CN112007659A - Rare earth doped indium sulfide nanosheet/TiO2Preparation method of composite photoelectric anode film and product thereof - Google Patents
Rare earth doped indium sulfide nanosheet/TiO2Preparation method of composite photoelectric anode film and product thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 25
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 22
- 239000002135 nanosheet Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims abstract description 20
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- -1 thulium ions Chemical class 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000003618 dip coating Methods 0.000 claims abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 21
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 15
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 229940043237 diethanolamine Drugs 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical group O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 239000002055 nanoplate Substances 0.000 claims 8
- 230000004044 response Effects 0.000 abstract description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 54
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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Abstract
Rare earth doped indium sulfide nanosheet/TiO2The preparation method of the composite photoelectric anode film and the product thereof comprise the following steps: mixing absolute ethyl alcohol with a titanium source to obtain a solution, uniformly mixing the solution with an ethanol water solution, adding diethanolamine, standing and aging to obtain titanium dioxide gel, and preparing a titanium dioxide film by adopting a dip-coating method; dissolving thulium nitrate, ytterbium nitrate, indium source and sulfur source in deionized water to obtain precursor solution, transferring the precursor solution into a reaction kettle, leaning a titanium dioxide film in the reaction kettle, preserving heat, cooling, taking out and drying to obtain the rare earth doped indium sulfide nanosheet/TiO2A composite photoelectric anode film material. The preparation method is characterized in that thulium ions and ytterbium ions are doped in indium sulfide nanosheets and are grown on the surface of a titanium dioxide film in situPreparing a composite film of TiO2The photocurrent response of the film in a visible light wave band is greatly improved.
Description
Technical Field
The invention relates to the technical field of photocatalysis/photoelectrocatalysis, in particular to rare earth doped indium sulfide nanosheet/TiO2A preparation method of a composite photoelectric anode film and a product thereof.
Background
With the increasing severity of energy crisis, clean energy represented by solar energy has received much attention. Semiconductive titanium dioxide (TiO)2) Has excellent photoelectrochemical properties, and can be widely applied to the fields of solar cells, photocatalytic degradation of pollutants, water photolysis and the like. The titanium dioxide material has good application in the fields as an environment-friendly and efficient semiconductor material, and is considered as the most promising photovoltaic material. However, TiO2The forbidden band width of the film is (3.2eV), the optical and electrical properties of the film are poor, the photovoltaic response can be realized only under the irradiation of ultraviolet light, most visible light cannot be effectively absorbed, and the recombination rate of the generated photo-generated electron-hole pairs in a dark state is high. In order to widen the light absorption range and improve the photoelectric conversion efficiency, TiO is required2And (5) modifying the film.
Currently, semiconductor metal sulfides have been extensively studied, among which indium sulfide (In)2S3) Has the characteristics of good narrow band gap, high stability, low toxicity and the like, and various shapes including nano sheets, nano tubes, nano rods and hollow microspheres, so that the nano-composite material not only can be used as good broad-spectrum photocatalysis/photoelectrocatalysisCandidate materials, and can be used as an excellent sensitizer for wide band gap photocatalysts. However, due to In2S3The self photon-generated carriers are easy to quickly recombine, and the wide application of the photon-generated carriers is limited. The transition metal ion doping can inhibit the combination of photoelectrons and holes and improve the photocatalysis/photoelectrocatalysis efficiency of the material, and moreover, the transition metal ion doping can also cause band gap reduction or band gap internal state formation so as to more effectively enhance light absorption and capture-release electrons. Unlike transition metal ions, trivalent lanthanide rare earth ions have abundant energy level structures and excellent optical properties, and are considered to be expected to efficiently inhibit the recombination of photo-generated electrons and holes. Thus, rare earth doped indium sulfide nanosheets and TiO2The composite photoelectric anode film is compositely constructed, and the obtained composite photoelectric anode material with wide spectral response range, high solar energy utilization rate and excellent photocatalysis/photoelectrocatalysis performance has important significance for realizing the maximum utilization of solar energy and solving the problems of environment and energy.
