CN114657587A - Preparation method of cauliflower-shaped titanium dioxide - Google Patents
Preparation method of cauliflower-shaped titanium dioxide Download PDFInfo
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- CN114657587A CN114657587A CN202210257405.8A CN202210257405A CN114657587A CN 114657587 A CN114657587 A CN 114657587A CN 202210257405 A CN202210257405 A CN 202210257405A CN 114657587 A CN114657587 A CN 114657587A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims description 48
- 239000010936 titanium Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910003080 TiO4 Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000000969 carrier Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 241000345998 Calamus manan Species 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 235000012950 rattan cane Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01G23/04—Oxides; Hydroxides
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- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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Abstract
The invention relates to a preparation method of a cauliflower-shaped nano titanium dioxide catalyst used in the field of photoelectrocatalysis. In particular to TiO2 with a nano cauliflower-like structure obtained by roasting a sample in a certain atmosphere by using a hydrothermal synthesis method. The cauliflower-shaped nanoparticles prepared by the hydrothermal method have uniform appearance and controllable size. The preparation method is simple, simplifies the implementation process of the titanium dioxide preparation process, has low cost and is beneficial to large-scale preparation. The material has great application potential in the aspects of photoelectrocatalysis, electrochemical catalysis and the like.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a preparation method of cauliflower-shaped titanium dioxide.
Background
The development of global sustainable clean energy is driven by increasingly severe energy crisis and environmental problems. Photoelectrochemical water splitting to produce hydrogen is considered to be a sustainable clean energy production method. Over the past decades, great efforts have been made to achieve efficient photoelectrochemical water splitting. In 1972, the rattan island and Honda were first in TiO2The photoelectrochemistry water decomposition hydrogen production is realized on the electrode. Currently, among the numerous high activity photoelectrodes, TiO2The wide band gap semiconductor photo-anode is the most commonly used wide band gap semiconductor photo-anode in photoelectrochemical water splitting application due to the advantages of high photocatalytic activity, good stability, long diffusion length, low cost and the like. However, TiO2The electrons generated in (1 cm) have low electron mobility2 V-1s-1) The separation efficiency of the photon-generated carriers is low, the service life of the charge carriers is short, and the application of the photo-generated carriers in photoelectrochemical water decomposition hydrogen production is limited. Thus, TiO enhancement2The charge fraction efficiency of the photo-anode material has important significance for improving the hydrogen production efficiency of the photo-anode material. Recent studies have shown that control of morphology and structure, elemental doping and narrow bandgap semiconductor compounding can all enhance TiO2Photoelectrochemical water splitting performance of (1).
For photo-electrolytic materials, TiO2The preparation process and preparation conditions of the semiconductor material have important influence on the optical properties and the photoelectric chemical properties of the material. In the presence of TiO2As for the current development of semiconductor materials, the preparation methods thereof are various. Methods such as sol-gel, anodic, hydrothermal methods for preparing TiO are summarized in the literature (Stepan knent, francisca Riboni, et al chem. soc. rev.,2017,46, 3716)2And a photo-anode. Among the various preparation methods, the hydrothermal method has: (1) the applicability is wide; (2) the process is simple; (3) modification of the reactionThe factors such as temperature, pressure, reaction time and the like can effectively control the grain size and crystal growth and the like in the hydrothermal process, so the method is often used for preparing titanium dioxide nano materials. The titanium dioxide nano-particles with controllable morphology are mainly prepared on the conductive substrate by adopting a hydrothermal synthesis method, and due to the characteristics of large specific surface area, capability of providing a diffusion channel for electron transmission, excellent transmission performance of photon-generated carriers and the like, the titanium dioxide nano-particles have great application prospects in the fields of hydrogen production by photoelectrolysis and the like.
Disclosure of Invention
The invention provides a simple and feasible method for preparing a titanium dioxide catalyst with cauliflower-like nano morphology, and finds application of the titanium dioxide catalyst in electrocatalysis and photoelectrocatalysis. The invention aims to provide a preparation method which can be widely applied to cauliflower-shaped nano-morphology titanium dioxide. The method has the advantages of simple operation, low cost and easy obtaining, the prepared film is in the form of cauliflower-shaped nano particles, the large-scale preparation is facilitated, and the like.
