CN109133166B - Titanium dioxide porous nanowire and preparation method thereof - Google Patents
Titanium dioxide porous nanowire and preparation method thereof Download PDFInfo
- Publication number
- CN109133166B CN109133166B CN201811001853.1A CN201811001853A CN109133166B CN 109133166 B CN109133166 B CN 109133166B CN 201811001853 A CN201811001853 A CN 201811001853A CN 109133166 B CN109133166 B CN 109133166B
- Authority
- CN
- China
- Prior art keywords
- nanowire
- titanium dioxide
- titanium
- precursor
- semiconductor compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Abstract
The invention provides a titanium dioxide porous nanowire and a preparation method thereof. The method comprises the following steps: dispersing a titanium source in a hydrogen peroxide aqueous solution containing lithium hydroxide, and stirring to form a transparent solution A; heating the transparent solution A for reaction to obtain a precursor B of the nanowire structure; separating the precursor B of the nanowire structure, and performing low-temperature annealing treatment to obtain a precursor C of the nanowire structure; dispersing the precursor C of the nano linear structure in an acid solution for hydrogen ion exchange to obtain a precursor D of the nano linear structure; and (3) carrying out high-temperature annealing treatment on the nanometer linear structure precursor D to obtain a porous nanometer linear structure titanium dioxide product E, namely the titanium dioxide porous nanowire. The invention also provides the titanium dioxide porous nanowire prepared by the method. The titanium dioxide nanowire has a porous structure, so that the specific surface area of the nanowire structure can be greatly increased, and the application effect of the material in the fields of battery electrodes, catalysis, photocatalysis, sensing, solar cells, hydrophilicity and hydrophobicity, biology and the like is improved.
Description
Technical Field
The invention relates to a titanium dioxide porous nanowire and a preparation method thereof, belonging to the technical field of preparation of nano materials.
Background
The titanium dioxide has wide application prospect in the fields of water photolysis, catalysis, photocatalysis, lithium ion batteries, sodium ion batteries, potassium ion batteries, dye-sensitized solar cells, sensors and the like, and is a hotspot of material field research.
The application performance of the titanium dioxide is closely related to the shape and structure of the titanium dioxide. For example, compared with single-crystal titanium dioxide nanoparticles, the one-dimensional titanium dioxide nanoparticles can reduce grain boundaries among particles, are beneficial to the transportation of carriers in the long axis direction, and have the following characteristics: (1) under the nanometer scale, the specific surface area and active sites of the titanium dioxide can be increased sharply, and the surface reaction and the interaction with the medium can be greatly accelerated; (2) in the field of photocatalysis, photoproduction electron-hole pairs can be moved freely in the long axis direction, the recombination probability of electron holes is reduced, and the photocatalysis efficiency is improved; (3) in the field of battery electrode materials, the long axis is beneficial to effective migration of electrons, the short axis is beneficial to the rapid embedding and embedding processes of lithium, sodium or potassium ions, and compared with nanoparticles, the one-dimensional structure has better charge and discharge performance; (4) in the field of dye-sensitized solar cells, the one-dimensional nano structure can greatly reduce grain boundaries among particles, is beneficial to the transmission of electrons on a photo-anode and greatly improves the efficiency of the cell; (5) the one-dimensional nano structure has larger specific surface area, and a single nano wire has larger mass, so that the nano wire is easy to separate by self-sedimentation after photocatalytic reaction, and the recycling effect of the material is improved.
The porous titanium dioxide material has large specific surface area and high porosity, so that the porous titanium dioxide material has many excellent characteristics in application. However, the porous titanium dioxide materials reported at present are granular, such as porous spheres, porous nano-mesomorphic particles, etc., have more crystal boundaries, and are easy to become the recombination center of photo-generated electrons-holes.
Therefore, the preparation of the titanium dioxide nanomaterial with the one-dimensional porous nanowire structure by combining the one-dimensional structure and the porous structure greatly improves the specific surface area of the material, reduces the grain boundaries among particles, solves the problem that the electron-hole is easy to recombine, and improves the effective transport of electrons in the long axis direction, which is a problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a titanium dioxide porous nanowire, the titanium dioxide nanowire prepared by the method has a porous structure, the specific surface area of the nanowire structure can be greatly increased, and the application effect of the material in the fields of battery electrodes, catalysis, photocatalysis, sensing, solar cells, hydrophilicity and hydrophobicity, biology and the like is improved.
