CN107959009B - Carbon-coated TiO2Preparation method of nanotube material - Google Patents

Carbon-coated TiO2Preparation method of nanotube material Download PDF

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CN107959009B
CN107959009B CN201711113272.2A CN201711113272A CN107959009B CN 107959009 B CN107959009 B CN 107959009B CN 201711113272 A CN201711113272 A CN 201711113272A CN 107959009 B CN107959009 B CN 107959009B
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严微微
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China Jiliang University
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Abstract

The invention discloses carbon-coated TiO2A preparation method of a nanotube material belongs to the technical field of nanocomposite materials. The invention uses potassium permanganate and ammonium fluoride as raw materials, adopts a hydrothermal method to prepare MnO firstly2Nanowire template material, then hydrolyzing in MnO by isopropyl titanate2Nano TiO coated on the surface of the nano wire2Further coating carbon by a dopamine polymerization carbonization method, and finally reacting with MnO by sodium thiosulfate in an acid environment2By chemical reaction of2Template to obtain carbon-coated TiO2A nanotube material. The invention provides carbon-coated TiO2The template preparation method of the nanotube material has the advantages of simple synthesis process, mild reaction conditions, low cost, stable and adjustable nanotube structure and suitability for large-scale synthesis.

Description

Carbon-coated TiO2Preparation method of nanotube material
Technical Field
The invention relates to the technical field of nano composite materials, in particular to carbon-coated TiO2A method for preparing a nanotube material.
Background
Nano TiO 22The composite material is an important inorganic functional material, has the advantages of no toxicity, gas sensitivity, humidity sensitivity, dielectric effect, photoelectric conversion, photochromism, high catalytic activity, strong oxidation capacity, good stability and the like, and is widely applied to various functional occasions, such as gas-sensitive and humidity-sensitive elements, hydrogen production by photolysis of water, photocatalytic degradation of organic pollutants, dye-sensitized solar cells and biosensors. In the field of new energy materials, nano TiO2Also has important application value, can be used for lithium-sulfur batteries, lithium ion batteries and super batteriesAnd a capacitor. In the field of lithium-sulfur batteries, TiO2Can be used as a material for catching lithium polysulfide to obviously improve the cycle stability of a sulfur anode, and can be used in lithium ion batteries, supercapacitors and TiO2Can be directly used as an active material to participate in electrochemical energy storage reaction.
In contrast to other nanostructures, TiO2Nanotubes have a larger specific surface area, which is the case for TiO2The functional application of (A) is of great significance, for example, in the field of gas-sensitive and moisture-sensitive devices, the nanotube structure can improve TiO2The nano tube structure can obviously enhance TiO in the field of photocatalytic degradation of organic pollutants, and has response capability to a detected object2Can effectively improve TiO when used as the electrode material nanotube structure of lithium ion batteries and super capacitors2Electrochemical activity and charge-discharge properties of the cell.
TiO2The preparation method of the nanotube mainly comprises 3 methods, namely an anodic oxidation method, a hydrothermal synthesis method and a template synthesis method. The anodic oxidation method adopts an electrochemical method, takes a high-purity Ti sheet as a working anode, and obtains TiO by anodic oxidation in a fluorine-containing electrolyte solution2An array of nanotubes. For example, chinese patent publication No. CN104894627A discloses a titanium dioxide nanotube loaded with molybdenum disulfide and a method for synthesizing the same, in which TiO2The nanotubes are prepared by an anodic oxidation process. The anodic oxidation method is mainly used for preparing TiO2Nanotube array materials unsuitable for preparing TiO2A nanotube powder material. In addition, the anodic oxidation method needs high-purity Ti sheets, has higher cost and is not suitable for large-scale preparation. The hydrothermal method uses water as a reaction medium, and usually uses nano TiO2(e.g., type P25) with a high-concentration NaOH solution (10 mol L)-1) Uniformly mixing, carrying out hydrothermal reaction, and carrying out acid pickling and high-temperature calcination to obtain TiO2A nanotube. For example, Chinese patent publication No. CN105271388A discloses a high specific surface area ultralong TiO2The preparation method of the nano tube adopts nano TiO2Prepared by a concentrated alkali hydrothermal method. TiO can be synthesized by hydrothermal synthesis method2The inner diameter of the nanotube is too small, the utilization efficiency of the inner wall of the nanotube is extremely low, and high-concentration alkali solution is required to be used,require multiple treatment steps to obtain TiO2Nanotube, the process is complicated.