A method for preparing cauliflower-shaped titanium dioxide nanoparticles comprises the steps of pretreating a conductive substrate, immersing the conductive substrate into a solution containing Ti4+ precursor, and depositing a layer of titanium oxide film on the surface of the conductive substrate by a high-temperature hydrothermal method; and then, thoroughly cleaning the obtained film, and then placing the film in a certain atmosphere for high-temperature calcination to obtain a titanium dioxide film, wherein the titanium dioxide prepared by the method has a uniform cauliflower-shaped nano morphology.
The preparation method comprises the following specific steps:
1) the pretreatment process is as follows: firstly, sequentially putting a conductive substrate into acetone, ethanol and deionized water, respectively, ultrasonically cleaning, cleaning by using a deionized water solution, drying, and sealing a conductive surface and a back surface of the conductive substrate, which do not need to be deposited;
2) the hydrothermal synthesis process comprises the following steps: the hydrothermal kettle is utilized to form a high-pressure environment. Firstly, preparing a precursor solution containing 2-48mM of Ti4+, wherein the solution contains 0.1M hydrochloric acid and is uniformly stirred; two pretreated conductive substrates are symmetrically stuck in the lining of the hydrothermal kettle by using a sealing medium, and the conductive surfaces face the center of the lining of the hydrothermal kettle. After the hydrothermal kettle is sealed, putting the hydrothermal kettle into an oven to be heated for 1-15h at the temperature of 120-;
3) after the reaction is finished, cooling the hydrothermal kettle to room temperature, taking out the conductive substrate from the hydrothermal kettle, cleaning the conductive substrate by absolute ethyl alcohol and deionized water, removing the sealing medium, calcining the obtained sample in an atmosphere of 400-550 ℃ for 2 hours at the heating rate of 1-8 ℃/min to obtain a titanium dioxide film, wherein the titanium dioxide prepared by the method has uniform cauliflower-like nano morphology;
the conductive substrate is conductive glass (FTO) or other conductive flat plates, such as a Ti plate, a Ti net, a stainless steel plate and the like;
the surface resistance of the conductive glass is more than or equal to 10 omega/sq, the thickness of the surface conductive layer is more than or equal to 300nm, and the thickness of the conductive glass is more than or equal to 2mm, such as indium tin oxide conductive glass (ITO) or F-doped indium tin oxide conductive glass (FTO) and the like; the other conductive flat plates are substrate plates with at least one conductive surface, such as Ti plates, Ti nets, stainless steel plates and the like;
the sealing medium is sealed by adopting an insulating high-pressure-resistant medium (such as an insulating tape and the like), and the sealing medium is removed after the hydrothermal reaction;
the precursor aqueous solution of Ti4+ is 2-48mM of C16H36TiO4, C12H28O4Ti, TiCl4 or other solutions containing Ti4+ ions;
the temperature of the hydrothermal reaction is 120-170 ℃, and the time of the hydrothermal reaction is 1-15 h;
the temperature in the calcining process is 400-550 ℃, and the temperature rise rate is 1-8 ℃/min;
the atmosphere of the calcination process is air or 99.9% nitrogen, etc
The invention has the characteristics and beneficial effects that:
(1) the invention takes a conductive substrate as a substrate for deposition, and a hydrothermal method is utilized in the synthesis process to prepare the photoelectric catalyst;
(2) the method can quickly and accurately prepare the TiO2 semiconductor film on the surface of the conductive substrate, and the film sample prepared by the scanning electron microscope characterization is the titanium dioxide nano-particles with uniform cauliflower-like morphology.
The film has the advantages of stability, easy operation in the implementation process, low cost and the like. The TiO2 oxide prepared by the method can be used as a photoelectric catalyst, can be applied to the field of hydrogen production by solar energy water decomposition, and has good application prospects in the fields of electrocatalysis and other catalysis.
Drawings
In fig. 1, a is a schematic diagram of an insulating tape sealed conductive substrate, b is a hydrothermal kettle lining, and c is a hydrothermal kettle. 1 is an insulating tape sealing part, 2 is a conductive surface exposed by a conductive substrate, 3 is a hydrothermal kettle lining, 4 is a conductive substrate, and 5 is a precursor solution, wherein the conductive surface faces to the center of the hydrothermal kettle lining.