In order to achieve the above purpose, the present invention provides a method for preparing a titanium dioxide porous nanowire, which comprises the following steps (the flow is shown in fig. 1):
s1, dispersing a titanium source in a hydrogen peroxide aqueous solution containing lithium hydroxide, and stirring to form a transparent solution A;
s2, carrying out heating reaction on the transparent solution A to obtain a precursor B of the nanowire structure;
s3, separating the precursor B of the nanowire structure, and performing low-temperature annealing treatment to obtain a precursor C of the nanowire structure;
s4, dispersing the nanowire-shaped precursor C in an acid solution for hydrogen ion exchange to obtain a nanowire-shaped precursor D;
s5, carrying out high-temperature annealing treatment on the nanowire-shaped structure precursor D to obtain a porous nanowire-shaped structure titanium dioxide product E, namely the titanium dioxide porous nanowire.
In the above production method, preferably, in S1, the molar concentration of the titanium source is 0.01 mol/l to 1 mol/l; the molar ratio of titanium to lithium hydroxide in the titanium source is 1:100 to 1: 1; more preferably, the titanium source is selected from one or more of titanium ethoxide, titanium propoxide, tetrabutyl titanate, titanium ethoxide, titanium propoxide, titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, ammonium fluotitanate, titanic acid and the like.
In the above preparation method, preferably, in the aqueous solution of hydrogen peroxide containing lithium hydroxide, the concentration of lithium hydroxide is 0.4 mol/l to 1.0 mol/l, and the volume fraction of hydrogen peroxide is five per thousand to ten per cent.
In the above production method, preferably, the temperature of the heating reaction is 60 to 100 degrees celsius; the heating reaction time is 0.5 to 24 hours.
In the above preparation method, preferably, the temperature of the low-temperature annealing treatment is 150 to 250 ℃; the time of the low-temperature annealing treatment is 1 hour to 24 hours.
In the above preparation method, preferably, the acid of the acid solution is selected from one or a combination of several of hydrochloric acid, nitric acid, sulfuric acid and acetic acid; the acid solution has a concentration of 0.001 mol/l to 0.1 mol/l. The ratio of the precursor C to the acid solution is not specifically required, and may be controlled according to actual needs.
In the above preparation method, preferably, the temperature of the high-temperature annealing is 300 to 1500 degrees celsius, more preferably 300 to 1000 degrees celsius; the time of the high-temperature annealing treatment is 1 hour to 24 hours.
The invention also provides the titanium dioxide porous nanowire prepared by the preparation method.
The invention also provides a method for carrying out surface modification on the titanium dioxide porous nanowire; the surface modification comprises one or more of loaded carbon, loaded carbon nanotubes, loaded graphene, loaded black phosphorus, loaded ruthenium oxide, loaded lead oxide, loaded nickel oxide, loaded metal platinum, loaded metal gold, loaded metal silver and loaded metal copper.
The invention also provides a method for semiconductor compounding of the titanium dioxide porous nanowire; the semiconductor compound comprises one or more of cadmium sulfide semiconductor compound, lead sulfide semiconductor compound, copper oxide semiconductor compound, cuprous oxide semiconductor compound, ferric oxide semiconductor compound, ferrous oxide semiconductor compound, tungsten oxide semiconductor compound, zinc oxide semiconductor compound, gallium phosphide semiconductor compound, cadmium stannide semiconductor compound, molybdenum sulfide semiconductor compound and carbon nitride semiconductor compound.
The invention also provides the application of the titanium dioxide porous nanowire in one or more of lithium ion battery materials, sodium ion battery materials, potassium ion battery materials, catalytic hydrogenation materials, photocatalytic degradation of organic pollutants, photocatalytic decomposition of water for hydrogen production, gas sensing, dye-sensitized solar cells, perovskite solar cells, hydrophilic and hydrophobic materials, the biomedical field and the like.
