CN115418668A - Titanium homologous semiconductor heterojunction photo-anode and preparation method thereof - Google Patents
Titanium homologous semiconductor heterojunction photo-anode and preparation method thereof Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 74
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 46
- 239000004065 semiconductor Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 251
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 125
- 239000002073 nanorod Substances 0.000 claims abstract description 77
- 239000002135 nanosheet Substances 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000000137 annealing Methods 0.000 claims abstract description 30
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 18
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
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- UKGZHELIUYCPTO-UHFFFAOYSA-N dicesium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Cs+].[Cs+] UKGZHELIUYCPTO-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 14
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- 230000005540 biological transmission Effects 0.000 description 6
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
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- 238000002441 X-ray diffraction Methods 0.000 description 3
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
The invention discloses a titanium homologous semiconductor heterojunction photo-anode and a preparation method thereof, wherein the titanium homologous semiconductor heterojunction photo-anode comprises a conductive substrate and a titanium dioxide nanorod array growing on the conductive substrate, and a titanium dioxide nanosheet of a non-metal doped phase is modified on the titanium dioxide nanorod array to form a titanium homologous heterojunction, and the preparation method comprises the following steps: growing a titanium dioxide nanorod array on the conductive substrate; carrying out high-temperature annealing treatment on the titanium dioxide nanorod array; carrying out surface modification on the obtained titanium dioxide nanorod array by using a titanium dioxide nanosheet suspension liquid doped with a nonmetal, so that the titanium dioxide nanorod array forms a titanium homoheterojunction, and a titanium dioxide-based nano heterojunction is obtained; and annealing the titanium dioxide-based nano heterojunction at high temperature to obtain the titanium homologous semiconductor heterojunction photoanode. The preparation method provided by the invention solves the problem of low water decomposition capability of the titanium dioxide photo-anode by constructing the heterojunction.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a titanium homologous semiconductor heterojunction photo-anode and a preparation method thereof.
Background
Hydrogen energy has received much attention as the most promising clean energy for solving the environmental and pollution problems caused by fossil fuels, and among various hydrogen production methods, photoelectrochemical water splitting is considered as an excellent hydrogen production technique. The performance of the hydrogen produced by photoelectric decomposition of water is different under the action of different catalysts, so that a high-efficiency photoelectric catalyst material is required for obtaining high-purity high-efficiency hydrogen energy. The titanium dioxide is a photoelectric catalyst with prospect due to low cost, no toxicity, good chemical stability and good optical stability. However, the wide forbidden band width, the poor light capturing capability and the slow surface hydro-oxidation kinetics of the titanium dioxide make it difficult to reach the theoretical performance peak, and various strategies such as element doping, crystal face modification, heterojunction construction and the like are used for improving the photoelectrocatalysis performance of the titanium dioxide in the past.
The FTO glass has high physical and chemical stability, good conductivity and various excellent electrochemical properties. The nanorod array structure has a high specific surface area, and can provide more active sites in electrolyzed water, so that a more efficient catalytic conversion process is realized. However, the prepared titanium dioxide material has certain defects in catalytic efficiency and surface reaction activity, and the prepared photo-anode has insufficient charge transfer capacity, so that appropriate surface modification is required to generate more active sites on the surface and improve the surface charge transfer, and further the catalytic total water decomposition efficiency of titanium dioxide is improved.
In the surface modification means of various materials, the construction of a heterojunction to improve the electrochemical property of the heterojunction is a very efficient and convenient treatment method, and is also an effective strategy for improving the catalytic performance of titanium dioxide.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a titanium homologous semiconductor heterojunction photo-anode and a preparation method thereof, and aims to solve the problem that the existing titanium dioxide photo-anode is low in water decomposition capability.
In order to solve the above problems, the present invention firstly provides a titanium homologous semiconductor heterojunction photoanode, which includes a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate, wherein a titanium dioxide nanosheet of a non-metal doped phase is modified on the titanium dioxide nanorod array, and the titanium dioxide nanorod array and the titanium dioxide nanosheet of the non-metal doped phase form a titanium homologous heterojunction.