The template method can synthesize TiO with adjustable pipe diameter and wall thickness2The nanotube material is especially suitable for application in lithium sulfur battery, lithium ion battery, super capacitor, biosensor and other fields. TiO 22The preparation of the nanotube by the template method usually adopts an organic polymer template or a surfactant template and a nano-array pore membrane plate, such as an alumina template, and then prepares TiO by the techniques of electrochemical deposition, sol-gel method, sol-gel-polymerization method and the like2A nanotube. For example, Chinese patent publication No. CN104386743A discloses an anatase type TiO compound2Solvothermal preparation of nanotubes using F127 (block copolymer, polyoxyethylene-polyoxypropylene-polyoxyethylene) as template to prepare TiO2A nanotube. Wangjin Shu et al reported that the AAO template was dipped in (NH)4)2TiF6In the solution, depositing at a constant temperature of 40 ℃, placing the AAO template in the air for drying, and finally performing heat treatment at 400 ℃ to obtain TiO2Nanotube (Ration wave, King golden shu, Lihongyi, etc., AAO template to liquid phase deposition TiO2Influence of the nano-array structure, journal of inorganic chemistry, 2009, 25 (7): 1274-1278). The organic polymer template or the surfactant template has shorter length and smaller diameter, and can only prepare shorter TiO2A nanotube material; the synthesis process of the nano-array porous membrane is complex, and TiO is2The process of filling the inside of the hole is also complicated. The above templates are not conducive to structure-adjustable TiO2And (3) large-scale production of nanotube materials.
In view of the above, TiO is currently used2The preparation methods of the nanotubes have respective disadvantages, so the method has low cost and simple synthesis process, and needs to be further developed without using high-concentration strong alkali solution.
Disclosure of Invention
The invention provides carbon-coated TiO2The preparation method of the nanotube material has the advantages of simple synthesis steps, low cost, mild reaction conditions, suitability for large-scale synthesis, and capability of preparing long-length and long-junctionCarbon-coated TiO with stable structure and good electric conduction2The structure of the nanotube is adjustable, and the carbon coating layer and the nanotube are adjustable.
The method comprises the following specific steps:
potassium permanganate, ammonium fluoride and deionized water are mixed according to the mass ratio of 1 (5-13): (350) and 450), mixing, dissolving completely to obtain a precursor solution, pouring the precursor solution into a hydrothermal reaction kettle, sealing the reaction kettle, putting the reaction kettle into an oven, carrying out hydrothermal reaction for 12-36 h at 160-220 ℃, carrying out centrifugal separation, washing the product with deionized water and absolute ethyl alcohol for multiple times, and drying at 80 ℃ to obtain MnO2A nanowire template material.
MnO of2The nanowire template material is dispersed in a mixed solution (MnO) of absolute ethyl alcohol and water2And absolute ethyl alcohol in a mass ratio of 1: 250-350), slowly dropping isopropyl Titanate (TIP) under the conditions of room temperature and vigorous stirring (volume ratio of TIP to water is 0.1: 1) stirring to react for 1-5 h, centrifugally separating, washing the product with deionized water and absolute ethyl alcohol for multiple times, and drying at 80 ℃ to obtain MnO2@TiO2（TiO2Coating MnO2) A nanowire composite.
MnO of2@TiO2The nanowire composite material is dispersed in the concentration of 1.21g L-1In Tris buffer (MnO)2@TiO2The mass ratio of the Tris solution to the Tris solution was 1: 950-1050), adding dopamine under the conditions of room temperature and vigorous stirring, stirring and reacting for 10-20 h, washing the product for multiple times by deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain MnO2@TiO2@ PDA (polydopamine (PDA) coating MnO)2@TiO2) A nanowire composite.
MnO of2@TiO2The @ PDA nanowire composite material is placed in a quartz tube furnace, argon is introduced, and the quartz tube furnace is heated to 480 ℃ plus 520 ℃ for heat preservation for 1-4 h to obtain MnO2@TiO2@ carbon composite.