The preparation method of the invention has the advantages that:
(1) the preparation technology of the titanium dioxide porous nanowire provided by the method cannot be realized by other methods.
(2) The porous structure provided by the method can increase the specific surface area of the nanowire and increase the active sites of the reaction.
(3) The one-dimensional linear structure provided by the method can reduce grain boundaries among particles, is favorable for transporting current carriers in the long axis direction, and improves the application effect of the material.
(4) The titanium dioxide porous nanowire prepared by the method has high photocatalytic performance and application effect of a lithium ion battery.
(5) The method has simple preparation process, easily controlled process parameters and easy large-scale industrial production.
(6) The method has easily obtained raw materials and low production cost.
The titanium dioxide porous nanowire has the advantages that:
(1) the long axis structure of the titanium dioxide porous nanowire is beneficial to effective migration of electrons, the porous structure is beneficial to the rapid embedding and embedding processes of lithium ions, sodium ions or potassium ions, the large specific surface area is beneficial to the contact area of electrolyte and an electrode, the current density is reduced, and the rapid charging and discharging performance of the battery is better.
(2) The structure of the titanium dioxide porous nanowire is beneficial to electron-hole separation, increases catalytic reaction active sites, has higher photocatalytic activity, and is beneficial to hydrogen production by photolysis or organic pollutant photocatalytic degradation.
(3) The titanium dioxide porous nanowire has a large specific surface area, can adsorb more dyes, and has a one-dimensional structure favorable for electron transmission and an advantage in the aspect of dye-sensitized solar cells.
(4) The structure of the titanium dioxide porous nanowire is beneficial to gas sensing, and is applied to sensing of gases such as hydrogen, oxygen, formaldehyde, propane, ethane, methane, carbon monoxide, carbon dioxide, water vapor and the like.
(5) The titanium dioxide porous nanowire has a larger specific surface area, can adsorb more organic matters or heavy metal ions, and has the effect of adsorption and separation.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of a titanium dioxide porous nanowire provided by the invention.
Fig. 2 is an SEM image of nanowire-like structure precursor B of example 1.
Fig. 3 is an SEM image of the porous nanowire titanium dioxide product E of example 1.
Fig. 4 is an XRD pattern of the porous nanowire titanium dioxide product E of example 1, which is an anatase phase.
Fig. 5 is a graph of the rate of photocatalytic degradation of rhodamine B for the porous nanowire titanium dioxide product E of example 1.
Figure 6 is a SEM morphology and XRD structure chart of the porous nanowire titanium dioxide product E of example 6.
Figure 7 is a SEM morphology and XRD structure chart of the porous nanowire titanium dioxide product E of example 7.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Reference will now be made in detail to the present embodiments of the invention, examples of which are illustrated in the accompanying drawings. It should be understood that the embodiments of the invention are not so limited in scope. The embodiments of the invention include many variations, modifications and equivalents within the spirit and scope of the appended claims.
Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments, in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein, is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps or components.
Any numerical value recited herein includes all values from the lower value to the upper value that are incremented by one unit, provided that there is a separation of at least two units between any lower value and any higher value. For example, if it is stated that the number of a component or a value of a process variable (e.g., temperature, pressure, time, etc.) is from 1 to 90, preferably from 20 to 80, and more preferably from 30 to 70, it is intended that equivalents such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 are also expressly enumerated in this specification. For values less than 1, one unit is suitably considered to be 0.0001, 0.001, 0.01, 0.1. These are only examples of what is intended to be explicitly recited, and all possible combinations of numerical values between the lowest value and the highest value that are explicitly recited in the specification in a similar manner are to be considered.
Unless otherwise indicated, all ranges include the endpoints and all numbers between the endpoints. The use of "about" or "approximately" with a range applies to both endpoints of the range. Thus, "about 20 to about 30" is intended to cover "about 20 to about 30", including at least the endpoints specified.
All articles and references disclosed, including patent applications and publications, are hereby incorporated by reference for all purposes. The term "consisting essentially of …" describing a combination shall include the identified element, ingredient, component or step as well as other elements, ingredients, components or steps that do not materially affect the basic novel characteristics of the combination. The use of the terms "comprising" or "including" to describe combinations of elements, components, or steps herein also contemplates embodiments that consist essentially of such elements, components, or steps. By using the term "may" herein, it is intended to indicate that any of the described attributes that "may" include are optional.