Preferably, the titanium dioxide nanosheets of the non-metal doped phase are nitrogen-doped titanium dioxide nanosheets.
The invention also provides a preparation method of the titanium homologous semiconductor heterojunction photo-anode, which comprises the following steps:
s1, growing a titanium dioxide nanorod array on a conductive substrate;
s2, carrying out high-temperature annealing treatment on the titanium dioxide nanorod array obtained in the step S1;
s3, preparing a titanium dioxide nanosheet suspension of the non-metal doped phase by using the titanium dioxide nanosheet of the non-metal doped phase;
s4, performing surface modification on the titanium dioxide nanorod array obtained in the step S2 by using a titanium dioxide nanosheet suspension of a non-metal doped phase, so that the titanium dioxide nanorod array forms a titanium homoheterojunction, and a titanium dioxide-based nano heterojunction is obtained;
and S5, carrying out high-temperature annealing treatment on the titanium dioxide-based nano heterojunction to obtain the titanium homologous semiconductor heterojunction photo-anode.
Preferably, the growing of the titanium dioxide nanorod array on the conductive substrate in the step S1 includes: and (3) placing the conductive substrate in the mixed solution of titanium (IV) isopropoxide and dilute hydrochloric acid after ultrasonic treatment, and treating the mixed solution of the titanium (IV) isopropoxide and the dilute hydrochloric acid containing the conductive substrate at high temperature to grow the titanium dioxide nanorod array on the conductive substrate.
Preferably, the volume ratio of the titanium (IV) isopropoxide to the dilute hydrochloric acid is 1.
Preferably, the mass fraction of the dilute hydrochloric acid is 18-19%.
Preferably, the temperature for treating the mixed solution of the titanium (IV) isopropoxide and the dilute hydrochloric acid containing the conductive substrate at high temperature is 230-300 ℃, and the treatment time is 2-4 h.
Preferably, the temperature for performing the high-temperature annealing treatment on the titanium dioxide nanorod array in the step S2 is 300-500 ℃, and the treatment time is 1-3 h.
Preferably, the preparation of the suspension of the non-metal doped titanium dioxide nanosheets in the step S3 includes: high temperature calcination of cesium titanate (Cs) in an ammonia atmosphere 0.68 Ti 1.83 O 4 ) Powdering to obtain nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x Powder of Cs 0.68 Ti 1.83 O 4-x N x The powder is placed in HCl solution and H + Ion exchange takes place to give H 0.68 Ti 1.83 O 4-x N x Is prepared from H 0.68 Ti 1.83 O 4-x N x Dispersing in tetrabutylammonium hydroxide solution and shaking up to obtain nitrogen-doped titanium dioxide nanosheet (N-TiO) 2 ) And (4) suspending the solution.
Preferably, the performing of the high temperature annealing process on the titanium dioxide-based nano-heterojunction in the step S5 includes: and (3) carrying out high-temperature annealing treatment on the titanium dioxide-based nano heterojunction in an argon atmosphere, wherein the treatment temperature is 300-500 ℃, and the treatment time is 1-3 h.
The invention provides a titanium homologous semiconductor heterojunction photo-anode and a preparation method thereof.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a titanium dioxide nanorod array in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the titanium dioxide nanorod array in example 1 of the present invention;
FIG. 3 is a scanning Transmission Electron Microscope (TEM) image of a titanium dioxide nanorod array in example 1 of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the surface-modified titanium dioxide rod nanorod array structure in example 1 of the present invention;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the surface-modified titanium oxide rod nanorod array structure in example 2 of the invention;
FIG. 6 is a scanning Transmission Electron Microscope (TEM) image of the surface-modified titanium dioxide rod nanorod array structure in example 2 of the present invention;
FIG. 7 shows different loadings of N-TiO according to an embodiment of the present invention 2 Photo-catalytic performance (LSV) diagram of the modified titanium dioxide nanorod array.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are merely exemplary and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment firstly provides a titanium homologous semiconductor heterojunction photoanode, which includes a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate, wherein a titanium dioxide nanosheet of a non-metal doped phase is modified on the titanium dioxide nanorod array, and the titanium dioxide nanorod array and the titanium dioxide nanosheet of the non-metal doped phase form a titanium homologous semiconductor heterojunction.