FIG. 2 is the TiO prepared2The digital photograph of (1). 1 is TiO prepared on FTO2Film, 2 is TiO prepared on Ti sheet2Film, 3 is TiO prepared on Ti net2Films corresponding to examples 1, 2, 3, respectively.
FIG. 3 is the TiO prepared2Scanning electron micrographs at 250000 Xmagnification, with the scale bar at 100nm, corresponding to example 1.
FIG. 4 is the TiO prepared2In particular at a scan rate of 5 deg./min from 10 deg. to 80 deg., the black diamonds represent the characteristic XRD peaks of titanium dioxide, corresponding to example 1.
FIG. 5 shows TiO prepared on FTO, Ti plate, respectively2Corresponds to examples 1, 2 and 3. The photoelectric properties were tested in an electrolyte of 1M NaOH (pH 13.6) in an H-type cell with a Pt electrode as counter electrode and Ag/AgCl (sat. kcl) as reference electrode. The light source was a 300W xenon lamp.
Detailed Description
In order to explain in detail possible application scenarios, technical principles, practical embodiments, and the like of the present application, the following detailed description is given with reference to the accompanying drawings in conjunction with the listed embodiments. The embodiments described herein are merely for more clearly illustrating the technical solutions of the present application, and therefore, the embodiments are only used as examples, and the scope of the present application is not limited thereby.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase "an embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or related to other embodiments specifically defined. In principle, in the present application, the technical features mentioned in the embodiments can be combined in any manner to form a corresponding implementable technical solution as long as there is no technical contradiction or conflict.
Unless otherwise defined, technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the use of relational terms herein is intended only to describe particular embodiments and is not intended to limit the present application.
The development of global sustainable clean energy is driven by increasingly severe energy crisis and environmental problems. Photoelectrochemical water splitting to produce hydrogen is considered to be a sustainable clean energy production method. Over the past decades, great efforts have been made to achieve efficient photoelectrochemical water splitting. In 1972, photoelectrochemical water splitting hydrogen production was first realized on a TiO2 electrode by rattan island and Honda. At present, among numerous high-activity photoelectrodes, TiO2 is the most commonly used wide-bandgap semiconductor photoanode in photoelectrochemical water splitting applications due to its advantages of high photocatalytic activity, good stability, long diffusion length, low cost, and the like. However, electrons generated in TiO2 have low electron mobility (1cm 2V-1 s-1), which leads to low separation efficiency of photon-generated carriers and short life of charge carriers, and limits the application of the electrons in photoelectrochemical water splitting hydrogen production. Therefore, the improvement of the charge fraction efficiency of the TiO2 photo-anode material is of great significance for improving the hydrogen production efficiency. Recent research shows that the photoelectrochemical water splitting performance of TiO2 can be improved by controlling the appearance and the structure, doping elements and compounding a narrow-bandgap semiconductor.
For the photo-electrolytic material, the preparation process and preparation conditions of the TiO2 semiconductor material have important influence on the optical and photoelectric properties of the material. In view of the current development of TiO2 semiconductor materials, the methods of preparation are diverse. Methods such as sol-gel, anodization, and hydrothermal methods are summarized in the literature (Stepan knent, francisca Riboni, et al chem.soc.rev.,2017,46, 3716) for the preparation of TiO2 photoanodes. Among the various preparation methods, the hydrothermal method has: (1) the applicability is wide; (2) the process is simple; (3) the crystal grain size and crystal growth can be effectively controlled in the hydrothermal process by changing factors such as reaction temperature, pressure, reaction time and the like, so the method is often used for preparing titanium dioxide nano materials. The titanium dioxide nano-particles with controllable morphology are mainly prepared on the conductive substrate by adopting a hydrothermal synthesis method, and due to the characteristics of large specific surface area, capability of providing a diffusion channel for electron transmission, excellent transmission performance of photon-generated carriers and the like, the titanium dioxide nano-particles have great application prospects in the fields of hydrogen production by photoelectrolysis and the like.