A plurality of elements, components, parts or steps can be provided by a single integrated element, component, part or step. Alternatively, a single integrated element, component, part or step may be divided into separate plural elements, components, parts or steps. The disclosure of "a" or "an" to describe an element, ingredient, component or step is not intended to foreclose other elements, ingredients, components or steps.
The principles of the present invention are described in detail below in connection with various embodiments.
Example 1
The embodiment provides a preparation method of a titanium dioxide porous nanowire, which comprises the following steps:
first, hydrogen peroxide and lithium hydroxide were dissolved in water to prepare an aqueous solution having a lithium hydroxide concentration of 0.6 mol/liter and a hydrogen peroxide volume fraction of 2%. To the above 100 ml of aqueous solution, 1 g of titanyl sulfate was slowly added with stirring to form a yellow transparent solution. And then, heating the yellow transparent solution to 70 ℃, stirring at a constant temperature for 6 hours, stopping the reaction, and separating to obtain a white solid, namely the nanowire-shaped structure precursor B. And then, drying the white solid, and then putting the white solid into an oven at the temperature of 200 ℃ for constant-temperature annealing treatment for 6 hours to remove hydrogen peroxide adsorbed and contained in the white solid. And then, washing the treated white solid for multiple times by using deionized water, then putting the white solid into a nitric acid solution of 0.1 mol/L for hydrogen ion exchange, and washing the white solid for multiple times by using deionized water after the hydrogen ion exchange until the pH value of the washing liquid is close to neutral and drying the white solid. And then, putting the dried white solid into a muffle furnace, and annealing at 550 ℃ for 4 hours to obtain an anatase phase titanium dioxide porous nanowire product E.
Fig. 2 is an SEM image of nanowire-like structure precursor B according to the present example. As can be seen from fig. 2: the diameter of the material prepared by the embodiment is not more than 2 micrometers, most of the material is in a nanometer scale, the length-diameter ratio is more than 10, the material belongs to a linear structure, and the material has a long-axis structure, which is beneficial to the effective migration of electrons. Fig. 3 is an SEM image of the porous nanowire titanium dioxide product E of the present example. As can be seen from fig. 3: the surface of the porous nanowire titanium dioxide product E prepared in this example had a porous structure. The porous structure is beneficial to the rapid intercalation and deintercalation process of lithium ions, sodium ions or potassium ions. Fig. 4 is an XRD pattern of the porous nanowire titanium dioxide product E of this example, which is an anatase phase. Fig. 5 is a graph of the rate of photocatalytic degradation of rhodamine B for the porous nanowire titanium dioxide product E of this example, as determined by: dispersing the 50mg porous nanowire titanium dioxide product prepared in the embodiment into 10mg/L rhodamine B solution, and adopting a rate diagram of photocatalytic degradation of rhodamine B under the irradiation of a 3-watt LED ultraviolet lamp; under the same test conditions, P25 was used as a comparative material. It can be seen that the product of the present embodiment has higher photocatalytic decomposition performance of organic matters than the existing commercialized P25 product, and has better application prospect of photocatalytic decomposition of organic pollutants.
Example 2
The embodiment provides a preparation method of a titanium dioxide porous nanowire, which comprises the following steps:
first, hydrogen peroxide and lithium hydroxide were dissolved in water to form an aqueous solution having a lithium hydroxide concentration of 0.8 mol/liter and a hydrogen peroxide volume fraction of 5%. To the above 100 ml of the aqueous solution, 2 g of titanium tetrachloride was slowly added with stirring, and stirred to form a yellow transparent solution. Subsequently, the above yellow transparent solution was heated to 100 ℃ and stirred at a constant temperature for 3 hours, the reaction was stopped and a white solid was isolated. And then, drying the white solid, and then putting the white solid into an oven at 180 ℃ for constant-temperature annealing treatment for 24 hours to remove hydrogen peroxide adsorbed and contained in the white solid. And then, washing the treated white solid for multiple times by using deionized water, then putting the white solid into 0.01 mol/L hydrochloric acid solution for hydrogen ion exchange, and washing the white solid for multiple times by using deionized water after the hydrogen ion exchange until the pH value of the washing solution is close to neutral and drying the white solid. And then, putting the dried white solid into a muffle furnace, and annealing at 350 ℃ for 6 hours to obtain an anatase phase titanium dioxide porous nanowire product.