Specifically, the titanium dioxide nanosheet of the non-metal doped phase is a nitrogen-doped titanium dioxide nanosheet.
The titanium homologous heterojunction can increase the surface reaction active sites of the titanium dioxide and enhance the charge transmission efficiency, thereby improving the surface catalytic activity of the titanium dioxide.
The embodiment also provides a preparation method of the titanium homologous semiconductor heterojunction photo-anode, and the preparation method comprises the following steps:
s1, growing a titanium dioxide nanorod array on a conductive substrate;
s2, carrying out high-temperature annealing treatment on the titanium dioxide nanorod array obtained in the step S1;
s3, preparing a titanium dioxide nanosheet suspension of the non-metal doped phase by using the titanium dioxide nanosheet of the non-metal doped phase;
s4, performing surface modification on the titanium dioxide nanorod array obtained in the step S2 by using a titanium dioxide nanosheet suspension of a non-metal doped phase, so that the titanium dioxide nanorod array forms a titanium homoheterojunction, and a titanium dioxide-based nano heterojunction is obtained;
and S5, carrying out high-temperature annealing treatment on the titanium dioxide-based nano heterojunction to obtain the titanium homologous semiconductor heterojunction photo-anode.
According to the preparation method of the titanium homologous semiconductor heterojunction photoanode, the titanium homologous heterojunction is constructed by modifying the titanium dioxide nanorod array through the titanium dioxide nanosheet suspension liquid of the non-metal doped phase, the reactive sites on the surface of titanium dioxide are increased, and the charge transmission efficiency is enhanced, so that the surface catalytic activity of the titanium dioxide is improved, the efficient total water decomposition is realized, and the problem of low water decomposition capability of the titanium dioxide photoanode is solved.
In a preferred embodiment, the step S1 of growing the titanium dioxide nanorod array on the conductive substrate includes: and (3) placing the conductive substrate in the mixed solution of the titanium (IV) isopropoxide and the dilute hydrochloric acid after ultrasonic treatment, and treating the mixed solution of the titanium (IV) isopropoxide and the dilute hydrochloric acid containing the conductive substrate at high temperature to grow the titanium dioxide nanorod array on the conductive substrate.
In a preferred scheme, the volume ratio of the titanium (IV) isopropoxide to the dilute hydrochloric acid is 1.
In a preferable scheme, the mass fraction of the dilute hydrochloric acid is 18-19%.
In a preferred scheme, the temperature of the mixed solution of the titanium (IV) isopropoxide and the dilute hydrochloric acid containing the conductive substrate is 230-300 ℃ in the high-temperature treatment, and the treatment time is 2-4 h.
Specifically, in this example, titanium (IV) isopropoxide and dilute hydrochloric acid are mixed and stirred in a glove box according to a volume ratio for 10min to 30min, and then subjected to ultrasonic treatment for 5min to 10min, the obtained mixed solution is transferred to a reaction kettle liner after the ultrasonic treatment, then a conductive substrate is placed in the reaction kettle liner, and finally the conductive substrate is subjected to high temperature treatment and cooled to room temperature, so that a titanium dioxide nanorod array can grow on the conductive substrate.
In a preferred scheme, the temperature for performing the high-temperature annealing treatment on the titanium dioxide nanorod array in the step S2 is 300-500 ℃, and the treatment time is 1-3 h.
Specifically, after the titanium dioxide nanorod array is prepared on the conductive substrate, deionized water is used for cleaning for a plurality of times, drying treatment is carried out at the temperature of 60 ℃, and then high-temperature annealing treatment is carried out.
Specifically, in this example, the titanium dioxide nanorod array can be placed in a muffle furnace, heated from room temperature to the high-temperature annealing treatment temperature in an air atmosphere for the high-temperature annealing treatment time, and then naturally cooled to room temperature to complete the annealing treatment.
