CN115094432A - Preparation method of structure function integrated transition metal carbide/single-walled carbon nanotube composite film - Google Patents
Preparation method of structure function integrated transition metal carbide/single-walled carbon nanotube composite film Download PDFInfo
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention relates to the field of controllable preparation of carbon nanotube composite macroscopic bodies, in particular to a preparation method of a structure-function integrated transition metal carbide/single-walled carbon nanotube composite film. Depositing transition metal oxide nanoparticles on the functionalized carbon nanotube film by physical sputtering, chemical vapor deposition, hydrothermal synthesis and other methods; and then the carbon nano tube is taken as a carbon source, and is carbonized at high temperature to generate transition metal carbide, and the carbide and the carbon nano tube are combined by chemical bonds to form the transition metal carbide/single-walled carbon nano tube composite film with integrated structure and function. The density and size of the transition metal carbide in the composite film are optimized by regulating and controlling the preparation process conditions of the transition metal oxide, and a high-performance carbon nano tube macroscopic body is obtained. The transition metal carbide/single-walled carbon nanotube composite film prepared by the method can be directly used as an electrocatalytic hydrogen evolution electrode, and low-cost large-scale application of hydrogen energy is promoted.
Description
Technical Field
The invention relates to the field of controllable preparation of carbon nanotube composite macroscopic bodies, in particular to a preparation method of a structure-function integrated transition metal carbide/single-walled carbon nanotube composite film.
Background
Energy and environmental pollution are two major problems restricting the development of the current society, and the greenhouse gas emitted by fossil fuel causes irreversible serious damage to the global environment. The lack of fossil fuels due to non-regeneration will also seriously affect the sustainable development of economy and society. Hydrogen is considered one of the clean green energy carriers that can replace fossil fuels. But low cost, large-scale and green hydrogen production is not realized yet. The hydrogen production by electrolyzing water by using electric energy provided by renewable energy sources (wind energy, solar energy, tidal energy and the like) is a clean and environment-friendly hydrogen production scheme. However, the existing catalyst for hydrogen production by water electrolysis is mainly limited to precious metals such as Pt, Ir, Ru and the like, and the limited reserves lead to high price, thereby limiting the large-scale application of hydrogen production by water electrolysis.
The transition metal carbide is an electrocatalytic hydrogen evolution catalyst which has rich reserves, low price and platinum-like catalytic activity. Tungsten carbide (W) was reported by Levy et al as early as 1973 x C) Has the activity of electrocatalytic decomposition of water, which attracts the attention of researchers (literature 1, Levy R.B., Boudart M.science,1973,181, 547-549). Gong et al impregnated and supported WO on multi-walled carbon nanotubes 3 And carbonizing at low pressure and high temperature to prepare W 2 A C/multi-walled carbon nanotube powder electrocatalyst with high activity (low onset potential 50mV) and excellent dispersion. However, the catalyst prepared by the method is in powder form and needs to be bonded by coatingUse onto electrodes leads to reduced active sites, blockage of mass transfer channels (document 2, Gong q., Wang y., Hu q., et al. nature Communications,2016,7: 13216). Moreover, the size of the transition metal carbide nanoparticles prepared by the method is large, the interaction between the carbide and the carbon nanotubes is weak, and the catalytic activity and stability still need to be improved (document 3, Fan XJ., Zhou hq., ACS Nano,2015,9(5), 5125-51).
In conclusion, the transition metal carbide/carbon nanotube composite material has good application prospect in the field of hydrogen evolution by electrocatalysis, but still has some problems: (1) most of the transition metal carbide/carbon nanotube composite structure is in powder form, and needs to be bonded on a conductive carrier for use, which causes the reduction of the activity of the catalyst. (2) The transition metal carbide is generally generated by a carbon source provided by gaseous alkane decomposition after high-temperature long-time heat treatment (more than or equal to 700 ℃), so that the carbon deposition of the catalyst covers active sites and the carbide is agglomerated and grown. (3) The transition metal carbide is stacked on the carbon nano tube and is easy to fall off in an acid environment, so that the stability of the catalytic performance is poor.
Disclosure of Invention
The invention aims to provide a preparation method of a structure function integrated transition metal carbide/single-walled carbon nanotube composite film, which realizes chemical bond connection through a carbonization reaction between a transition metal oxide and a carbon nanotube to obtain a structure function integrated self-supporting single-walled carbon nanotube film which can be directly used as a catalytic hydrogen evolution film electrode.