Example 3
The embodiment provides a preparation method of a titanium dioxide porous nanowire, which comprises the following steps:
first, hydrogen peroxide and lithium hydroxide were dissolved in water to form an aqueous solution having a lithium hydroxide concentration of 1.0 mol/liter and a hydrogen peroxide volume fraction of 6%. To the above 100 ml of aqueous solution, 5 g of titanium sulfate was slowly added with stirring, and the mixture was stirred to form a yellow transparent solution. Subsequently, the above yellow transparent solution was heated to 90 ℃ and stirred at a constant temperature for 4 hours, the reaction was stopped and a white solid was isolated. And then, drying the white solid, and then putting the white solid into an oven at 220 ℃ for constant-temperature annealing treatment for 4 hours to remove hydrogen peroxide adsorbed and contained in the white solid. And then, washing the treated white solid for multiple times by using deionized water, then putting the white solid into 0.05 mol/L acetic acid solution for hydrogen ion exchange, and washing the white solid for multiple times by using deionized water after the hydrogen ion exchange until the pH value of the washing liquid is close to neutral and drying the white solid. And then, putting the dried white solid into a muffle furnace, and annealing at 650 ℃ for 4 hours to obtain an anatase phase titanium dioxide porous nanowire product.
Example 4
The embodiment provides a preparation method of a titanium dioxide porous nanowire, which comprises the following steps:
first, hydrogen peroxide and lithium hydroxide were dissolved in water to form an aqueous solution having a lithium hydroxide concentration of 0.5 mol/liter and a hydrogen peroxide volume fraction of 2%. To the above 100 ml of aqueous solution, 1 g of titanium isopropoxide was slowly added with stirring to form a yellow transparent solution. Subsequently, the above yellow transparent solution was heated to 80 ℃ and stirred at a constant temperature for 5 hours, the reaction was stopped and a white solid was isolated. And then, drying the white solid, and then putting the white solid into an oven at 250 ℃ for constant-temperature annealing treatment for 4 hours to remove hydrogen peroxide adsorbed and contained in the white solid. And then, washing the treated white solid for multiple times by using deionized water, then putting the white solid into a nitric acid solution of 0.001 mol/L for hydrogen ion exchange, and washing the white solid for multiple times by using deionized water after the hydrogen ion exchange until the pH value of the washing liquid is close to neutral and drying the white solid. And then, putting the dried white solid into a muffle furnace, and annealing at 750 ℃ for 2 hours to obtain an anatase phase titanium dioxide porous nanowire product.
Example 5
The embodiment provides a preparation method of a titanium dioxide porous nanowire, which comprises the following steps:
first, hydrogen peroxide and lithium hydroxide were dissolved in water to prepare an aqueous solution having a lithium hydroxide concentration of 0.7 mol/liter and a hydrogen peroxide volume fraction of 4%. To the above 100 ml of aqueous solution, 3 g of tetrabutyl titanate was slowly added with stirring to form a yellow transparent solution. Subsequently, the above yellow transparent solution was heated to 85 ℃ and stirred at a constant temperature for 4 hours, the reaction was stopped and a white solid was isolated. And then, drying the white solid, and then putting the white solid into an oven at the temperature of 200 ℃ for constant-temperature annealing treatment for 12 hours to remove hydrogen peroxide adsorbed and contained in the white solid. And then, washing the treated white solid for multiple times by using deionized water, then putting the white solid into a nitric acid solution of 0.01 mol/L for hydrogen ion exchange, and washing the white solid for multiple times by using deionized water after the hydrogen ion exchange until the pH value of a washing solution is close to neutral and drying the white solid. And then, putting the dried white solid into a muffle furnace, and annealing at 550 ℃ for 4 hours to obtain an anatase phase titanium dioxide porous nanowire product.
