CN109292815B - TiO 22In-situ preparation method of nanosheet cluster film - Google Patents
TiO 22In-situ preparation method of nanosheet cluster film Download PDFInfo
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Abstract
The invention discloses a TiO2An in-situ preparation method of a nano-sheet cluster film comprises the steps of firstly adopting a high-purity metal Ti foil to carry out etching for 20-40 h by using an HCl solution with the mass concentration of 20-25% under a water bath at 25-50 ℃ to obtain a porous Ti foil, and then cleaning porous Ti foil is placed in Na with the concentration of 0.1 mol/L-5 mol/L2Carrying out hydrothermal reaction in the S solution to obtain a sodium titanate nanosheet cluster film, then carrying out ion exchange in acid on the dried sodium titanate nanosheet to obtain a metatitanic acid nanosheet cluster film, finally annealing the metatitanic acid nanosheet cluster film, and forming TiO after complete decomposition reaction2A nanosheet cluster film. The in-situ preparation method solves the problems that the nano powder prepared by the existing preparation method is easy to agglomerate and the diameter of the one-dimensional nanowire is larger.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic nano materials, and particularly relates to TiO2An in-situ preparation method of a nano-sheet cluster film.
Background
TiO2The material is an important inorganic functional material with very stable chemical properties, and has wide application prospects in the aspects of solar cells, photocatalysis, photolysis water, sensors, food packaging, coatings, functional ceramics, high-grade paint, magnetic recording materials and the like. Ultrathin two-dimensional nanosheet TiO2Has remarkable shielding effect and capability of emitting light due to unique morphological structure, large surface-to-volume ratio and atomic-scale layer thickness, and thus shows superior performance to other shapes in the fields of pigment or paint, and the like.
To date, various preparations of TiO have been reported2The method of the nano structure comprises a chemical assembly method, an electrostatic spinning method, a chemical vapor deposition method, an electrochemical anode oxidation method, a sol-gel method and an alkaline solution hydrothermal method. The sol-gel method and the alkaline solution hydrothermal method are the most mature preparation methods, and the sol-gel method generally uses Ti alkoxide as a raw material, and the nano TiO is obtained through the processes of hydrolysis, gelation and the like, low-temperature drying and sintering2Granule or flake powder, such as Chinese patent No. CN 200510111204.3, published as 2006.06.21, patent and literature (meaningful et al, TiO 2) entitled "A method for preparing rutile phase Nano titanium dioxide2Research on preparation of flaky powder, Chinese powder technology 2005,6:9-12), the most commonly used Ti alkoxide of the method has extremely strong volatility, and can be rapidly hydrolyzed once encountering air, so that the operation is difficult, and the prepared nano powder is easy to agglomerate or has bulk phase size, so that the good effect expected by theory is difficult to achieve. Hydrothermal preparation of alkali solutionTiO2The nano material is prepared by adding Ti precursor (titanium foil or titanium oxide powder) into NaOH aqueous solution, performing hydrothermal reaction to obtain sodium titanate nano material, then placing the sodium titanate nano material in acid for ion exchange to obtain titanic acid nano material, and finally converting the titanic acid nano material into TiO through hydrothermal reaction or roasting2The nanometer material, such as Que, etc. adopts Ti foil, and carries out hydrothermal reaction at 220 ℃ in NaOH solution with the concentration of 1mol/L to obtain a sodium titanate nanowire array, and then the sodium titanate nanowire array is converted into TiO by ion exchange in acid and roasting process2Nanowire arrays [ L.Que, Z.Lan, W.Wu, et al. Journal of Power Sources,2014,266:440-](ii) a Wang et al reported that Ti foil undergoes hydrothermal reaction in 10mol/L NaOH solution at 180 ℃ to obtain a sodium titanate nanowire array, and then the sodium titanate nanowire array is converted into TiO by ion exchange in acid and roasting processes2Nanowire array [ W.Wang, H.Lin, J.Li, et al., J.Am.Ceram.Soc., 2008,91: 628-631-](ii) a Preparation of TiO from Ti foil2The nano material does not need a template and a catalyst, is simple and easy to operate and has low cost, but the TiO prepared by the method2Are all one-dimensional nanowire arrays with larger diameter ratio, and in addition, the hydrothermal method is used for preparing two-dimensional TiO in situ2The preparation of the nanosheet membrane has not been reported.