Referring to fig. 1 to 5, the conductive substrate is sequentially immersed in acetone, ethanol and deionized water for 30min, cleaned by deionized water, dried by cold air, and the conductive surface of the conductive substrate, which does not need to be deposited, and the back surface of the conductive substrate are sealed; placing the pretreated conductive substrate in the inner container of a hydrothermal kettle as shown in figure 1, adding hydrochloric acid and Ti4+Uniformly mixing the aqueous solution of the precursor; putting the hydrothermal kettle into an oven for heating after sealing; after the reaction is finished, cooling the hydrothermal kettle to room temperature; and (2) taking out the conductive glass from the hydrothermal kettle, cleaning the conductive glass by absolute ethyl alcohol and deionized water, then taking out the insulating tape, calcining the conductive glass film sample in air or nitrogen, and naturally cooling to room temperature to obtain a titanium dioxide film, wherein the titanium dioxide prepared by the method has a very uniform cauliflower-like nano-morphology.
Example 1
The above-described pretreatment process is performed on a conductive glass (FTO) substrate using the substrate as the substrate. Sealing the back surface of the conductive substrate and the part which does not need to be deposited by using an insulating tape; and placing the pretreated conductive substrate in the inner liner of the hydrothermal reaction kettle, wherein the conductive surface faces to the center of the inner liner of the hydrothermal reaction kettle. Hydrothermal kettle inner lining is added with 1M HCl and 16mM C12H28O4Ti aqueous solution and mixing evenly; after the hydrothermal kettle is sealed, putting the hydrothermal kettle into an oven to be heated for 3 hours at the temperature of 140 ℃; after the reaction is finished, the hydrothermal kettle is placed in the air and cooled to room temperature; taking out the conductive glass from the hydrothermal kettle, and passing through anhydrous ethanolAnd cleaning with deionized water, removing the insulating tape, then putting the conductive glass film sample into nitrogen for program temperature rise, heating for 2h from room temperature to 450 ℃ at the temperature rise rate of 2 ℃/min, and naturally cooling to room temperature to obtain the titanium dioxide film.
Example 2
A Ti sheet was used as a conductive substrate, and the substrate was subjected to the above-described pretreatment. Sealing the part of the conductive substrate, which does not need to be deposited, by using an insulating tape; and placing the pretreated conductive substrate in the hydrothermal reaction kettle lining, wherein the conductive surface faces the center of the hydrothermal reaction kettle lining. Adding 1M HCl and 10mM C to the hydrothermal kettle inner lining12H28O4Ti aqueous solution and mixing evenly; after the hydrothermal kettle is sealed, putting the hydrothermal kettle into an oven to be heated for 4 hours at the temperature of 140 ℃; after the reaction is finished, the hydrothermal kettle is placed in the air and cooled to room temperature; and taking out the Ti sheet substrate from the hydrothermal kettle, cleaning the Ti sheet substrate by absolute ethyl alcohol and deionized water, removing the insulating adhesive tape, then putting the conductive film sample into air for program temperature rise, heating the sample from room temperature to 500 ℃ at the temperature rise rate of 5 ℃/min for 2h, and naturally cooling the sample to the room temperature to obtain the titanium dioxide film.
Example 3
A Ti mesh was used as a conductive substrate, and the substrate was subjected to the above-described pretreatment. Sealing the part of the conductive substrate, which does not need to be deposited, by using an insulating tape; the pretreated conductive substrate is placed in the chamber with the conductive surface facing the center of the inner container. Adding 1M HCl and 2mM C into the inner container of the hydrothermal kettle12H28O4Ti aqueous solution and mixing evenly; after the hydrothermal kettle is sealed, putting the hydrothermal kettle into an oven and heating the hydrothermal kettle for 3 hours at the temperature of 120 ℃; after the completion, the hydrothermal kettle is placed in the air and cooled to room temperature; and taking the Ti net substrate out of the hydrothermal kettle, cleaning the Ti net substrate by absolute ethyl alcohol and deionized water, removing the insulating adhesive tape, putting the film sample into air, raising the temperature by a program, raising the temperature from room temperature to 450 ℃ at a heating rate of 5 ℃/min, heating for 2h, and naturally cooling to room temperature, thereby obtaining the titanium dioxide film on the surface of the Ti net.
Finally, it should be noted that, although the above embodiments have been described in the text and drawings of the present application, the scope of the patent protection of the present application is not limited thereby. All technical solutions which are generated by replacing or modifying the equivalent structure or the equivalent flow according to the contents described in the text and the drawings of the present application, and which are directly or indirectly implemented in other related technical fields, are included in the scope of protection of the present application.