Example 6
The embodiment provides a preparation method of a titanium dioxide porous nanowire, which comprises the following steps:
first, hydrogen peroxide and lithium hydroxide were dissolved in water to prepare an aqueous solution having a lithium hydroxide concentration of 0.6 mol/liter and a hydrogen peroxide volume fraction of 2%. To the above 100 ml of aqueous solution, 1 g of titanium isopropoxide was slowly added with stirring to form a yellow transparent solution. Subsequently, the above yellow transparent solution was heated to 90 ℃ and stirred at a constant temperature for 5 hours, the reaction was stopped and a white solid was isolated. And then, drying the white solid, and then putting the white solid into an oven at 250 ℃ for constant-temperature annealing treatment for 10 hours to remove hydrogen peroxide adsorbed and contained in the white solid. And then, washing the treated white solid for multiple times by using deionized water, then putting the white solid into a nitric acid solution of 0.001 mol/L for hydrogen ion exchange, and washing the white solid for multiple times by using deionized water after the hydrogen ion exchange until the pH value of the washing liquid is close to neutral and drying the white solid. And then, putting the dried white solid into a muffle furnace, and annealing at 1100 ℃ for 2 hours to obtain a titanium dioxide porous nanowire product with anatase phase and rutile phase mixed, wherein the SEM morphology and XRD structure of the product are shown in figure 6, and the product is a porous anatase phase and rutile phase composite structure.
Example 7
The embodiment provides a preparation method of a titanium dioxide porous nanowire, which comprises the following steps:
first, hydrogen peroxide and lithium hydroxide were dissolved in water to prepare an aqueous solution having a lithium hydroxide concentration of 0.6 mol/liter and a hydrogen peroxide volume fraction of 2%. To the above 100 ml of aqueous solution, 1 g of titanium isopropoxide was slowly added with stirring to form a yellow transparent solution. Subsequently, the above yellow transparent solution was heated to 90 ℃ and stirred at a constant temperature for 5 hours, the reaction was stopped and a white solid was isolated. And then, drying the white solid, and then putting the white solid into an oven at 250 ℃ for constant-temperature annealing treatment for 10 hours to remove hydrogen peroxide adsorbed and contained in the white solid. And then, washing the treated white solid for multiple times by using deionized water, then putting the white solid into a nitric acid solution of 0.001 mol/L for hydrogen ion exchange, and washing the white solid for multiple times by using deionized water after the hydrogen ion exchange until the pH value of the washing liquid is close to neutral and drying the white solid. And then, putting the dried white solid into a muffle furnace, and annealing at 1300 ℃ for 2 hours to obtain a rutile phase titanium dioxide porous nanowire product, wherein the SEM morphology and XRD structure of the product are shown in figure 7, and the product is a porous rutile phase structure.
It is to be understood that the above description is intended to be illustrative, and not restrictive. Many embodiments and many applications other than the examples provided will be apparent to those of skill in the art upon reading the above description. The scope of the invention should, therefore, be determined not with reference to the above description, but instead should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are hereby incorporated by reference for all purposes. The omission in the foregoing claims of any aspect of subject matter that is disclosed herein is not intended to forego such subject matter, nor should the inventors be construed as having contemplated such subject matter as being part of the disclosed subject matter.
Claims (10)
1. A preparation method of a titanium dioxide porous nanowire comprises the following steps:
s1, dispersing a titanium source in a hydrogen peroxide aqueous solution containing lithium hydroxide, and stirring to form a transparent solution A; in the aqueous solution of hydrogen peroxide containing lithium hydroxide, the concentration of the lithium hydroxide is 0.4 mol/L to 1.0 mol/L, and the volume fraction of the hydrogen peroxide is five per thousand to ten per cent;
s2, carrying out heating reaction on the transparent solution A to obtain a precursor B of the nanowire structure;
s3, separating the precursor B of the nanowire structure, and performing low-temperature annealing treatment to obtain a precursor C of the nanowire structure;
s4, dispersing the nanowire-shaped precursor C in an acid solution for hydrogen ion exchange to obtain a nanowire-shaped precursor D;
s5, carrying out high-temperature annealing treatment on the nanowire-shaped structure precursor D to obtain a porous nanowire-shaped structure titanium dioxide product E, namely the titanium dioxide porous nanowire;
wherein, in S1, the molar concentration of the titanium source is 0.01 mol/L to 1 mol/L; the molar ratio of titanium to lithium hydroxide in the titanium source is 1:100 to 1: 1;
the temperature of the heating reaction is 60-100 ℃;
the temperature of the low-temperature annealing treatment is 150-250 ℃;
the high-temperature annealing temperature is 300-1500 ℃.