In a preferred embodiment, the preparation of the suspension of the non-metal doped titanium dioxide nanosheets in step S3 includes: high temperature calcination of cesium titanate (Cs) in an ammonia atmosphere 0.68 Ti 1.83 O 4 ) Powdering to obtain nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x Powder of Cs 0.68 Ti 1.83 O 4-x N x The powder is placed in HCl solution and H + Ion exchange takes place to give H 0.68 Ti 1.83 O 4-x N x Is prepared from H 0.68 Ti 1.83 O 4-x N x Dispersing in tetrabutylammonium hydroxide solution and shaking up to obtain nitrogen-doped titanium dioxide nanosheet (N-TiO) 2 ) And (4) suspending the solution.
Specifically, white cesium titanate (Cs) is calcined at a temperature of 750 ℃ to 800 ℃ in an ammonia gas atmosphere 0.68 Ti 1.83 O 4 ) The powder is used for 2 to 3 hours, and the nitrogen-doped Cs can be obtained 0.68 Ti 1.83 O 4-x N x Powder, nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x Powder and H + Ion exchange was carried out in 1mol/L HCl solution for 3 days to give H 0.68 Ti 1.83 O 4-x N x (protonated state); preparing tetrabutylammonium hydroxide (TABOH) solution with concentration of 0.2mol/L, and mixing with H 0.68 Ti 1.83 O 4-x N x Dispersing in prepared tetrabutylammonium hydroxide (TABOH) solution, shaking at room temperature for 8 days, and shakingHomogenizing to obtain uniformly dispersed nitrogen-doped titanium dioxide nanosheets (Ti) 0.91 O 2-x N x Abbreviated to N-TiO 2 ) And (4) suspending the solution.
In particular, by changing the N-TiO 2 And carrying out surface treatment with different dosages on the titanium dioxide nanorod array by using the loading amount of the nanosheet suspension, naturally drying to obtain the surface-modified titanium dioxide nanorod array, and forming a titanium homologous heterojunction by using the modified titanium dioxide nanorod array.
Wherein, N-TiO 2 The amount of supported nanosheet suspension is preferably 100. Mu.L to 400. Mu.L.
Wherein, N-TiO 2 The concentration of the nanosheet suspension is preferably 1 mg/mL-10 mg/mL.
In a more preferred embodiment, N-TiO 2 The loading capacity of the nano-sheet suspension is 200 mu L, and the N-TiO content is 2 The titanium homologous semiconductor heterojunction photo-anode prepared by the nano-sheet suspension with the concentration of 1.5mg/mL has the best performance.
In a preferred embodiment, the performing of the high temperature annealing process on the titanium dioxide-based nano-heterojunction in the step S5 includes: and (3) carrying out high-temperature annealing treatment on the titanium dioxide-based nano heterojunction in an argon atmosphere, wherein the treatment temperature is 300-500 ℃, and the treatment time is 1-3 h.
Specifically, in this embodiment, the modified titanium dioxide nanorod array is placed in a tube furnace, and heated from room temperature to the annealing temperature at a rate of 2.3 ℃/min under the argon atmosphere, and then naturally cooled to room temperature after annealing for 1h to 3h, so as to obtain the final titanium homogeneous semiconductor heterojunction photoanode.
In a preferred embodiment, in step S1, the conductive substrate is a pretreated FTO glass, wherein the method for pretreating the FTO glass includes:
firstly, soaking FTO glass in a mixed solution of acetone and absolute ethyl alcohol for ultrasonic cleaning, and soaking the cleaned FTO glass in a mixed solution of hydrogen peroxide and sulfuric acid; secondly, cleaning the FTO glass by absolute ethyl alcohol; and finally, drying the FTO glass in a nitrogen atmosphere.
Specifically, the volume ratio of acetone to absolute ethyl alcohol in the mixed solution of acetone and absolute ethyl alcohol is 1.
The volume ratio of hydrogen peroxide to sulfuric acid in the mixed solution of hydrogen peroxide and sulfuric acid is 3.