Claims (9)
1. A method for preparing cauliflower-shaped titanium dioxide nanoparticles is characterized by comprising the following steps: after pretreating the conductive substrate, immersing the conductive substrate in a solution containing Ti4+Depositing a layer of Ti oxide film on the surface of the precursor solution by a high-temperature hydrothermal method; and then, thoroughly cleaning the obtained film, and then placing the film in a certain atmosphere for high-temperature calcination to obtain a titanium dioxide film, wherein the titanium dioxide prepared by the method has a uniform cauliflower-shaped nano morphology.
2. The method of claim 1, wherein:
the preparation method comprises the following specific steps:
1) the pretreatment process is as follows: firstly, sequentially putting a conductive substrate into acetone, ethanol and deionized water, respectively, ultrasonically cleaning, cleaning by using a deionized water solution, drying, and sealing a conductive surface and a back surface of the conductive substrate, which do not need to be deposited;
2) the hydrothermal synthesis process comprises the following steps: using a hydrothermal reactor to form a high-pressure environment, Ti with a concentration of 2-48mM is prepared4+Precursor solution, which contains 0.1M hydrochloric acid and is uniformly stirred; symmetrically sticking two pretreated conductive substrates in the lining of the hydrothermal kettle by using a sealing medium, wherein the conductive surfaces face the center of the lining of the hydrothermal kettle; after the hydrothermal kettle is sealed, putting the hydrothermal kettle into an oven to be heated for 1-15h at the temperature of 120-;
3) after the reaction is finished, cooling the hydrothermal kettle to room temperature, taking out the conductive substrate from the hydrothermal kettle, cleaning the conductive substrate by absolute ethyl alcohol and deionized water, removing the sealing medium, putting the obtained sample into an atmosphere of 400-550 ℃ for calcining for 2h, wherein the heating rate is 1-8 ℃/min, and obtaining the titanium dioxide film, and the titanium dioxide prepared by the method has uniform cauliflower-shaped nanometer morphology.
3. The production method according to claim 1 or 2, characterized in that: the conductive substrate is conductive glass (FTO) or other conductive flat plates, such as Ti plates, Ti nets, stainless steel plates and the like.
4. The production method according to claim 3, characterized in that: the conductive glass has surface resistance of more than or equal to 10 omega/sq, surface conductive layer thickness of more than or equal to 300nm and conductive glass thickness of more than or equal to 2mm, such as indium tin oxide conductive glass (ITO) or F-doped indium tin oxide conductive glass (FTO) and the like; the other conductive flat plate is a substrate plate with at least one conductive surface, such as a Ti plate, a Ti net, a stainless steel plate, etc.
5. The production method according to claim 1 or 2, characterized in that: the sealing medium is sealed by adopting an insulating high-pressure-resistant medium (such as an insulating tape and the like), and the sealing medium is removed after the hydrothermal reaction.
6. The production method according to claim 1 or 2, characterized in that: ti4+The precursor aqueous solution of (A) is 2-48mM of C16H36TiO4、C12H28O4Ti、TiCl4Or other containing Ti4+A solution of ions.
7. The production method according to claim 1 or 2, characterized in that: the temperature of the hydrothermal synthesis process is 120-170 ℃, and the time of the hydrothermal reaction is 1-15 h.
8. The production method according to claim 1 or 2, characterized in that: the calcining temperature is 400-550 ℃, and the heating rate is 1-8 ℃/min.
9. The production method according to claim 1 or 2, characterized in that: the atmosphere for calcination is air or 99.9% nitrogen, etc.
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| CN103771505A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide self-assembled particles |
| CN107254690A (en) * | 2017-06-20 | 2017-10-17 | 中国科学院新疆理化技术研究所 | TiO with three-dimensional hierarchical structure2The preparation method of nano wire/micro-flowers light anode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103771505A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide self-assembled particles |
| CN107254690A (en) * | 2017-06-20 | 2017-10-17 | 中国科学院新疆理化技术研究所 | TiO with three-dimensional hierarchical structure2The preparation method of nano wire/micro-flowers light anode |
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