Disclosure of Invention
In order to solve the technical problems, the invention provides rare earth doped indium sulfide nanosheet/TiO2A preparation method of a composite photoelectric anode film and a product thereof.
Rare earth doped indium sulfide nanosheet/TiO2The preparation method of the composite photoelectric anode film comprises the following steps:
(1) taking two parts of anhydrous ethanol with equal amount, and mixing one part of anhydrous ethanol with a titanium source to obtain a solution A; mixing one part of the mixture with deionized water to obtain solution B, mixing the solution A and the solution B, adding diethanolamine, stirring, standing and aging for two to three days to obtain titanium dioxide gel; firstly, respectively and uniformly dispersing butyl titanate and water into ethanol by a sol-gel method, then mixing the butyl titanate and the water to slowly hydrolyze the butyl titanate and the water, and the diethanolamine plays a role in regulating the hydrolysis and polycondensation balance;
(2) plating a wet film by using the titanium dioxide gel prepared in the step (1) as a precursor solution by adopting a dipping and pulling method, and performing annealing treatment after drying to obtain a titanium dioxide film; the titanium dioxide film is an anatase phase titanium dioxide film; the dip-coating method is most suitable for gel precursor solution coating;
(3) dissolving thulium nitrate, ytterbium nitrate, indium source and sulfur source in deionized water, and stirring to obtain a precursor solution;
(4) transferring the precursor solution prepared in the step (3) into a reaction kettle, enabling the titanium dioxide film prepared in the step (2) to face downwards to lean against the reaction kettle, preserving the heat for 20-24 h at the temperature of 170-200 ℃, cooling, taking out and drying to obtain the rare earth doped indium sulfide nanosheet/TiO2A composite photoelectric anode film material. The process is to plate anatase phase TiO2In-situ growth on surface2S3The obtained product is a composite film with two layers distributed.
Preferably, in the step (1), the titanium source is butyl titanate, and the ratio of titanium source: the total consumption of absolute ethyl alcohol: deionized water: the mol ratio of the diethanol amine is 1:20:1:1, and the stirring time is 4 hours.
Preferably, the annealing temperature in the step (2) is 450 ℃.
Preferably, a wet film is plated on the glass in the step (2) by adopting a dip-coating method, wherein the coating speed is 7-9 cm/min.
Preferably, the sulfur source in the step (3) is thioacetamide, the indium source is indium trichloride tetrahydrate, and the stirring time is 30 min-1 h.
Preferably, in the step (3), the ratio of the amounts of indium trichloride tetrahydrate, ytterbium nitrate and thulium nitrate is 197:2:1 to 189:10:1, and the ratio of the sum of the amounts of cationic substances to the amount of the sulfur source substance is 1:2.6 to 1: 3.
Preferably, in the step (3), the amount ratio of the ytterbium ion doping substance in the rare earth-doped indium sulfide nanosheet is 1% -5%, and the amount ratio of the thulium ion doping substance is 0.5%. Too much doping results in a decrease in the energy transfer efficiency between Yb and Tm.
Preferably, the sum of the quantity concentration of the thulium nitrate, the ytterbium nitrate and the indium source in the precursor solution is 24 mM-33 mM.
The invention also provides the rare earth doped indium sulfide nanosheet/TiO2Rare earth doped indium sulfide nanosheet/TiO prepared by preparation method of composite photoelectric anode film2And compounding the photoelectric anode film.
Compared with the prior art, the invention has the following beneficial effects:
1.TiO2the thin film is used as an electron transport layer and a hole blocking layer to promote Yb3+/Tm3+Co-doping of beta-In2S3After the electron hole pairs are separated, electrons can be quickly guided away to reach the FTO conductive substrate and reach the counter electrode along the outer loop to participate in hydrogen production.
2.Yb3+/Tm3+Co-doping of beta-In2S3Effectively promote TiO2The absorption of visible light improves the photoelectrochemical property of the visible light part.
3. After rare earth is doped, the recombination of electron hole pairs is effectively inhibited through a semiconductor sensitization up-conversion strategy and the synergistic effect of an interband state formed by doping or intrinsic defects.