Example 1
The embodiment provides a preparation method of a titanium homologous semiconductor heterojunction photo-anode, which comprises the following steps:
(1) Selection and pretreatment of substrates
FTO glass is selected as a substrate, and the size is 4cm multiplied by 2cm. Secondly, pretreating the substrate, specifically, putting the FTO glass in a mixed solution of acetone and absolute ethyl alcohol, wherein the volume ratio of the mixed solution of acetone and absolute ethyl alcohol is 1; soaking the FTO glass in a mixed solution of hydrogen peroxide and sulfuric acid, wherein the volume ratio of the mixed solution of hydrogen peroxide to sulfuric acid is 3; cleaning the FTO glass by using absolute ethyl alcohol; finally, the FTO glass was dried with nitrogen.
(2) Preparation of titanium dioxide nanorod array
And preparing the titanium dioxide nanorod array by adopting a hydrothermal synthesis method. Using a hydrothermal explosion-proof reaction vessel having a volume of 50mL as a reaction vessel, 0.4mL of titanium (IV) isopropoxide (Ti (OCH (CH)) was each extracted in a glove box using a pipette 3 ) 2 ) 4 ) Mixing with 30mL of dilute hydrochloric acid solution (the mass fraction is 18-19%); adding titanium (IV) isopropoxide into a dilute hydrochloric acid solution, stirring for 10 minutes, then performing ultrasonic treatment for 5 minutes to obtain a transparent solution, transferring the transparent solution into a 50mL inner container of a reaction kettle, finally placing the pretreated FTO glass in the inner container of the reaction kettle with the conductive surface facing downwards in an inclined manner, preserving the heat at 230 ℃ for 2 hours, cooling to room temperature, and preparing a titanium dioxide nanorod array on the FTO glass; washing with deionized water for several times, drying at 60 deg.C in a drying oven, and annealing at high temperature in air atmosphere to obtain dioxygen with stable structureAnd (3) titanium nano-rod arrays.
And (3) carrying out X-ray diffraction analysis on the prepared titanium dioxide nanorod array, wherein figure 1 is an X-ray diffraction (XRD) pattern of the titanium dioxide nanorod array in the embodiment 1 of the invention, and the titanium dioxide nanorod array can be determined to be obtained according to the diffraction angle corresponding to the pattern spectrum peak.
The prepared titanium dioxide nanorod array is subjected to electron microscope scanning, fig. 2 is a Scanning Electron Microscope (SEM) image of the titanium dioxide nanorod array in example 1 of the invention, and a uniform nanorod array structure can be seen in fig. 2. FIG. 3 is a scanning Transmission Electron Microscope (TEM) image of the nano-rod array of titanium dioxide in example 1 of the present invention, from which the shapes and smooth sidewalls of the nano-rods can be seen in FIG. 3.
(3) Nitrogen-doped titanium dioxide nanosheet (N-TiO) 2 ) Preparation and treatment of suspensions
Preparation of nitrogen-doped titanium dioxide nanosheet (N-TiO) by adopting powder calcination and ion exchange method 2 ) Suspending in a powder-calcining method to obtain white cesium titanate (Cs) 0.68 Ti 1.83 O 4 ) Calcining the powder in an ammonia atmosphere at 750 ℃ for 2 hours to obtain nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x Powder, obtained Cs 0.68 Ti 1.83 O 4-x N x Ion exchange of the powder with H + in 1mol/L HCl solution for 3 days to obtain H 0.68 Ti 1.83 O 4-x N x (protonated state), the resulting H was dissolved in TABOH solution of 0.2mol/L 0.68 Ti 1.83 O 4-x N x Dispersing in the solution, oscillating for 8 days at room temperature, shaking up to obtain uniformly dispersed nitrogen-doped titanium dioxide nanosheets (Ti) 0.91 O 2-x N x N-TiO for short 2 ) And (4) suspending the solution.
(4) Surface modified titanium dioxide nanorod array
Using N-TiO with a loading of 100 μ L 2 And (3) carrying out surface treatment on the titanium dioxide nanorod array by using the nanosheet suspension, then naturally drying at room temperature, and annealing to obtain a surface-modified titanium dioxide heterojunction photo-anode sample 1. It is provided withThe obtained surface-modified titanium dioxide heterojunction photo-anode sample 1 is subjected to electron microscope scanning, as shown in fig. 4, fig. 4 is a Scanning Electron Microscope (SEM) image of the surface-modified titanium dioxide rod nanorod array structure in example 1 of the present invention.