2. The method of claim 1, wherein:
the titanium source is selected from one or a combination of more of titanium ethoxide, titanium propoxide, tetrabutyl titanate, ethylene glycol titanium, titanium propoxide, titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium tetrafluoride, ammonium fluotitanate and titanic acid.
3. The method of claim 1, wherein: the heating reaction time is 0.5 to 24 hours.
4. The method of claim 1, wherein: the time of the low-temperature annealing treatment is 1 hour to 24 hours.
5. The method of claim 1, wherein: the acid of the acid solution is selected from one or a combination of more of hydrochloric acid, nitric acid, sulfuric acid and acetic acid; the acid solution has a concentration of 0.001 mol/l to 0.1 mol/l.
6. The method of claim 1, wherein: the high-temperature annealing temperature is 300-1000 ℃; the time of the high-temperature annealing treatment is 1 hour to 24 hours.
7. The porous nano-wire of titanium dioxide prepared by the preparation method of any one of claims 1 to 6.
8. A method of surface modification or semiconductor compounding of the titanium dioxide porous nanowire according to claim 7; wherein the surface modification comprises one or more of loaded carbon, loaded black phosphorus, loaded ruthenium oxide, loaded lead oxide, loaded nickel oxide, loaded metal platinum, loaded metal gold, loaded metal silver and loaded metal copper;
the semiconductor compound comprises one or more of cadmium sulfide semiconductor compound, lead sulfide semiconductor compound, copper oxide semiconductor compound, cuprous oxide semiconductor compound, ferric oxide semiconductor compound, ferrous oxide semiconductor compound, tungsten oxide semiconductor compound, zinc oxide semiconductor compound, gallium phosphide semiconductor compound, cadmium stannide semiconductor compound, molybdenum sulfide semiconductor compound and carbon nitride semiconductor compound.
9. The method of claim 8, wherein the supported carbon is a supported carbon nanotube or a supported graphene.
10. The use of the porous titanium dioxide nanowires as defined in claim 7 in one or more of the fields of lithium ion battery materials, sodium ion battery materials, potassium ion battery materials, catalytic hydrogenation materials, photocatalytic degradation of organic pollutants, photocatalytic decomposition of water for hydrogen production, gas sensing, dye-sensitized solar cells, perovskite solar cells, hydrophilic and hydrophobic materials, and biomedicine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811001853.1A CN109133166B (en) | 2018-08-30 | 2018-08-30 | Titanium dioxide porous nanowire and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811001853.1A CN109133166B (en) | 2018-08-30 | 2018-08-30 | Titanium dioxide porous nanowire and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109133166A CN109133166A (en) | 2019-01-04 |
| CN109133166B true CN109133166B (en) | 2021-01-29 |
Family
ID=64829367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811001853.1A Active CN109133166B (en) | 2018-08-30 | 2018-08-30 | Titanium dioxide porous nanowire and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109133166B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627117A (en) * | 2019-09-23 | 2019-12-31 | 聊城大学 | Porous anatase type TiO2Preparation method and application of nanowire bundle |
| CN112920445B (en) * | 2020-10-12 | 2021-11-19 | 广东特普爱高分子材料有限公司 | High-strength antibacterial plastic and preparation method thereof |
| CN113912109B (en) * | 2021-11-23 | 2023-04-25 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of nano titanium dioxide porous material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531050A (en) * | 2010-12-30 | 2012-07-04 | 北京大学 | Method for preparing TiO2 (B) nano wires and application of prepared TiO2 (B) nano wires |
| CN104064735A (en) * | 2013-03-18 | 2014-09-24 | 海洋王照明科技股份有限公司 | Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof |
| CN104201364A (en) * | 2014-09-15 | 2014-12-10 | 李建明 | Method for preparing spinel lithium titanate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8440162B1 (en) * | 2006-12-18 | 2013-05-14 | The Research Foundation Of State University Of New York | Titanate and titania nanostructures and nanostructure assemblies, and methods of making same |
-
2018
- 2018-08-30 CN CN201811001853.1A patent/CN109133166B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531050A (en) * | 2010-12-30 | 2012-07-04 | 北京大学 | Method for preparing TiO2 (B) nano wires and application of prepared TiO2 (B) nano wires |
| CN104064735A (en) * | 2013-03-18 | 2014-09-24 | 海洋王照明科技股份有限公司 | Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof |
| CN104201364A (en) * | 2014-09-15 | 2014-12-10 | 李建明 | Method for preparing spinel lithium titanate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109133166A (en) | 2019-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109319832B (en) | Linear porous titanium dioxide material and preparation method and application thereof | |
| Zhong et al. | Two-dimensional MXene-based and MXene-derived photocatalysts: Recent developments and perspectives | |
| CN110180548B (en) | One-dimensional indium oxide hollow nanotube/two-dimensional zinc ferrite nanosheet heterojunction composite material and application thereof in removing water pollutants | |
| Zhu et al. | CeO2 nanocrystal-modified layered MoS2/g-C3N4 as 0D/2D ternary composite for visible-light photocatalytic hydrogen evolution: Interfacial consecutive multi-step electron transfer and enhanced H2O reactant adsorption | |
| Li et al. | Vacancy-enabled mesoporous TiO2 modulated by nickel doping with enhanced photocatalytic nitrogen fixation performance | |
| Imran et al. | Highly efficient sustainable photocatalytic Z-scheme hydrogen production from an α-Fe2O3 engineered ZnCdS heterostructure | |
| Zarrin et al. | Photocatalytic activity of TiO2/Nb2O5/PANI and TiO2/Nb2O5/RGO as new nanocomposites for degradation of organic pollutants | |
| An et al. | Oxygen vacancy mediated construction of anatase/brookite heterophase junctions for high-efficiency photocatalytic hydrogen evolution | |
| Pan et al. | The enhanced photocatalytic hydrogen production of the fusiform g-C3N4 modification CaTiO3 nano-heterojunction | |
| CN108946805B (en) | Preparation method of porous titanium dioxide nanowire | |
| Shen et al. | Converting CO2 into fuels by graphitic carbon nitride-based photocatalysts | |
| Chong et al. | Enhanced photocatalytic activity of Ag3PO4 for oxygen evolution and Methylene blue degeneration: Effect of calcination temperature | |
| CN109133166B (en) | Titanium dioxide porous nanowire and preparation method thereof | |
| JP2020033249A (en) | Preparation method of titanate, titanic acid and titanium dioxide having hierarchical structure capable of controlling particle size | |
| Saini et al. | Role of ZnO in ZnO nanoflake/Ti3C2 MXene composites in photocatalytic and electrocatalytic hydrogen evolution | |
| JP6870044B2 (en) | Manufacturing method of nano-linear structure lithium titanate | |
| Tao et al. | Strong hollow spherical La2NiO4 photocatalytic microreactor for round-the-clock environmental remediation | |
| Wang et al. | Modified nano-TiO2 based composites for environmental photocatalytic applications | |
| Pan et al. | Graphene-based photocatalysts for oxygen evolution from water | |
| Salman et al. | Lysozyme-templated meso-macroporous hollow TiO2 for lithium ion battery anode | |
| Stelmachowski et al. | Carbon-based composites as electrocatalysts for oxygen evolution reaction in alkaline media | |
| Fang et al. | Effect of surface self-heterojunction existed in Bi x Y1–x VO4 on photocatalytic overall water splitting | |
| Alhaddad et al. | Promoting Visible Light Generation of Hydrogen Using a Sol–Gel-Prepared MnCo2O4@ g-C3N4 p–n Heterojunction Photocatalyst | |
| CN108615904A (en) | A kind of cobalt acid nickel hollow ball/carbonitride quantum dot composite material and its preparation method and application | |
| Luo et al. | Visible-light-driven HSr2Nb3O10/CdS heterojunctions for high hydrogen evolution activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |