阅读说明：本技术 氮化钛纳米管及其制备方法和应用 (Titanium nitride nanotube and preparation method and application thereof ) 是由 李武义 张正 郭华彬 洪伟峰 胡海玲 李海军 蔡惠群 于 2020-11-25 设计创作，主要内容包括：本发明提供了一种氮化钛纳米管及其制备方法和应用。该氮化钛纳米管的孔径为10～100nm,氮化钛纳米管的长度为0.1～2μm。氮化钛纳米管以分散的方式存在,而不是氮化钛纳米管阵列,其独立于钛金属之外,因此其可以根据应用的需求而制作为相应的形态,且利于分散使用。另外,由于本申请的氮化钛纳米管的孔径和长度特点,适用于作为载体,为活性成分提供稳定的负载环境。(The invention provides a titanium nitride nanotube and a preparation method and application thereof. The titanium nitride nanotube has a pore diameter of 10 to 100nm and a length of 0.1 to 2 μm. The titanium nitride nanotube exists in a dispersed mode, but not a titanium nitride nanotube array, is independent of titanium metal, so that the titanium nitride nanotube array can be manufactured into a corresponding form according to the application requirements, and is favorable for dispersed use. In addition, due to the characteristics of the aperture and the length of the titanium nitride nanotube, the titanium nitride nanotube is suitable for being used as a carrier and provides a stable loading environment for active ingredients.)

1. The titanium nitride nanotube is characterized in that the aperture of the titanium nitride nanotube is 10-100 nm, and the length of the titanium nitride nanotube is 0.1-2 mu m.

2. The titanium nitride nanotubes of claim 1, wherein the titanium nitride nanotubes are face centered cubic titanium nitride.

3. A catalyst comprising a support and an active ingredient, characterized in that the support is the titanium nitride nanotubes of claim 1 or 2, preferably the active ingredient is platinum.

4. A method for preparing titanium nitride nanotubes, which is characterized by comprising the following steps:

step S1, mixing tetrabutyl titanate and a zinc oxide nanorod and hydrolyzing the tetrabutyl titanate to coat titanium dioxide on the surface of the zinc oxide nanorod to obtain a titanium dioxide coated zinc oxide nanorod;

step S2, sufficiently carrying out acidolysis on the zinc oxide in the titanium dioxide coated zinc oxide nano-rod to obtain a titanium dioxide nano-tube;

and step S3, nitriding the titanium dioxide nanotube to obtain the titanium nitride nanotube.

5. The method for preparing a composite material according to claim 4, wherein the step S1 includes:

mixing 0.1-1 g of the zinc oxide nano rod with 50-500 mL of ethanol solution for the first time to form a first mixed system;

mixing the first mixed system and 2-20 mL of ammonia water for the second time to form a second mixed system;

and mixing the second mixed system with 2-20 mL of tetrabutyl titanate solution with the mass concentration of 80% for hydrolysis reaction to obtain the titanium dioxide coated zinc oxide nanorod.

6. The preparation method according to claim 5, wherein the first mixing is ultrasonic mixing, preferably the ultrasonic mixing has an ultrasonic power of 50-100 and a time of 30-90 min; preferably, the second mixing is stirring mixing, and preferably, the stirring speed of the stirring mixing is 500-1000 rpm, and the time is 30-60 min.

7. The preparation method according to claim 5, wherein stirring is performed during the hydrolysis reaction, and preferably the stirring speed is 500-1000 rpm and the stirring time is 5-10 h.

8. The method according to claim 5, wherein the ethanol solution has a volume concentration of 5 to 50% and the ammonia water has a mass concentration of 25 to 35%.

9. The preparation method according to claim 4, wherein the acid used for acidolysis in step S2 is any one or more of hydrochloric acid, sulfuric acid and nitric acid, and the mass concentration of the acid is 5-20%.

10. The method for preparing a composite material according to claim 4, wherein the step S3 includes:

and calcining the titanium dioxide nanotube in ammonia gas to obtain the titanium nitride nanotube, wherein the flow of the ammonia gas is preferably 80-120 mL/min, the calcining temperature is preferably 600-900 ℃, and the calcining time is 2-6 h.

Technical Field

The invention relates to the field of titanium nitride material preparation, in particular to a titanium nitride nanotube and a preparation method and application thereof.