Example 2
The embodiment provides a method for preparing a titanium homologous semiconductor heterojunction photo-anode, which comprises the following steps:
using N-TiO with the loading of 200 mu L 2 And (3) carrying out surface treatment on the titanium dioxide nanorod array by using the nanosheet suspension, then naturally drying at room temperature, and annealing to obtain a surface-modified titanium dioxide heterojunction photo-anode sample 2. The rest of the procedure was the same as in example 1. Wherein, the obtained titanium dioxide heterojunction photoanode sample 2 with the modified surface is subjected to electron microscope scanning, as shown in fig. 5, fig. 5 is a Scanning Electron Microscope (SEM) image of the surface modified titanium oxide rod nanorod array structure in example 2 of the present invention. FIG. 6 is a scanning Transmission Electron Microscope (TEM) image of the surface-modified titania rod nanorod array structure in example 2 of the present invention.
Example 3
The embodiment provides a preparation method of a titanium homologous semiconductor heterojunction photo-anode, which comprises the following steps:
using N-TiO with a loading of 400 μ L 2 And (3) carrying out surface treatment on the titanium dioxide nanorod array by using the nanosheet suspension, then naturally drying at room temperature, and annealing to obtain a surface-modified titanium dioxide heterojunction photo-anode sample 3. The rest of the procedure was the same as in example 1.
Samples 1, 2 and 3 prepared in examples 1, 2 and 3 were subjected to cyclic voltammetric scanning, and then to a photocatalytic performance test.
Firstly, a sample is subjected to cyclic voltammetry testing, the contingency of an experiment is eliminated, so that the electrolyzed water performance of the sample tends to be stable, the cyclic voltammetry testing voltage range is-0.2V to 1.5V (vs RHE), the scanning speed is 50m V/s, the interval voltage is 0.001V, and the cycle is carried out for 20 times.
Secondly, the samples are respectively subjected to photoelectrochemical performance tests, and the samples are subjected to photoelectrocatalysis water splitting reaction tests by adopting a Linear Sweep Voltametry (LSV) mode of an electrochemical workstation.
Specifically, FTO in a sample is cut into 2cm multiplied by 1cm, a three-electrode system is adopted to carry out photoelectrochemical performance test on the sample by utilizing an electrochemical workstation, and photoelectrocatalysis water decomposition is carried out, wherein the electrochemical test electrolyte is 0.05M Na 2 SO 4 And (3) solution.
As shown in FIG. 7, FIG. 7 shows different N-TiO loadings provided by examples of the present invention 2 Photo-catalytic performance (LSV) diagram of modified titanium dioxide nanorod array, and 200 muL of N-TiO load can be seen from FIG. 7 2 The corresponding samples have the best photocatalytic performance.
In summary, according to the titanium homologous semiconductor heterojunction photo-anode and the preparation method thereof provided by the embodiment of the invention, the titanium dioxide nanorod array grows on the conductive substrate, then the titanium dioxide nanorod array is subjected to high-temperature annealing treatment, the titanium dioxide nanosheet suspension with the non-metal doped phase is used for preparing the titanium dioxide nanosheet suspension with the non-metal doped phase, the titanium dioxide nanorod array subjected to high-temperature annealing treatment is modified by the titanium dioxide nanosheet suspension with the non-metal doped phase, so that the titanium dioxide nanorod array forms the titanium homologous heterojunction, and finally the modified titanium dioxide nanorod array is subjected to high-temperature annealing treatment, so that the titanium homologous semiconductor heterojunction photo-anode is obtained.
The foregoing is illustrative of the present disclosure and it will be appreciated by those skilled in the art that changes may be made in this embodiment without departing from the principles of the disclosure, the scope of which is defined by the appended claims.