Disclosure of Invention
The invention aims to provide TiO2The in-situ preparation method of the nano-sheet cluster film solves the problem of TiO prepared by the existing preparation method2Easy agglomeration of nanometer powder and larger diameter of one-dimensional nanometer line.
The invention adopts a technical scheme that TiO2The in-situ preparation method of the nanosheet cluster film is implemented specifically according to the following steps:
The invention is also characterized in that:
the specific process of step 1 is as follows:
and placing the cleaned Ti foil in HCl solution for reaction etching, then taking out the etched Ti foil, and sequentially cleaning and drying to obtain the porous Ti foil.
In the step 1, the mass concentration of the HCl solution is 20-25%.
In the step 1, the etching temperature is 25-50 ℃, and the etching time is 20-40 h.
In the step 1, the etched Ti foil is washed for multiple times by deionized water until the pH value of the washing liquid is 7, and then the Ti foil is dried for 10 to 15 hours in a vacuum environment at the temperature of between 60 and 80 ℃ to obtain the porous Ti foil.
The specific process of step 2 is as follows:
sequentially adding Na into a hydrothermal reaction kettle2And (2) sealing the reaction liquid and the porous Ti foil obtained in the step (1), then placing the hydrothermal reaction kettle in a forced air oven at the temperature of 180-220 ℃ for hydrothermal reaction for 12-24 h, then taking out the Ti foil load after the reaction, and sequentially cleaning and drying the Ti foil load to obtain the Ti foil loaded sodium titanate nanosheet cluster film.
In step 2, Na2The concentration of the S reaction solution is 0.1 mol/L-5 mol/L.
The specific process of step 3 is as follows:
step 3.1, sequentially adding an HCl solution and the Ti foil loaded sodium titanate nanosheet cluster film obtained in the step 2 into a sealable glass container, sealing, and then placing the glass container into a water bath with the temperature of 30-50 ℃ to react for 5-10 h;
step 3.2, taking out the reacted Ti foil loaded sodium titanate nanosheet cluster film, and sequentially cleaning and drying the reacted Ti foil loaded sodium titanate nanosheet cluster film to obtain a Ti foil loaded metatitanic acid nanosheet cluster film;
step 3.3, carrying out air environment annealing treatment on the titanium foil loaded metatitanic acid nanosheet cluster film, and obtaining TiO after metatitanic acid is completely thermally decomposed2A nanosheet cluster film.
In step 3.1, the HCl solution has a mass concentration of 10-20% and a volume of 100 ml.
In the step 3.3, the annealing temperature is 350-500 ℃, and the annealing time is 3-5 h.
The beneficial effect of the invention is that,
TiO of the invention2The in-situ preparation method of the nanosheet cluster film has the advantages of simple process, low cost and good repeatability, and the most critical technology in the whole process is as follows: firstly, the HCl concentration, the etching temperature and the etching time adopted for etching the metal Ti foil, and secondly, Na in the hydrothermal reaction of the aqueous alkali2The concentration, the reaction temperature and the reaction time of the S reaction liquid are adjusted by simply adjusting Na in the reaction liquid2The concentration of S reaction solution can be adjusted to TiO2The size and the void structure of the nanosheets; TiO prepared by the invention2The nano-sheet cluster film can be used for a load support of a counter electrode catalytic material in a sensitized solar cell, and can also be used for a support frame and a current collector of an electrode material in a flexible super capacitor.
Drawings
FIG. 1 is an SEM image of the Ti foil surface after etching for 12 h;
FIG. 2 is an SEM image of the Ti foil surface after 24h etching;
FIG. 3 is an SEM image of the Ti foil surface after etching for 36 h;
FIG. 4 is an SEM image of the Ti foil surface at 48h etching;
FIG. 5 shows 0mol/L Na2TiO prepared by S reaction liquid hydrothermal method2SEM images of nanosheet cluster films;
FIG. 6 shows 0.1mol/L Na2TiO prepared by S reaction liquid hydrothermal method2SEM images of nanosheet cluster films;
FIG. 7 shows 0.5mol/L Na2TiO prepared by S reaction liquid hydrothermal method2SEM images of nanosheet cluster films;
FIG. 8 shows 1mol/L Na2TiO prepared by S reaction liquid hydrothermal method2SEM images of nanosheet cluster films;
FIG. 9 shows 2mol/L Na2TiO prepared by S reaction liquid hydrothermal method2SEM images of nanosheet cluster films;
FIG. 10 shows 3mol/L Na2TiO prepared by S reaction liquid hydrothermal method2SEM images of nanosheet cluster films;
FIG. 11 shows saturated Na2Hydrothermally prepared TiO in S solution2The nano-sheet cluster film is low in powerSEM pictures under numbers;
FIG. 12 shows saturated Na2Hydrothermally prepared TiO in S solution2SEM images of the nanoplatelet cluster films at high magnification.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Two-dimensional TiO prepared by sol-gel method2The metal Ti alkoxide adopted by the nano material is extremely volatile in the air, the operation is difficult, the nano powder is easy to agglomerate, and the TiO prepared by the aqueous alkali (NaOH, KOH) hydrothermal method2The invention provides a TiO nano material which is a one-dimensional nano wire with a larger diameter2The in-situ preparation method of the nano-sheet cluster film is realized by simply adjusting Na2The concentration of S in the reaction solution can be adjusted to TiO2Size and void structure of the nanoplatelets.