MnO of2@TiO2@ carbon nanowire composite material with concentration of 4g L-1In aqueous solution of sodium thiosulfate (MnO)2@TiO2The mass ratio of @ carbon to the sodium thiosulfate solution is 1: 450-550) at room temperature under vigorous stirring, and slowly adding dropwise a solution with a concentration of 18.25g L-1Stirring the diluted hydrochloric acid solution for reaction for 1-5 h, centrifugally separating the product, washing the product for multiple times by using carbon disulfide, deionized water and absolute ethyl alcohol, and drying the product at 80 ℃ to obtain TiO2@ carbon (carbon coated TiO)2) A nanotube material.
The carbon-coated TiO prepared by the process2Nanotube material, TiO2The length of the nano tube is 1-20 um, the inner diameter of the nano tube is 10-100 nm, and TiO is2The thickness of the tube wall is 5-60 nm, and the thickness of the carbon coating layer is 1-20 nm.
The carbon-coated TiO prepared by the invention2The nanotube material is an excellent functional material, can be used for gas-sensitive and moisture-sensitive elements, hydrogen production by photolysis water, photocatalytic degradation and other functional occasions, and is particularly suitable for new energy materials such as lithium ion batteries, super capacitors, lithium sulfur batteries and the like. TiO 22The nanotube has thin wall, large specific surface area, high activity and strong reaction capability, and the TiO can be further improved by coating carbon2The nanotube has stable structure, makes up the defect of low conductivity, and can be used as a new energy material to remarkably improve the electrochemical performance.
Compared with the prior art, the invention has the following advantages:
(1) the invention adopts MnO2Nanowire as template, MnO2The nano-wire has simple synthesis process, mild reaction condition, uniform size, controllable structure and easy removal, and is an excellent template material.
(2) In MnO2The nano wire is taken as a template to prepare TiO with longer length and larger inner diameter than other methods2The nano tube has high yield and is suitable for large-scale production.
(3) Coating and carbonizing TiO with polydopamine2The surface of the nanotube is coated with a nano carbon layer, so that TiO can be further improved2The structural stability and the conductivity of the nanotube improve the electrochemical performance of the nanotube.
Drawings
FIG. 1 shows MnO prepared in example 12A nanowire template material.
FIG. 2 shows MnO prepared in example 12@TiO2A nanowire composite.
FIG. 3 shows carbon-coated TiO prepared in example 12A nanotube material.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
Dissolving 0.1g of potassium permanganate and 0.9g of ammonium fluoride in 40mL of deionized water until the potassium permanganate and the ammonium fluoride are completely dissolved to form a clear mauve solution; then transferring the solution into a reaction kettle with the volume of 100mL, sealing the reaction kettle, putting the reaction kettle into an oven, heating to 200 ℃, keeping the temperature for 24 hours, washing the product with deionized water and absolute ethyl alcohol for multiple times after centrifugal separation, and drying at 80 ℃ to obtain MnO2A nanowire template material. FIG. 1 is a view of the synthesis of MnO2SEM photograph of the nanowire, MnO can be seen2The surface of the nanowire is smooth, the average diameter is about 50 nm, and the length is 10-15 um.
Adding 0.1g MnO2Dispersing the nanowire template material in a mixed solution of 30mL of absolute ethyl alcohol and 0.8mL of water, slowly dropwise adding 0.08mL of isopropyl Titanate (TIP) at room temperature under the condition of vigorous stirring, stirring for reaction for 3h, washing a product for multiple times by deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain TiO2Coating MnO2（MnO2@TiO2) A nanowire composite. FIG. 2 is the MnO synthesized2@TiO2SEM photograph of nanowire composite at MnO2The surface of the nanowire can be clearly seen to be attached with a layer of nanoparticles, so that the surface is changed from smooth to rough. TiO 22The cladding layer was about 10 nm thick.
Adding 0.1g MnO2@TiO2The nanowire composite material is dispersed in 100mL of Tris buffer (concentration 1.21g L)-1) Adding 15 mg of dopamine at room temperature under the condition of vigorous stirring, stirring for reacting for 15h, washing the product for multiple times by using deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain Polydopamine (PDA) coated MnO2@TiO2（MnO2@TiO2@ PDA) nanowire composites.
MnO of2@TiO2The @ PDA nanowire composite material is placed in a quartz tube furnace, argon is introduced, the temperature is increased to 500 ℃, and the temperature is kept for 2h to obtain MnO2@TiO2@ carbon nanowire composites. The carbon coating is not obvious under a scanning electron microscope, and the thickness of the carbon layer can be found to be about 2-4 nm by observation under a high-resolution transmission electron microscope.
