analytical ethanol, acetone, ethyl acetate and high-grade ethanol for 20min each time;
(2) Preparing 100mL of an aqueous solution containing 0.0187mol/L ferric chloride hexahydrate and 0.125mol/L sodium nitrate in a beaker, carrying out ultrasonic treatment for 20min, adding 175 mu L of a titanium tetrachloride ethanol solution with a volume percentage of 1% (the volume ratio of the mixed aqueous solution of the ferric chloride and the sodium nitrate to the titanium tetrachloride ethanol solution is 100000:175), and stirring for 20min to obtain a precursor solution;
(3) Placing the cleaned FTO in a high-pressure reaction kettle liner, pouring the precursor solution prepared in the step (2), placing in an electrothermal blowing drying oven for reaction at 100 ℃ for 12 hours, cooling to room temperature after the reaction is completed, drying in a nitrogen atmosphere after water washing, heating to 550 ℃ at a heating rate of 2 ℃/min, and calcining in air for 2 hours to obtain the alpha-ferric oxide film electrode;
(4) Placing an FTO conductive film with an alpha-ferric oxide film in a high-pressure reaction kettle liner in a downward inclined manner by 45 degrees, pouring the precursor solution prepared in the step (2), placing the precursor solution in an electrothermal blowing drying box for reacting for 12 hours at the temperature of 100 ℃, cooling to room temperature after the reaction is finished, drying in a nitrogen atmosphere after washing, heating to 550 ℃ at the heating rate of 2 ℃/min, and calcining in air for 2 hours to obtain the alpha/gamma-ferric oxide film electrode.
Example 2
The preparation method of the alpha/gamma-ferric oxide film electrode comprises the following specific steps:
(1) Ultrasonically washing 1cm multiplied by 2.5cm FTO conductive glass sequentially with dilute hydrochloric acid, analytical ethanol, acetone, ethyl acetate and high-grade ethanol for 20min each time;
(2) Preparing 100mL of an aqueous solution containing 0.0187mol/L ferric chloride hexahydrate and 0.125mol/L sodium nitrate in a beaker, carrying out ultrasonic treatment for 20min, adding 175 mu L of a titanium tetrachloride ethanol solution with a volume percentage of 1% (the volume ratio of the mixed aqueous solution of the ferric chloride and the sodium nitrate to the titanium tetrachloride ethanol solution is 100000:175), and stirring for 20min to obtain a precursor solution;
(3) Placing the cleaned FTO in a high-pressure reaction kettle liner, pouring the precursor solution prepared in the step (2), placing in an electrothermal blowing drying oven for reaction at 100 ℃ for 12 hours, cooling to room temperature after the reaction is completed, drying in a nitrogen atmosphere after water washing, heating to 550 ℃ at a heating rate of 2 ℃/min, and calcining in air for 2 hours to obtain the alpha-ferric oxide film electrode;
(4) Preparing 100mL of aqueous solution containing 0.075mol/L ferric chloride hexahydrate and 0.5mol/L sodium nitrate in a beaker, carrying out ultrasonic treatment for 20min, adding 75 mu L of 1% by volume of titanium tetrachloride ethanol solution (the volume ratio of the mixed aqueous solution of ferric chloride and sodium nitrate to the titanium tetrachloride ethanol solution is 100000:75), and stirring for 20min to obtain a precursor solution;
(5) Placing an FTO conductive film with an alpha-ferric oxide film in a high-pressure reaction kettle liner in a downward inclined manner by 45 degrees, pouring the precursor solution prepared in the step (4), placing the precursor solution in an electrothermal blowing drying box for reacting for 12 hours at the temperature of 100 ℃, cooling to room temperature after the reaction is finished, drying in a nitrogen atmosphere after washing, heating to 550 ℃ at the heating rate of 2 ℃/min, and calcining in air for 2 hours to obtain the alpha/gamma-ferric oxide film electrode.
Example 3
The preparation method of the alpha/gamma-ferric oxide film electrode comprises the following specific steps:
(1) Ultrasonically washing 1cm multiplied by 2.5cm FTO conductive glass sequentially with dilute hydrochloric acid, analytical ethanol, acetone, ethyl acetate and high-grade ethanol for 20min each time;
(2) Preparing 100mL of aqueous solution containing 0.075mol/L ferric chloride hexahydrate and 0.5mol/L sodium nitrate in a beaker, carrying out ultrasonic treatment for 20min, adding 75 mu L of 1% by volume of titanium tetrachloride ethanol solution (the volume ratio of the mixed aqueous solution of ferric chloride and sodium nitrate to the titanium tetrachloride ethanol solution is 100000:75), and stirring for 20min to obtain a precursor solution;
(3) Placing the cleaned FTO in a high-pressure reaction kettle liner, pouring the precursor solution prepared in the step (2), placing in an electrothermal blowing drying oven for reaction at 100 ℃ for 12 hours, cooling to room temperature after the reaction is completed, drying in a nitrogen atmosphere after water washing, heating to 550 ℃ at a heating rate of 2 ℃/min, and calcining in air for 2 hours to obtain the alpha-ferric oxide film electrode;
(4) Placing an FTO conductive film with an alpha-ferric oxide film in a high-pressure reaction kettle liner in a downward inclined manner by 45 degrees, pouring the precursor solution prepared in the step (2), placing the precursor solution in an electrothermal blowing drying box for reacting for 12 hours at the temperature of 100 ℃, cooling to room temperature after the reaction is finished, drying in a nitrogen atmosphere after washing, heating to 550 ℃ at the heating rate of 2 ℃/min, and calcining in air for 2 hours to obtain the alpha/gamma-ferric oxide film.
Comparative example 1
(1) Ultrasonically washing 1cm multiplied by 2.5cm FTO conductive glass sequentially with dilute hydrochloric acid, analytical ethanol, acetone, ethyl acetate and high-grade ethanol for 20min each time;
(2) Preparing 100mL of aqueous solution containing 0.075mol/L ferric chloride hexahydrate and 0.5mol/L sodium nitrate in a beaker, carrying out ultrasonic treatment for 20min, adding 75 mu L of 1% by volume of titanium tetrachloride ethanol solution (the volume ratio of the mixed aqueous solution of ferric chloride and sodium nitrate to the titanium tetrachloride ethanol solution is 100000:75), and stirring for 20min to obtain a precursor solution;
(3) Placing the cleaned FTO into a high-pressure reaction kettle liner, pouring the precursor solution prepared in the step (2), placing the precursor solution into an electrothermal blowing drying box for reaction at 100 ℃ for 12 hours, cooling to room temperature after the reaction is completed, drying the precursor solution in a nitrogen atmosphere after water washing, heating to 550 ℃ at a heating rate of 2 ℃/min, and calcining the precursor solution in air for 2 hours to obtain the alpha-ferric oxide film electrode.
The XRD patterns of the α -ferric oxide film and the α/γ -ferric oxide film prepared in example 2 were analyzed at a scanning rate of 10 °/min from 10 ° to 80 ° using an X-ray diffractometer, and the results are shown in fig. 2. In fig. 2, curve 1 shows the XRD pattern of the α/γ -iron oxide film, and curve 2 shows the XRD pattern of the α -iron oxide film. As can be seen from fig. 2, the α -ferric oxide was synthesized after the first hydrothermal calcination treatment, and characteristic peaks thereof were observed at 35.6 ° and 64 °, which correspond to characteristic peaks of α -ferric oxide standard card (JCPDS No. 33-0664), and after the second hydrothermal calcination treatment, a new characteristic peak of 31.2 ° was observed in addition to characteristic peaks of α -ferric oxide, which correspond to characteristic peaks of γ -ferric oxide standard card (JCPDS No. 39-1346), which demonstrated that the α -ferric oxide of the first layer was converted into γ -ferric oxide during the second hydrothermal calcination, thereby producing an α/γ -ferric oxide film.
Photoelectrochemical properties of the thin film electrodes prepared in examples 1 to 3 and comparative example 1 were tested: the system used for the photoelectrochemical test was a three-electrode system in which the thin film electrodes prepared in examples 1 to 3 and comparative example 1 were used as working electrodes, saturated Ag/AgCl electrodes were used as reference electrodes, pt wires were used as counter electrodes, the electrolyte used for the test was 1mol/LKOH (pH=13.6), the Light source used was a 300W xenon lamp (Micro Solar 300Perfect Light) equipped with AM 1.5G, and the Light intensity was adjusted to 100mW/cm by a radiometer 2 The photo-current density-voltage (J-V) curve of the photo-anode was recorded by an electrochemical workstation, and the result was shown in FIG. 3 (curve 3 in FIG. 3 is the thin film electrode prepared in example 2, curve 4 is the thin film electrode prepared in example 1, curve 5 is the thin film electrode prepared in example 3, curve 6 is the thin film electrode prepared in comparative example 1), the light control area was 0.298cm 2 The thin film electrode calculated from the photocurrent density-voltage (J-V) curve was the photocurrent of the photoanode at a potential of 1.23vvs.
TABLE 1 photoelectrochemical properties of thin film electrodes obtained in examples 1 to 3 and comparative example 1
| Photocurrent (mA/cm) 2 ) | |
| Example 1 | 1.4 |
| Example 2 | 2.4 |
| Example 3 | 0.5 |
| Comparative example 1 | 0.3 |
As can be seen from table 1, the photoelectric properties of the thin film electrodes prepared in examples 1 to 3 are superior to those of comparative example 1, and the α/γ -iron sesquioxide phase can improve the photoelectric properties of the single crystal phase iron sesquioxide, and the photoelectric properties of the thin film electrodes can be further adjusted by changing the concentration of the precursor solution.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. The preparation method of the alpha/gamma-ferric oxide film electrode comprises the following steps:
(1) Pouring the precursor solution on the surface of a matrix, performing first hydrothermal reaction, and then performing first calcination treatment to obtain an alpha-ferric oxide film electrode;
(2) Pouring the precursor solution on the surface of the alpha-ferric oxide film electrode obtained in the step (1), performing a second hydrothermal reaction, and then performing a second calcination treatment to obtain an alpha/gamma-ferric oxide film electrode;
the precursor solution in the step (1) and the step (2) is formed by mixing a mixed aqueous solution of ferric chloride and sodium nitrate with an ethanol solution of titanium tetrachloride; the concentration of ferric chloride in the mixed aqueous solution used for preparing the precursor solutions in the step (1) and the step (2) is independently 0.0187-0.075 mol/L, and the concentration of sodium nitrate is independently 0.125-0.5 mol/L; the volume percentage of titanium tetrachloride in the ethanol solution used for preparing the precursor solutions in the step (1) and the step (2) is independently 0.5-1.5%; the volume ratio of the mixed aqueous solution and the ethanol solution used for preparing the precursor solutions in the step (1) and the step (2) is 100000 independently: (75-175); the temperature of the first hydrothermal reaction in the step (1) is 80-120 ℃, and the time of the first hydrothermal reaction is 10-15 h; the temperature of the first calcination treatment in the step (1) is 500-600 ℃, and the time of the first calcination treatment is 1-4 hours; the temperature of the second hydrothermal reaction in the step (2) is 80-120 ℃, and the time of the second hydrothermal reaction is 10-15 h; the temperature of the second calcination treatment in the step (2) is 500-600 ℃, and the time of the second calcination treatment is 1-4 hours.
2. The use of the α/γ -iron sesquioxide thin film electrode prepared by the preparation method of claim 1 as a photo-anode in photoelectrochemical decomposition of water.
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| "Enhanced photoelectrochemical water splitting efficiency of hematite (α-Fe2O3)-Based photoelectrode by the introduction of maghemite (γ-Fe2O3) nanoparticles";Tsuyoshi Tokubuchi et al.;《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY》;第410卷;第1-7页 * |
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