The method is implemented according to the following steps:
firstly, ultrasonically cleaning a Ti foil with the thickness of 0.01-0.06 mm and the purity of 99.99% for 3-4 times by using deionized water and absolute ethyl alcohol, then placing the cleaned Ti foil into an HCl solution with the mass concentration of 20-25%, and carrying out reaction etching for 20-40 h in hydrothermal at the temperature of 25-50 ℃; and then taking out the etched Ti foil to be washed for a plurality of times by deionized water until the pH value of the washing liquid is close to 7, and drying the Ti foil in a vacuum drying oven at the temperature of 60-80 ℃ for 10-15 h to obtain the porous Ti foil for later use.
first, Na is prepared2S reaction solution: to 40ml of deionized water, Na was added2S, stirring until the Na is completely dissolved to obtain Na with the concentration of 0.1-5 mol/L2S, reaction liquid;
sequentially adding Na into a 50ml hydrothermal reaction kettle with a polytetrafluoroethylene lining2Sealing the S reaction solution and the porous Ti foil obtained in the step 1, then placing the hydrothermal reaction kettle in a forced air oven with the temperature of 180-220 ℃ for hydrothermal reaction for 12-24 h, then taking out the Ti foil load after the reaction, and reacting the Ti foil load after the reactionAnd (3) washing with deionized water for multiple times until the pH value of the washing liquid is close to 7, and drying the washing liquid in a vacuum drying oven at the temperature of 60-80 ℃ for 10-15 h to obtain the Ti-loaded porous sodium titanate nanosheet cluster film.
the specific process is as follows:
step 3.1, sequentially adding 100ml of HCl solution with the mass concentration of 10-20% and the Ti foil loaded sodium titanate nanosheet cluster film obtained in the step 2 into a sealable glass container, sealing, placing the sealed glass container into a water bath with the temperature of 30-50 ℃ for reaction for 5-10 h, and performing acid replacement reaction on sodium titanate;
step 3.2, taking out the reacted Ti foil load, washing the Ti foil load for multiple times by using deionized water until the pH value of the washing liquid is close to 7, and drying the Ti foil load for 10-15 hours in a vacuum drying oven at the temperature of 60-80 ℃ to obtain the metatitanic acid nanosheet cluster film loaded by the Ti foil;
step 3.3, placing the titanium foil loaded metatitanic acid nanosheet cluster film in a muffle furnace at the temperature of 350-500 ℃ for air environment annealing treatment for 3-5 h, and obtaining TiO after metatitanic acid is completely thermally decomposed2A nanosheet cluster film.
TiO of the invention2The in-situ preparation method of the nanosheet cluster film has the advantages of simple process, low cost and good repeatability, and the most critical technology in the whole process is as follows: firstly, the HCl concentration, the etching temperature and the etching time adopted for etching the metal Ti foil, and secondly, Na in the hydrothermal reaction of the aqueous alkali2The concentration, the reaction temperature and the reaction time of the S reaction liquid are adjusted by simply adjusting Na in the reaction liquid2The concentration of S reaction solution can be adjusted to TiO2The size and the void structure of the nanosheets; TiO prepared by the invention2The nano-sheet cluster film can be used for a load support of a counter electrode catalytic material in a sensitized solar cell, and can also be used for a support frame and a current collector of an electrode material in a flexible super capacitor.