Background

Titanium nitride is a novel golden yellow inorganic semiconductor material, and has the advantages of high hardness, high melting point, small friction coefficient, heat conduction and electric conduction. Titanium nitride therefore has many good properties and is widely used in several fields. Titanium nitride is often used as a cutting tool and abrasive material, a lubricating and wear-resistant lubricant for bearings, and a corrosion-resistant and high-temperature-resistant material for radiators. Because of good heat conduction, electric conduction and corrosion resistance, the catalyst carrier is also researched and applied to the field of fuel cell catalyst carriers. Therefore, the research on the titanium nitride has important economic significance.

Chinese patent No. CN108163821B discloses a method for preparing spherical titanium nitride, which specifically relates to a method for preparing spherical titanium nitride by using rf plasma powder production equipment, and specifically comprises the following main steps: the titanium nitride powder is prepared by one step by adopting radio frequency plasma equipment as a reaction device, titanium hydride powder as a raw material and nitrogen as a reaction gas. The chinese patent application No. 201910446227.1 discloses a method for preparing porous titanium nitride, which comprises the following steps: mixing titanium powder, magnesium oxide and ammonium chloride according to a mass ratio and then carrying out ball milling; assembling and sealing the ball-milled powder and then washing gas; then igniting under nitrogen atmosphere; and then crushing the product, sieving the product, reacting the product with hydrochloric acid, and drying the centrifuged solid into powder to obtain the porous titanium nitride. Research shows that the titanium nitride has various preparation methods and has various advantages and disadvantages, but the prepared titanium nitride is mostly spherical and porous in a zero-dimensional material.

The shape of the titanium nitride reported at present is mainly spherical with a zero-dimensional structure, and the preparation method of the shape structure of the one-dimensional tubular structure is relatively less. At present, the conventional titanium nitride nanotube is a titanium nitride film formed by a titanium nitride nanotube array prepared by electrochemistry, and the titanium nitride film is difficult to separate from titanium metal, so the application of the titanium nitride film is limited.

Disclosure of Invention

The invention mainly aims to provide a titanium nitride nanotube, and a preparation method and application thereof, so as to solve the problem that the application of the titanium nitride nanotube in the prior art is limited.

In order to achieve the above object, according to one aspect of the present invention, there is provided a titanium nitride nanotube having a pore diameter of 10 to 100nm and a length of 0.1 to 2 μm.

Further, the titanium nitride nanotube is face-centered cubic titanium nitride.

According to another aspect of the present invention there is provided a catalyst comprising a support and an active ingredient, the support being any one of the titanium nitride nanotubes described above, preferably the active ingredient being platinum.

According to another aspect of the present invention, there is provided a method for preparing a titanium nitride nanotube, the method comprising: step S1, mixing tetrabutyl titanate and a zinc oxide nanorod and hydrolyzing the tetrabutyl titanate to coat titanium dioxide on the surface of the zinc oxide nanorod to obtain a titanium dioxide coated zinc oxide nanorod; step S2, performing full acidolysis on zinc oxide in the titanium dioxide-coated zinc oxide nano-rod to obtain a titanium dioxide nano-tube; and step S3, nitriding the titanium dioxide nanotube to obtain the titanium nitride nanotube.

Further, the step S1 includes: performing first mixing on 0.1-1 g of zinc oxide nano rod and 50-500 mL of ethanol solution to form a first mixed system; mixing the first mixed system and 2-20 mL of ammonia water for the second time to form a second mixed system; and mixing the second mixed system with 2-20 mL of tetrabutyl titanate solution with the mass concentration of 80% for hydrolysis reaction to obtain the titanium dioxide coated zinc oxide nanorod.

Further, the first mixing is ultrasonic mixing, preferably, the ultrasonic power of the ultrasonic mixing is 50-100W, and the time is 30-90 min; the second mixing is preferably stirring mixing, and the stirring speed of the stirring mixing is preferably 500-1000 rpm, and the time is preferably 30-60 min.

Further, stirring is carried out during the hydrolysis reaction, preferably at a speed of 500 to 1000rpm for 5 to 10 hours.

Furthermore, the volume concentration of the ethanol solution is 5-50%, and the mass concentration of ammonia water is 25-35%.

Further, the acid used for the acidolysis in the step S2 is any one or more of hydrochloric acid, sulfuric acid and nitric acid, and the mass concentration of the acid is 5% to 20%.