Adding 0.1g MnO2@TiO2@ carbon nanowire composite Material was placed in 50 mL of an aqueous solution of sodium thiosulfate (concentration 4g L)-1) Slowly adding dropwise 18.25g L solution at room temperature under vigorous stirring-15 ml of dilute hydrochloric acid solution, stirring and reacting for 3 hours, centrifugally separating a product, washing the product for multiple times by using carbon disulfide, deionized water and absolute ethyl alcohol, and drying the product at 80 ℃ to obtain TiO2@ carbon (carbon coated TiO)2) A nanotube material. FIG. 3 is TiO2The TEM photograph of the @ carbon nanotube material clearly shows the hollow structure of the nanotube, and the inner diameter of the nanotube is about 50 nm.
Example 2
Dissolving 0.1g of potassium permanganate and 0.6 g of ammonium fluoride in 40mL of deionized water until the potassium permanganate and the ammonium fluoride are completely dissolved to form a clear mauve solution; then transferring the solution into a reaction kettle with the volume of 100mL, sealing the reaction kettle, putting the reaction kettle into an oven, heating to 170 ℃, keeping the temperature for 15h, washing the product with deionized water and absolute ethyl alcohol for multiple times after centrifugal separation, and drying at 80 ℃ to obtain MnO2A nanowire template material. Synthetic MnO2The average diameter of the nano-wires is about 70 nm, and the length of the nano-wires is 5-10 um.
Adding 0.1g MnO2Dispersing the nanowire template material in a mixed solution of 30mL of absolute ethyl alcohol and 1.5 mL of water, slowly dropwise adding 0.15 mL of isopropyl Titanate (TIP) at room temperature under the condition of vigorous stirring, stirring for reacting for 2h, washing a product for multiple times by deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain MnO2@TiO2A nanowire composite. TiO 22The cladding layer was about 23 nm thick.
Adding 0.1g MnO2@TiO2The nano-wire composite material is dispersed in100mL Tris buffer (concentration 1.21g L-1) Adding 25 mg of dopamine at room temperature under the condition of vigorous stirring, stirring for reacting for 15h, washing a product for multiple times by using deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain MnO2@TiO2@ PDA nanowire composites.
MnO of2@TiO2The @ PDA nanowire composite material is placed in a quartz tube furnace, argon is introduced, the temperature is increased to 500 ℃, and the temperature is kept for 2h to obtain MnO2@TiO2@ carbon nanowire composites. The carbon layer is about 6-9 nm thick.
Adding 0.1g MnO2@TiO2@ carbon nanowire composite Material was placed in 50 mL of an aqueous solution of sodium thiosulfate (concentration 4g L)-1) Slowly adding dropwise 18.25g L solution at room temperature under vigorous stirring-15 ml of dilute hydrochloric acid solution, stirring and reacting for 3 hours, centrifugally separating a product, washing the product for multiple times by using carbon disulfide, deionized water and absolute ethyl alcohol, and drying the product at 80 ℃ to obtain TiO2@ carbon nanotube material, nanotubes having an inner diameter of about 70 nm.
Example 3
Dissolving 0.1g of potassium permanganate and 1.2 g of ammonium fluoride in 40mL of deionized water until the potassium permanganate and the ammonium fluoride are completely dissolved to form a clear mauve solution; then transferring the solution into a reaction kettle with the volume of 100mL, sealing the reaction kettle, putting the reaction kettle into an oven, heating to 220 ℃, keeping the temperature for 36 hours, washing the product with deionized water and absolute ethyl alcohol for multiple times after centrifugal separation, and drying at 80 ℃ to obtain MnO2A nanowire template material. Synthetic MnO2The average diameter of the nano-wires is about 30 nm, and the length is 13-17 um.
Adding 0.1g MnO2Dispersing the nanowire template material in a mixed solution of 30mL of absolute ethyl alcohol and 3 mL of water, slowly dropwise adding 0.3 mL of isopropyl Titanate (TIP) at room temperature under the condition of vigorous stirring, stirring for reaction for 5 hours, washing a product for multiple times by deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain MnO2@TiO2A nanowire composite. TiO 22The cladding layer was approximately 33 nm thick.
Adding 0.1g MnO2@TiO2The nano-wire composite material is dispersed in 100mL Tris bufferIn the flushing liquid (concentration 1.21g L)-1) Adding 50 mg of dopamine at room temperature under the condition of vigorous stirring, stirring for reacting for 15h, washing the product for multiple times by using deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain MnO2@TiO2@ PDA nanowire composites.
MnO of2@TiO2The @ PDA nanowire composite material is placed in a quartz tube furnace, argon is introduced, the temperature is increased to 500 ℃, and the temperature is kept for 2h to obtain MnO2@TiO2@ carbon nanowire composites. The carbon layer is about 10-16 nm thick.
Adding 0.1g MnO2@TiO2@ carbon nanowire composite Material was placed in 50 mL of an aqueous solution of sodium thiosulfate (concentration 4g L)-1) Slowly adding dropwise 18.25g L solution at room temperature under vigorous stirring-15 ml of dilute hydrochloric acid solution, stirring and reacting for 3 hours, centrifugally separating a product, washing the product for multiple times by using carbon disulfide, deionized water and absolute ethyl alcohol, and drying the product at 80 ℃ to obtain TiO2@ carbon nanotube material, nanotubes having an inner diameter of about 30 nm.
In summary, the template method used in the present invention is used to prepare TiO2Compared with an anodic oxidation method and a hydrothermal method, the nanotube has the advantages of simple synthesis steps, low cost, mild reaction conditions, suitability for large-scale synthesis and capability of preparing TiO with longer length2The nanotube has adjustable structure and practical value.

Claims (4)

1. Carbon-coated TiO2A method for preparing a nanotube material, characterized in that the method comprises the following steps:
step 1, mixing potassium permanganate, ammonium fluoride and deionized water according to a mass ratio of 1 (5-13): (350) and 450), mixing, dissolving completely to obtain a precursor solution, pouring the precursor solution into a hydrothermal reaction kettle, sealing the reaction kettle, putting the reaction kettle into an oven, carrying out hydrothermal reaction for 12-36 h at 160-220 ℃, carrying out centrifugal separation, washing the product with deionized water and absolute ethyl alcohol for multiple times, and drying at 80 ℃ to obtain MnO2A nanowire template material;
step 2, MnO2The nanowire template material is dispersed in absolute ethyl alcohol and waterSlowly dripping isopropyl titanate into the mixed solution at room temperature under the condition of violent stirring, stirring and reacting for 1-5 h, washing the product for multiple times by using deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain MnO2@TiO2A nanowire composite;
step 3, MnO2@TiO2The nano-wire composite material is dispersed in the solution with the concentration of 1.21gL-1Adding dopamine into the trihydroxymethyl aminomethane buffer solution, stirring and reacting for 10-20 h at room temperature under the condition of vigorous stirring, washing the product for multiple times by using deionized water and absolute ethyl alcohol after centrifugal separation, and drying at 80 ℃ to obtain MnO2@TiO2@ PDA nanowire composites;
step 4, MnO2@TiO2Putting the @ PDA nanowire composite material in a quartz tube furnace, introducing argon, heating to 480-520 ℃, and keeping the temperature for 1-4 h to obtain MnO2@TiO2@ carbon composite;
step 5, MnO2@TiO2@ carbon nanowire composite material with concentration of 4gL-1Slowly adding sodium thiosulfate solution into the solution with 18.25gL of concentration at room temperature under vigorous stirring-1Stirring the diluted hydrochloric acid solution for reaction for 1-5 h, centrifugally separating a product, washing the product for multiple times by using carbon disulfide, deionized water and absolute ethyl alcohol, and drying the product at 80 ℃ to obtain TiO2Material of @ carbon nanotubes, i.e. carbon-coated TiO2A nanotube material.
2. The carbon-coated TiO of claim 12The preparation method of the nanotube material is characterized by comprising the following steps: MnO in step 22And absolute ethyl alcohol in a mass ratio of 1: 250-350, wherein the volume ratio of isopropyl titanate to water is 0.1: 1.
3. the carbon-coated TiO of claim 12The preparation method of the nanotube material is characterized by comprising the following steps: MnO in step 32@TiO2The mass ratio of the solution to the tris solution is 1: 950 to 1050.
4. The carbon-coated TiO of claim 12The preparation method of the nanotube material is characterized by comprising the following steps: MnO in step 52@TiO2The mass ratio of @ carbon to the sodium thiosulfate solution is 1: 450 to 550.
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