Example 1
sequentially adding Na into a 50ml hydrothermal reaction kettle with a polytetrafluoroethylene lining2And (2) sealing the reaction solution S and the porous Ti foil obtained in the step (1), placing the hydrothermal reaction kettle in a forced air oven at the temperature of 180 ℃ for hydrothermal reaction for 12 hours, taking out the reacted Ti foil load, washing the reacted Ti foil load for multiple times by using deionized water until the pH of the washing liquid is close to 7, and drying the Ti foil load in a vacuum drying oven at the temperature of 60 ℃ for 10 hours to obtain the Ti foil loaded sodium titanate nanosheet cluster membrane.
The specific implementation steps in examples 2 to 11 are shown in example 1, and some of the parameter changes are shown in Table 1.
TABLE 1 distribution of partial reaction parameters in examples 1 to 11
FIGS. 1 to 4 are surface topography diagrams of Ti foils etched for different times in examples 1 to 4, as can be seen from FIG. 1: the diameter of the hole on the surface of the Ti foil is obviously increased along with the prolonging of the etching time; as shown in fig. 1 and 2, the depth of the hole increases significantly as the etching time is extended from 12h to 24h, but decreases significantly as the etching time is further extended to 36h and 48h, mainly because the walls of the hole are continuously etched away for a long time, as shown in fig. 3 and 4.
FIGS. 5 to 10 show Na concentrations in examples 5 to 102TiO prepared by S reaction liquid hydrothermal method2SEM image of the nanosheet cluster film, from which it can be seen: with Na2Increase in S concentration, TiO2The nanosheets increase in size, the clusters also gradually increase in diameter, and the voids between the clusters gradually decrease.
FIGS. 11 and 12 show saturated Na in example 112Hydrothermally prepared TiO in S solution2SEM images of the nanosheet cluster film at low magnification and high magnification show that large-area uniform clusters can be seen from fig. 11, i.e., the low magnification SEM image, and the clusters are also very uniform in size; from 12, namely a high-magnification SEM image, each cluster is composed of two-dimensional nanosheets with very thin thicknesses, the nanosheets are vertically assembled, and a proper void structure exists among the nanosheets.
Claims (4)
1. TiO 22The in-situ preparation method of the nanosheet cluster film is characterized by comprising the following steps:
step 1, preparing a porous Ti foil;
placing the cleaned Ti foil in HCl solution for reaction etching, then taking out the etched Ti foil, and sequentially cleaning and drying to obtain a porous Ti foil; the mass concentration of the HCl solution is 20-25%, the etching temperature is 25-50 ℃, and the etching time is 20-40 h; washing the etched Ti foil for multiple times by using deionized water until the pH value of the washing liquid is 7, and then drying for 10-15 h in a vacuum environment at the temperature of 60-80 ℃ to obtain a porous Ti foil;
step 2, preparing a sodium titanate nanosheet cluster film;
sequentially adding Na into a hydrothermal reaction kettle2Sealing the reaction liquid and the porous Ti foil obtained in the step 1, placing the hydrothermal reaction kettle in a forced air oven at the temperature of 180-220 ℃ for hydrothermal reaction for 12-24 h, taking out the Ti foil load after the hydrothermal reaction, and sequentially cleaning and drying the Ti foil load to obtain a Ti foil loaded sodium titanate nanosheet cluster film; the Na is2The concentration of the S reaction solution is 0.1-5 mol/L;
step 3, preparing TiO2A nanosheet cluster film.
2. A TiO compound according to claim 12The in-situ preparation method of the nanosheet cluster film is characterized in that the specific process of the step 3 is as follows:
step 3.1, sequentially adding an HCl solution and the Ti foil loaded sodium titanate nanosheet cluster film obtained in the step 2 into a sealable glass container, sealing, and then placing the glass container into a water bath with the temperature of 30-50 ℃ to react for 5-10 h;
step 3.2, taking out the reacted Ti foil loaded sodium titanate nanosheet cluster film, and sequentially cleaning and drying the reacted Ti foil loaded sodium titanate nanosheet cluster film to obtain a Ti foil loaded metatitanic acid nanosheet cluster film;
step 3.3, carrying out air environment annealing treatment on the titanium foil loaded metatitanic acid nanosheet cluster film, and obtaining TiO after metatitanic acid is completely thermally decomposed2A nanosheet cluster film.
3. A TiO compound according to claim 22The in-situ preparation method of the nanosheet cluster film is characterized in that in step 3.1, the HCl solution is 10-20% in mass concentration and 100ml in volume.
4. A TiO compound according to claim 22The in-situ preparation method of the nanosheet cluster film is characterized in that in step 3.3, the annealing temperature is 350-500 ℃, and the annealing time is 3-5 hours.
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