Further, the step S3 includes: and calcining the titanium dioxide nanotube in ammonia gas to obtain the titanium nitride nanotube, wherein the flow of the ammonia gas is preferably 80-120 mL/min, the calcining temperature is preferably 600-900 ℃, and the calcining time is 2-6 h.

By applying the technical scheme of the invention, the titanium nitride nanotube exists in a dispersed mode, but not a titanium nitride nanotube array, and is independent of titanium metal, so that the titanium nitride nanotube array can be made into a corresponding form according to the application requirement and is beneficial to dispersed use. In addition, due to the characteristics of the aperture and the length of the titanium nitride nanotube, the titanium nitride nanotube is suitable for being used as a carrier and provides a stable loading environment for active ingredients.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate exemplary embodiments of the invention and, together with the description, serve to explain the invention and are not intended to limit the invention. In the drawings:

FIG. 1 shows a titanium dioxide Tube (TiO) prepared in example 1₂NTs) XRD pattern;

FIG. 2 shows XRD of titanium nitride nanotubes prepared in example 1;

FIG. 3 shows an SEM image of titanium nitride nanotubes prepared in example 1;

FIG. 4 shows 0.5mol/L H saturated with nitrogen at room temperature₂SO₄Scanning the cyclic voltammetry curve of the titanium nitride obtained in example 1 in the solution; and

FIG. 5 shows 0.5M H at room temperature₂SO₄Scan in solution +0.1M methanol solution as in example 1And obtaining a time-measuring current curve chart of Pt/TiN NTs.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.

As analyzed by the background of the present application, the titanium nitride nanotube of the prior art is formed on titanium metal and is difficult to be separated from the titanium metal, so that the application of the titanium nitride nanotube is limited, and in order to solve the problem, the present application provides a titanium nitride nanotube, a carbon-coated titanium nitride nanotube and a method for preparing the titanium nitride nanotube and the carbon-coated titanium nitride nanotube.

In an exemplary embodiment of the present application, a titanium nitride nanotube is provided, wherein the diameter of the titanium nitride nanotube is 10 to 100nm, and the length of the titanium nitride nanotube is 0.1 to 2 μm.

The titanium nitride nanotube array exists in a dispersed mode, and is not a titanium nitride nanotube array, and is independent of titanium metal, so that the titanium nitride nanotube array can be manufactured into a corresponding form according to the application requirements, and is favorable for dispersed use. In addition, due to the characteristics of the aperture and the length of the titanium nitride nanotube, the titanium nitride nanotube is suitable for being used as a carrier and provides a stable loading environment for active ingredients.

In addition, the titanium nitride nanotube can also be face-centered cubic titanium nitride, so that the structure is stable.

In another exemplary embodiment of the present application, there is provided a catalyst comprising a support and an active ingredient, the support being any of the titanium nitride nanotubes described above, and preferably the active ingredient being platinum. The catalyst provided by the application provides a stable loading environment for active ingredients when being used as a carrier due to the characteristics of the aperture and the length of the carrier, so that the activity and the stability of the corresponding catalyst using conventional porous carbon as the carrier are obviously improved.

In another exemplary embodiment of the present application, there is provided a method for preparing a titanium nitride nanotube, the method comprising: step S1, mixing tetrabutyl titanate and a zinc oxide nano rod, and hydrolyzing tetrabutyl titanate to coat titanium dioxide on the surface of the zinc oxide nano rod to obtain a titanium dioxide coated zinc oxide nano rod; step S2, sufficiently carrying out acidolysis on zinc oxide in the titanium dioxide coated zinc oxide nanorod to obtain a titanium dioxide nanotube; and step S3, nitriding the titanium dioxide nanotube to obtain the titanium nitride nanotube.

According to the method, the zinc oxide nano-rod is used as a template for preparing the titanium dioxide nano-tube, so that the coated titanium dioxide with complete appearance is formed; then removing zinc oxide by utilizing the difference of the reactivity of zinc oxide and titanium dioxide with acid, thereby obtaining a titanium dioxide nanotube; and then nitridizing the titanium dioxide to obtain the titanium nitride nanotube. The whole process is simple to operate and easy to realize, and the obtained titanium nitride nanotube has complete appearance and stable structure.

The titanium nitride nanotube obtained by the preparation method has the aperture of 10-100 nm and the length of 0.1-2 mu m. The titanium nitride crystal has a face-centered cubic titanium nitride structure through XRD measurement.

The zinc oxide nano rod can be prepared by adopting commercial zinc oxide nano rods in the prior art or adopting a known method, for example, the method comprises the following steps: firstly, adding 0.1-10 g of zinc acetate into 10-100 mL of deionized water, and stirring to obtain a uniform solution; adding 0.1-10 g of sodium alginate solution into 10-100 mL of zinc acetate solution, then adding 0.1-10 mL of ammonia water, uniformly stirring, transferring the mixed solution into a hydrothermal kettle for hydrothermal reaction, cooling to room temperature, washing with deionized water, and drying to obtain the zinc oxide nanorod. Wherein the temperature of the hydrothermal reaction is 80-160 ℃ and the time is 5-24 h.

In one embodiment, the step S1 includes: mixing 0.1-1 g of zinc oxide nano rod and 50-500 mL of ethanol solution for the first time to form a first mixed system; mixing the first mixed system and 2-20 mL of ammonia water for the second time to form a second mixed system; and mixing the second mixed system with 2-20 mL of tetrabutyl titanate solution with the mass concentration of 80% for hydrolysis reaction to obtain the titanium dioxide coated zinc oxide nanorod. Firstly, mixing a zinc oxide nano rod, an ethanol solution and ammonia water to form an alkaline first mixed system, then mixing a tetrabutyl titanate solution with the first mixed system, and hydrolyzing tetrabutyl titanate in the presence of an alkaline environment and ethanol to form titanium dioxide to coat the zinc oxide nano rod. In the process, the proportion of the zinc oxide nanorod, the ethanol solution, the ammonia water solution and the tetrabutyl titanate is controlled, so that the tetrabutyl titanate is prevented from being gelatinized on one hand, and uniform titanium dioxide coating is formed on the zinc oxide nanorod as far as possible on the other hand.

In order to accelerate the mixing efficiency, the first mixing is preferably ultrasonic mixing, the ultrasonic power of the ultrasonic mixing is preferably 50-100W, the time is preferably 30-90 min, and the time is preferably 40-80 min. The second mixing is preferably stirring mixing, and the stirring speed of the stirring mixing is preferably 500-1000 rpm, and the time is preferably 30-60 min.

In order to enhance the effects of the respective substances to be fully exerted, the volume concentration of the ethanol solution is preferably 5% to 50%, and the mass concentration of the ammonia water is preferably 25% to 35%.

In the hydrolysis process, in order to coat titanium dioxide on the surfaces of the added zinc oxide nanorods and improve the yield of the titanium nitride nanotubes, stirring is preferably carried out in the hydrolysis reaction process, and the stirring speed is preferably 500-1000 rpm and the stirring time is preferably 5-10 h. Preferably, the hydrolysis is carried out at room temperature.

As described above, zinc oxide and titanium dioxide have different reactivity with acid, and the step S2 removes the zinc oxide nanorods among the titanium oxide-coated zinc oxide nanorods using acid. After removing the zinc oxide nano-rod, washing by deionized water, filtering and drying to prepare the titanium dioxide nano-tube.

In order to improve the removal efficiency of zinc oxide, the acid used for the acidolysis in step S2 is preferably one or more of hydrochloric acid, sulfuric acid, and nitric acid, and the mass concentration of the acid is preferably 5% to 20%.

In another embodiment of the present application, the step S3 includes: and calcining the titanium dioxide nanotube in ammonia gas to obtain the titanium nitride nanotube, wherein the flow of the ammonia gas is preferably 80-120 mL/min, the calcining temperature is preferably 600-900 ℃, and the calcining time is 2-6 h. During the above calcination process, the titanium dioxide is gradually nitrided and maintains the hollow tubular morphology of the nanotubes.

The calcination herein may be carried out in calcination equipment conventional in the art, such as a tube furnace or an atmosphere furnace, and the like.

When the preparation method is implemented, the adopted stirring can be magnetic stirring, mechanical stirring or glass rod stirring; the adopted cooling can be natural cooling; the drying used may be forced air drying oven, vacuum drying oven or muffle oven drying.

The advantageous effects of the present application will be further described below with reference to examples and comparative examples.

Example 1

1) Adding 3.3g of zinc acetate into 100mL of deionized water, and fully stirring to prepare a uniform solution; adding 0.1g of sodium alginate into 10mL of deionized water to prepare a uniform solution; adding the sodium alginate solution into the zinc acetate solution, then adding 10mL of 25% ammonia water, stirring at room temperature for 30min, carrying out hydrothermal reaction at 120 ℃ for 12h, and cooling to room temperature. And repeatedly centrifuging and washing the zinc oxide nano rod for 3 times by using deionized water, and drying the zinc oxide nano rod in a blast drying oven to obtain the zinc oxide nano rod.

2) Adding 0.5g of zinc oxide nano rod into 300mL of 30% ethanol solution, and performing ultrasonic dispersion for 60min at the power of 90W; then 15mL of 25% ammonia water was added thereto, and stirred at 800rpm for 40min, 15mL of 80% butyl titanate was slowly dropped by a dropper, and the mixture was stirred at 800rpm for reaction at room temperature for 6 hours. And after the reaction is finished, washing the reaction product for 3 times by using deionized water, and drying the reaction product in a blast drying oven to obtain the titanium dioxide coated zinc oxide nano rod.

3) And (3) putting the titanium dioxide coated zinc oxide nano-rod prepared in the step 2) into excessive 5% hydrochloric acid, stirring for 12 hours to completely dissolve zinc oxide, washing with deionized water, filtering and drying to obtain the titanium dioxide nano-tube.

4) Uniformly paving the titanium dioxide nanotubes obtained in the step 3) in a corundum ark, putting the corundum ark into a tube furnace for calcination, wherein ammonia gas is used as a nitrogen source, the flow of the ammonia gas is 100mL/min, the calcination temperature is set to 750 ℃, the calcination time is 4 hours, and the titanium nitride nanotubes are prepared by adopting a nitridation method.

FIG. 1 is a titanium dioxide Tube (TiO) prepared in example 1₂NTs) XRD pattern. As compared with the standard PDF # 21-1272 of XRD of titanium dioxide, it is known that anatase phase diffraction peaks appear in the vicinity of 2 θ of 25.45 °, 38.25 °, 48.42 °, 54.11 ° and 63.05 °, and the phases correspond to the (101), (004), (200), (105), (211) and (204) crystal planes of anatase phases, respectively, and are pure anatase phases. The prepared titanium dioxide nanotube is pure anatase phase titanium dioxide.

FIG. 2 is an XRD pattern of the titanium nitride nanotubes prepared in example 1, and in comparison with standard JCPDS NO.38-1420 of XRD of titanium nitride, the diffraction peaks of the prepared titanium nitride correspond to those of the standard titanium nitride one by one, which shows that the obtained final product is face-centered cubic titanium nitride.

Fig. 3 is an SEM image of the titanium nitride nanotubes prepared in example 1, showing that the prepared titanium nitride is tubular titanium nitride.

Example 2

1) Adding 0.1g of zinc acetate into 10mL of deionized water, and fully stirring to prepare a uniform solution; adding 10g of sodium alginate into 100mL of deionized water to prepare a uniform solution; adding the sodium alginate solution into the zinc acetate solution, then adding 5mL of 25% ammonia water, stirring at room temperature for 30min, carrying out hydrothermal reaction at 120 ℃ for 12h, and cooling to room temperature. And repeatedly centrifuging and washing the zinc oxide nano rod for 3 times by using deionized water, and drying the zinc oxide nano rod in a blast drying oven to obtain the zinc oxide nano rod.

2) Adding 0.1g of zinc oxide nano rod into 50mL of 30% ethanol solution, and performing ultrasonic dispersion for 30min with the power of 100W; then 2mL of 25% ammonia water was added thereto, and the mixture was stirred at 1000rpm for 30min, then 10mL of 80% tetrabutyl titanate was slowly dropped by a dropper, and the mixture was stirred at 1000rpm for 5h at room temperature. And after the reaction is finished, washing the reaction product for 3 times by using deionized water, and drying the reaction product in a blast drying oven to obtain the titanium dioxide coated zinc oxide nano rod.

3) And putting the titanium dioxide coated zinc oxide nano rod prepared in the step 2) into excessive 5% hydrochloric acid, and stirring for 12 hours to completely dissolve the zinc oxide. Washing with deionized water, filtering and drying to obtain the titanium dioxide nanotube.

4) Uniformly paving the titanium dioxide nanotubes obtained in the step 3) in a corundum ark, putting the corundum ark into a tube furnace for calcination, wherein ammonia gas is used as a nitrogen source, the flow of the ammonia gas is 80mL/min, the calcination temperature is set to be 600 ℃, the calcination time is 6 hours, and the titanium nitride nanotubes are prepared by adopting a nitridation method.

Example 3

1) Adding 10g of zinc acetate into 100mL of deionized water, and fully stirring to prepare a uniform solution; adding 5g of sodium alginate into 50mL of deionized water to prepare a uniform solution; the sodium alginate solution was added to the zinc acetate solution, followed by addition of 0.1mL of 25% strength ammonia, and stirring was carried out at room temperature for 30 min. Then transferring the solution into a hydrothermal kettle, carrying out hydrothermal reaction at 120 ℃ for 12h, and cooling to room temperature. And repeatedly centrifuging and washing the nano-rods for 3 times by using deionized water, and drying the nano-rods in a blast drying oven to obtain the zinc oxide nano-rods.

2) Adding 1g of zinc oxide nano rod into 500mL of 30% ethanol solution, ultrasonically dispersing for 90min at the power of 50W, then adding 20mL of 25% ammonia water, stirring at the speed of 500rpm, stirring for 60min, slowly dropwise adding 2mL of 80% tetrabutyl titanate by using a dropper, and stirring for reacting for 10h at room temperature at the speed of 500 rpm. And after the reaction is finished, washing the reaction product for 3 times by using deionized water, and drying the reaction product in a blast drying oven to obtain the titanium dioxide coated zinc oxide nano rod.

3) And putting the titanium dioxide coated zinc oxide nano rod prepared in the step 2) into excessive 5% hydrochloric acid, and stirring for 12 hours to completely dissolve the zinc oxide. Washing with deionized water, filtering and drying to obtain the titanium dioxide nanotube.

4) Uniformly paving the titanium dioxide nanotubes obtained in the step 3) in a corundum ark, putting the corundum ark into an atmosphere furnace for calcination, wherein ammonia gas is used as a nitrogen source, the flow of the ammonia gas is 120mL/min, the calcination temperature is set to 900 ℃, the calcination time is 2 hours, and the titanium nitride nanotubes are prepared by adopting a nitridation method.

Example 4

The difference from example 1 is that:

2) adding 0.5g of the zinc oxide nano rod prepared in the example 1 into 300mL of 5% ethanol solution, and ultrasonically dispersing for 30min with the power of 90W; then 15mL of 25% ammonia water was added thereto, and the mixture was stirred at 800rpm for 40min, and then 15mL of 80% butyl titanate was slowly dropped by a dropper, and the mixture was stirred at room temperature for 6 hours at 800rpm to react. And after the reaction is finished, washing the reaction product for 3 times by using deionized water, and drying the reaction product in a blast drying oven to obtain the titanium dioxide coated zinc oxide nano rod.

Example 5

The difference from example 1 is that:

2) adding 0.5g of the zinc oxide nano rod prepared in the example 1 into 300mL of 50% ethanol solution, and ultrasonically dispersing for 90min at the power of 90W; then 15mL of 25% ammonia water was added thereto, and stirred at 800rpm for 40min, 15mL of 80% butyl titanate was slowly dropped by a dropper, and stirred at room temperature for 6h, and the stirring speed was 800 rpm. And after the reaction is finished, washing the reaction product for 3 times by using deionized water, and drying the reaction product in a blast drying oven to obtain the titanium dioxide coated zinc oxide nano rod.

Example 6

The difference from example 1 is that:

2) adding 0.5g of the zinc oxide nano rod prepared in the example 1 into 300mL of 30% ethanol solution, and ultrasonically dispersing for 60min at the power of 90W; then 15mL of 35% ammonia water was added thereto, and stirred at 800rpm for 40min, 15mL of 80% butyl titanate was slowly dropped by a dropper, and stirred at room temperature for 6h, and the stirring speed was 800 rpm. And after the reaction is finished, washing the reaction product for 3 times by using deionized water, and drying the reaction product in a blast drying oven to obtain the titanium dioxide coated zinc oxide nano rod.

Example 7

The difference from example 1 is that:

2) adding 0.5g of the zinc oxide nano rod prepared in the example 1 into 300mL of 30% ethanol solution, and ultrasonically dispersing for 60min at the power of 90W; then 15mL of 25% ammonia water was added thereto, and stirred at 800rpm for 40min, 20mL of 80% butyl titanate was slowly dropped by a dropper, and the mixture was stirred at 500rpm for 10h at room temperature. And after the reaction is finished, washing the reaction product for 3 times by using deionized water, and drying the reaction product in a blast drying oven to obtain the titanium dioxide coated zinc oxide nano rod.

Example 8

The difference from example 1 is that:

2) adding 0.5g of the zinc oxide nano rod prepared in the example 1 into 300mL of 30% ethanol solution, and ultrasonically dispersing for 60min at the power of 90W; then 15mL of 25% ammonia water was added thereto, and stirred at 800rpm for 40min, then 30mL of 80% butyl titanate was slowly dropped by a dropper, and stirred at room temperature for reaction for 15h, with a stirring speed of 500 rpm. And after the reaction is finished, washing the reaction product for 3 times by using deionized water, and drying the reaction product in a blast drying oven to obtain the titanium dioxide coated zinc oxide nano rod.

Example 9

The difference from example 1 is that:

2) adding 0.5g of the zinc oxide nano rod prepared in the example 1 into 300mL of 30% ethanol solution, and ultrasonically dispersing for 60min at the power of 90W; then, 30mL of 25% ammonia water was added thereto, and the mixture was stirred at 800rpm for 40min, and then 15mL of 80% butyl titanate was slowly dropped using a dropper, and the mixture was stirred at 800rpm for reaction at room temperature for 6 hours.

Example 10

The difference from example 1 is that:

2) adding 0.5g of the zinc oxide nano rod prepared in the example 1 into 30mL of 30% ethanol solution, and ultrasonically dispersing for 60min at the power of 90%; then 15mL of 25% ammonia water was added thereto, and the mixture was stirred at 800rpm for 40min, and then 15mL of 80% butyl titanate was slowly dropped by a dropper, and the mixture was stirred at room temperature for 6 hours at 800rpm to react.

Example 11

The difference from example 1 is that:

4) uniformly paving the titanium dioxide nanotubes obtained in the step 3) in a corundum ark, putting the corundum ark into a tube furnace for calcination, wherein ammonia gas is used as a nitrogen source, the flow of the ammonia gas is 150mL/min, the calcination temperature is set to be 550 ℃, the calcination time is 6 hours, and the titanium nitride nanotubes are prepared by adopting a nitridation method.

In addition, structural characterization is performed on the titanium nitride nanotubes or carbon-coated titanium nitride nanotubes obtained in examples 1 to 11, wherein a field emission scanning electron microscope is used to detect the pore diameter and the length, and it is found that the pore diameter and the length of the titanium nitride nanotubes obtained in each example are all between 10 nm and 100nm, and the length is between 0.1 μm and 2 μm, but the collapse rate of the examples with higher calcination temperature and longer time is larger because of different collapse rates of calcination temperature.

FIG. 4 is a plot of cyclic voltammograms of titanium nitride from example 1 scanned in a 0.5mol/L H2SO4 solution saturated with nitrogen at room temperature. Wherein the scanning speed is 50mV/s, and the scanning range is-0.2-1.0V (vs. Ag/AgCl). As can be seen from fig. 4, no other peak of redox reaction occurred after 100 cycles, and the prepared titanium nitride has good electrochemical stability compared with the 1 st and 100 th cycles.

The titanium nitride nano-silicon tube material prepared in example 1 was mixed with chloroplatinic acid solution, and Pt/TiN NTs were prepared by ethylene glycol reduction.

Preparing an electrode: dissolving prepared Pt/TiN NTs in an ethanol solution to prepare slurry, coating 5 mu L of the slurry on the surface of a glassy carbon electrode by using a liquid transfer machine, coating 3 mu L of a proton exchange membrane (Nafion reagent) after drying, and drying to obtain two electrodes. FIG. 5 is a plot of chronoamperometry of scanning Pt/TiN NTs from example 1 in 0.5M H2SO4 solution +0.1M methanol solution at room temperature. From the comparative curves in the figures, the current density of the prepared catalyst decreased more slowly, indicating that the prepared Pt/TiN NTs catalyst has better catalytic stability and corrosion and poisoning resistance compared with the commercial catalyst (Pt/C).

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.