4. The experimental result proves that when the doping concentration is too high, the sensitization efficiency of the semiconductor is reduced, the energy transfer efficiency is reduced, the electron hole pair recombination is promoted, and the photoelectrochemical property is reduced.
Drawings
FIG. 1 is a scanning electron microscope image of a composite photoelectrode thin film prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction diagram of the composite photoelectrode thin film prepared in example 1 of the present invention;
FIG. 3 is a photo-current response-time curve diagram of the composite photo-anode film prepared in example 1 of the present invention;
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
This example prepares TiO2/β-In2S3:Yb3+-Tm3+Composite heterojunction Structure photoelectric ultrathin film Material, In3+:Yb3+:Tm3+193:6: 1; the raw materials used are shown in table 1;
TABLE 1
The preparation process comprises the following steps:
(1) according to the weight ratio of butyl titanate: total absolute ethanol: deionized water: diethanolamine 1:2Uniformly mixing tetrabutyl titanate and a half amount of absolute ethyl alcohol at room temperature to obtain a solution A, respectively stirring and uniformly mixing the other half amount of absolute ethyl alcohol and deionized water at room temperature to obtain a solution B, then mixing the solution A and the solution B, continuously adding diethanol amine until the solution becomes clear, stirring for 4 hours at room temperature, standing and aging for three days to form stable TiO2And (4) gelling.
(2) With TiO2The gel is a coating precursor solution, a layer of film is pulled on the glass by adopting a dipping pulling method (the aging temperature is 26 ℃, the aging time is 2 days, the pulling speed is 8cm/min), the glass is placed for 12 hours, the glass is aired and then is annealed for two hours at the temperature of 450 ℃, and TiO of anatase phase is obtained2A film.
(3) Weighing indium chloride, thioacetamide, ytterbium nitrate, thulium nitrate and 40ml of deionized water, transferring the materials into a beaker, and stirring the materials for 30min, wherein the amounts of the indium chloride, the thioacetamide, the ytterbium nitrate and the thulium nitrate are 0.9264mmol, 2.88mmol, 0.0288mmol and 0.0048mmol respectively, and ensuring In3+:Yb3+:Tm3+＝193:6:1，S2-The amount of the substance(s) is 3 times of the sum of the amounts of all the cationic substances, the concentration of indium chloride, ytterbium nitrate and thulium nitrate is 24mM, and the concentration of thioacetamide is 72 mM.
(4) Transferring the stirred solution into a high-pressure reaction kettle, and adding TiO2And (3) enabling the conductive surface of the film to face downwards to lean against the reaction kettle, preserving heat for 24 hours at 180 ℃, opening the reaction kettle after the heat preservation is finished, cooling to room temperature, opening the reaction kettle, taking out the prepared film, washing with deionized water, and drying.
As a result of examination, the composite film (YTS-3-TiO) obtained in this example2) The photocurrent density reaches 19.8 muA/cm under a visible light source with the wavelength of more than 420nm2With In2S3-TiO2Compared with the composite film, the photoelectrochemical property of the composite film is obviously improved, and the TiO is effectively improved2Photoelectrochemical properties In the visible portion of the spectrum, about In2S3-TiO2Composite film (11.3 muA/cm)2) 1.75 times of that of pure TiO2Film (0.5 muA/cm)2) 39.6 times as much as in fig. 3. The implementation is as shown in FIG. 1Example composite film (YTS-3-TiO)2) Scanning Electron Micrograph (SEM) of (g), In2S3Nanosheet successful in TiO2The surface of the film is grown, and the composite film (YTS-3-TiO) prepared in the example shown in FIG. 22) The X-ray diffraction pattern (XRD) of (D) shows that anatase phase TiO2And In2S3And (4) successfully compounding.
Example 2
The same as example 1, except that the amounts of indium chloride, thioacetamide, ytterbium nitrate and thulium nitrate were 0.9072mmol, 2.88mmol, 0.048mmol and 0.0048mmol, respectively, to ensure In3+:Yb3+:Tm3+＝189:10:1；S2-The amount of the substance(s) is 3 times of the sum of the amounts of all the cationic substances, the concentration of indium chloride, ytterbium nitrate and thulium nitrate is 24mM, and the concentration of thioacetamide is 72 mM.
As a result of examination, the composite film (YTS-3-TiO) obtained in this example2) The photocurrent density reaches 14.12 muA/cm under the visible light of more than 420nm2With In2S3-TiO2Compared with the composite film, the photoelectrochemical property of the composite film is obviously improved, and the TiO is effectively improved2Photoelectrochemical properties In the visible portion of the spectrum, about In2S3-TiO2Composite film (11.3 muA/cm)2) 1.25 times of that of pure TiO2Film (0.5 muA/cm)2) 28.25 times of.
Example 3
The same as example 1, except that the amounts of indium chloride, thioacetamide, ytterbium nitrate and thulium nitrate were 0.9456mmol, 2.88mmol, 0.0096mmol and 0.0048mmol, respectively, to ensure In3+:Yb3+:Tm3+＝197:2:1；S2-The amount of the substance(s) is 3 times of the sum of the amounts of all the cationic substances, the concentration of indium chloride, ytterbium nitrate and thulium nitrate is 24mM, and the concentration of thioacetamide is 72 mM.
As a result of examination, the film (YTS-3-TiO) obtained in this example2) The photocurrent density reaches 15.36 mu A/cm under the visible light of more than 420nm2With In2S3-TiO2Photoelectrochemical property of composite filmCan obviously improve and effectively improve TiO2Photoelectrochemical properties In the visible portion of the spectrum, about In2S3-TiO2Composite film (11.3 muA/cm)2) 1.36 times of that of pure TiO2Film (0.5 muA/cm)2) 30.73 times of.
Example 4
The same as example 1 except that the amounts of indium chloride, thioacetamide, ytterbium nitrate and thulium nitrate were 0.9553mmol, 2.58mmol, 0.0297mmol and 0.0049mmol, respectively, to ensure In3+:Yb3+:Tm3+＝193:6:1；S2-The amount of the substance (b) is 2.6 times of the sum of the amounts of all the cationic substances, the concentration of indium chloride, ytterbium nitrate and thulium nitrate is 33mM, and the concentration of thioacetamide is 86 mM.
As a result of examination, the film (YTS-3-TiO) obtained in this example2) The photocurrent density reaches 7.55 muA/cm under a light source with the wavelength of more than 420nm2With In2S3-TiO2Compared with the photoelectrochemical property, the composite film is obviously improved and is about In2S3-TiO2Composite film (5.0 muA/cm)2) 1.51 times of that of pure TiO2Film (0.5 muA/cm)2) 15.1 times of.
Example 5
The same as example 1, except that the amounts of indium chloride, thioacetamide, ytterbium nitrate and thulium nitrate were 0.8592mmol, 2.88mmol, 0.096mmol and 0.0048mmol, respectively, to ensure In3+:Yb3+:Tm3+＝179:20:1；S2-The amount of the substance(s) is 3 times of the sum of the amounts of all the cationic substances, the concentration of indium chloride, ytterbium nitrate and thulium nitrate is 24mM, and the concentration of thioacetamide is 72 mM.
As a result of examination, the film (YTS-3-TiO) obtained in this example2) The photocurrent density reaches 3.95 muA/cm under a light source with the wavelength of more than 420nm2With In2S3-TiO2Compared with the photoelectrochemical property of the composite film, the photoelectrochemical property of the composite film is obviously improved, and the TiO is effectively improved2Photoelectrochemical properties In the visible portion of the spectrum, about In2S3-TiO2Composite film (11.3 mu)A/cm2) 0.35 times of that of pure TiO2Film (0.5 muA/cm)2) 7.9 times of
Example 6
The same as example 1, except that the amounts of indium chloride, thioacetamide, ytterbium nitrate and thulium nitrate were 0.8112mmol, 2.88mmol, 0.144mmol and 0.0048mmol, respectively, to ensure In3+:Yb3+:Tm3+＝169:30:1；S2-The amount of the substance(s) is 3 times of the sum of the amounts of all the cationic substances, the concentration of indium chloride, ytterbium nitrate and thulium nitrate is 24mM, and the concentration of thioacetamide is 72 mM.
As a result of examination, the film (YTS-3-TiO) obtained in this example2) The photocurrent density reaches 3.2 muA/cm under a light source with the wavelength of more than 420nm2With In2S3-TiO2Compared with the photoelectrochemical property of the composite film, the photoelectrochemical property of the composite film is obviously improved, and the TiO is effectively improved2Photoelectrochemical properties In the visible portion, about In2S3-TiO2Composite film (11.3 muA/cm)2) 0.29 times of that of pure TiO2Film (0.5 muA/cm)2) 6.4 times of the total weight of the powder.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. Rare earth doped indium sulfide nanosheet/TiO2The preparation method of the composite photoelectric anode film is characterized by comprising the following steps:
(1) taking two parts of anhydrous ethanol with equal amount, and mixing one part of anhydrous ethanol with a titanium source to obtain a solution A; mixing one part of the mixture with deionized water to obtain solution B, mixing the solution A and the solution B, adding diethanolamine, stirring, standing and aging for two to three days to obtain titanium dioxide gel;
(2) plating a wet film by using the titanium dioxide gel prepared in the step (1) as a precursor solution by adopting a dipping and pulling method, and performing annealing treatment after drying to obtain a titanium dioxide film;
(3) dissolving thulium nitrate, ytterbium nitrate, indium source and sulfur source in deionized water, and stirring to obtain a precursor solution;
(4) transferring the precursor solution prepared in the step (3) into a reaction kettle, enabling the titanium dioxide film prepared in the step (2) to face downwards to lean against the reaction kettle, preserving the heat for 20-24 h at the temperature of 170-200 ℃, cooling, taking out and drying to obtain the rare earth doped indium sulfide nanosheet/TiO2A composite photoelectric anode film material.
2. Rare earth doped indium sulfide nanoplate/TiO according to claim 12The preparation method of the composite photoelectric anode film is characterized in that the titanium source in the step (1) is butyl titanate, and the titanium source comprises the following steps: the total consumption of absolute ethyl alcohol: deionized water: the mol ratio of the diethanol amine is 1:20:1:1, and the stirring time is 4 hours.
3. Rare earth doped indium sulfide nanoplate/TiO according to claim 12The preparation method of the composite photoelectric anode film is characterized in that the annealing temperature in the step (2) is 450 ℃.
4. Rare earth doped indium sulfide nanoplate/TiO according to claim 12The preparation method of the composite photoelectric anode film is characterized in that a wet film is plated on glass by adopting a dip-coating method in the step (2), and the coating speed is 7-9 cm/min.
5. Rare earth doped indium sulfide nanoplate/TiO according to claim 12The preparation method of the composite photoelectric anode film is characterized in that in the step (3), the sulfur source is thioacetamide, the indium source is indium trichloride tetrahydrate, and the stirring time is 30 min-1 h.
6. Rare earth doped indium sulfide nanoplate/TiO according to claim 12The preparation method of the composite photoelectrode film is characterized in that in the step (3), the ratio of the amounts of indium source, ytterbium nitrate and thulium nitrate is 197:2: 1-189: 10:1, and the ratio of the sum of the amounts of cationic substances and the amount of sulfur source substances is 1:2.6 ℃ @1:3。
7. Rare earth doped indium sulfide nanoplate/TiO according to claim 12The preparation method of the composite photoelectric anode film is characterized in that in the step (3), the amount proportion of ytterbium ion doping substances in the rare earth doped indium sulfide nanosheets is 1% -5%, and the amount proportion of thulium ion doping substances is 0.5%.
8. Rare earth doped indium sulfide nanoplate/TiO according to claim 12The preparation method of the composite photoelectric anode film is characterized in that the sum of the quantity concentration of substances such as thulium nitrate, ytterbium nitrate and indium source in the precursor solution is 24 mM-33 mM.
9. Rare earth doped indium sulfide nanoplate/TiO according to any one of claims 1 to 82Rare earth doped indium sulfide nanosheet/TiO prepared by preparation method of composite photoelectric anode film2And compounding the photoelectric anode film.
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