Claims (10)
1. The titanium homogeneous semiconductor heterojunction photo-anode is characterized by comprising a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate, wherein a titanium dioxide nanosheet with a non-metal doped phase is modified on the titanium dioxide nanorod array, and the titanium dioxide nanorod array and the titanium dioxide nanosheet with the non-metal doped phase form a titanium homogeneous heterojunction.
2. The titanium homologous semiconductor heterojunction photoanode of claim 1, wherein the titanium dioxide nanosheets of the non-metal doped phase are nitrogen doped titanium dioxide nanosheets.
3. The method for preparing the titanium homologous semiconductor heterojunction photoanode as claimed in claim 1, wherein the method comprises the following steps:
s1, growing a titanium dioxide nanorod array on a conductive substrate;
s2, carrying out high-temperature annealing treatment on the titanium dioxide nanorod array obtained in the step S1;
s3, preparing a titanium dioxide nanosheet suspension of the non-metal doped phase by using the titanium dioxide nanosheet of the non-metal doped phase;
s4, performing surface modification on the titanium dioxide nanorod array obtained in the step S2 by using a titanium dioxide nanosheet suspension of a non-metal doped phase, so that the titanium dioxide nanorod array forms a titanium homoheterojunction, and a titanium dioxide-based nano heterojunction is obtained;
and S5, carrying out high-temperature annealing treatment on the titanium dioxide-based nano heterojunction to obtain the titanium homologous semiconductor heterojunction photo-anode.
4. The method for preparing the titanium homologous semiconductor heterojunction photoanode as in claim 3, wherein the step S1 of growing the titanium dioxide nanorod array on the conductive substrate comprises: and (3) placing the conductive substrate in the mixed solution of the titanium (IV) isopropoxide and the dilute hydrochloric acid after ultrasonic treatment, and treating the mixed solution of the titanium (IV) isopropoxide and the dilute hydrochloric acid containing the conductive substrate at high temperature to grow the titanium dioxide nanorod array on the conductive substrate.
5. The method for preparing the titanium homologous semiconductor heterojunction photoanode as claimed in claim 4, wherein the volume ratio of the titanium (IV) isopropoxide to the dilute hydrochloric acid is 1 to 50-80.
6. The method for preparing the titanium homologous semiconductor heterojunction photoanode as claimed in claim 4, wherein the mass fraction of the dilute hydrochloric acid is 18-19%.
7. The method for preparing the titanium homologous semiconductor heterojunction photoanode as in claim 4, wherein the temperature of the mixed solution of titanium (IV) isopropoxide and dilute hydrochloric acid containing the conductive substrate is 230-300 ℃ and the treatment time is 2-4 h.
8. The method for preparing the titanium homologous semiconductor heterojunction photoanode as claimed in claim 3, wherein the temperature for performing the high temperature annealing treatment on the titanium dioxide nanorod array in the step S2 is 300-500 ℃, and the treatment time is 1-3 h.
9. The method for preparing the titanium homologous semiconductor heterojunction photoanode as in claim 3, wherein the step S3 of preparing the suspension of the titanium dioxide nanosheets doped with the non-metallic doping phase comprises: high temperature calcination of cesium titanate (Cs) in an ammonia atmosphere 0.68 Ti 1.83 O 4 ) Powdering to obtain nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x Powder of Cs 0.68 Ti 1.83 O 4-x N x The powder is placed in HCl solution and H + Ion exchange takes place to give H 0.68 Ti 1.83 O 4-x N x Is prepared from H 0.68 Ti 1.83 O 4-x N x Dispersing in tetrabutylammonium hydroxide solution and shaking up to obtain nitrogen-doped titanium dioxide nanosheet (N-TiO) 2 ) And (4) suspending the solution.
10. The method for preparing the titanium homologous semiconductor heterojunction photoanode as in claim 3, wherein the step S5 of annealing the titanium dioxide-based nano heterojunction at high temperature comprises: and (3) carrying out high-temperature annealing treatment on the titanium dioxide-based nano heterojunction in an argon atmosphere, wherein the treatment temperature is 300-500 ℃, and the treatment time is 1-3 h.
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