The technical scheme of the invention is as follows:
a preparation method of a structure function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the steps of controllably loading transition metal oxide nanoparticles on a functionalized high-quality single-walled carbon nanotube film by a chemical vapor deposition method, a physical sputtering method or a hydrothermal synthesis method; the carbon nano tube is used as a carbon source to react with transition metal oxide at low pressure and high temperature to generate transition metal carbide, and the transition metal carbide and the carbon nano tube are connected by covalent bonds to form a composite film macroscopic body with integrated structure and function; the self-supporting film is directly used as an electrocatalytic hydrogen evolution electrode and shows excellent catalytic activity and stability under an acidic condition.
The film used in the preparation method of the transition metal carbide/single-walled carbon nanotube composite film with integrated structure and function is a high-quality single-walled carbon nanotube film prepared by a floating catalyst chemical vapor deposition method, still has good structural integrity after being functionalized in strong acid, and is an independent self-supporting film macroscopic body.
The preparation method of the structure function integrated transition metal carbide/single-walled carbon nanotube composite film adopts a chemical vapor deposition method, a physical sputtering method or a hydrothermal synthesis method to controllably support transition metal oxide nanoparticles with adjustable density and size on the single-walled carbon nanotube film.
The preparation method of the structure function integrated transition metal carbide/single-walled carbon nanotube composite film takes the single-walled carbon nanotube as a carbon source and the transition metal oxide at the low pressure of 1 multiplied by 10 -4 Reacting at 1Pa and high temperature of 700-1100 ℃ to generate transition metal carbide, wherein the transition metal carbide is connected with the carbon nano tube by covalent bonds.
The preparation method of the structure function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the following steps of connecting the transition metal carbide in a prepared composite film macroscopic body with the carbon nanotube through a covalent bond; the film is directly used as an electrocatalytic hydrogen evolution electrode, avoids active site loss caused by electrode coating, enhances diffusion mass transfer, and improves the catalytic activity and stability of the electrode.
The preparation method of the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the step of functionalizing the carbon nanotubes by adopting a mixed solution of concentrated sulfuric acid with the concentration of 98 wt%, concentrated nitric acid with the concentration of 68 wt% and hydrogen peroxide aqueous solution with the concentration of 30 wt%, wherein the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide aqueous solution is 1:1: 1-8: 1:1, the treatment temperature is 50-80 ℃, the treatment time is 12-36 h, and the treated carbon nanotubes are still self-supporting film macroscopic bodies.
The preparation method of the structure function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the following chemical vapor deposition processes: at low pressure 1X 10 -4 Under the condition of-1 Pa, withThe metal organic matter is a precursor source, and the size and the dispersity of the transition metal oxide are controlled by regulating and controlling the heating temperature to be 100-300 ℃ and the time to be 1-10 h; preparing a transition metal carbide/single-walled carbon nanotube composite film by adopting different metal organics; wherein the transition metal carbide is Mo 2 C、W 2 C. TaC or ReC.
The preparation method of the structure function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the following physical sputtering process: in vacuum environment, the air pressure is 1.3 multiplied by 10 -4 ～1×10 -1 Pa or argon pressure of 1X 10 -1 Under the pressure of-1.5 Pa, the density and the size of the deposited transition metal oxide particles are regulated and controlled by regulating and controlling the sputtering power to be 20-70W and the deposition time to be 30-1800 s, and different transition metal oxide target materials are used for preparing the transition metal carbide single-walled carbon nanotube composite film; wherein the transition metal oxide is MoO 2 、WO 3 、Ta 2 O 5 Or Re 2 O 7 The corresponding transition metal carbide is Mo 2 C、W 2 C. TaC or ReC.
The preparation method of the structure function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the following hydrothermal synthesis processes: placing the single-walled carbon nanotube film in a transition metal oxometallate solution, obtaining transition metal oxide nanoparticles with adjustable size and density by changing the temperature of hydrothermal reaction to 180-250 ℃ and the time to 3-24 h, and preparing the transition metal carbide/single-walled carbon nanotube composite film by using different transition metal oxometallate; wherein the transition metal oxosalt is Na 2 MoO 4 、Na 2 WO 4 、NaTaO 3 Or NaReO 4 The corresponding transition metal carbide is Mo 2 C、W 2 C. TaC or ReC.
The design idea of the invention is as follows:
the invention adopts a single-walled carbon nanotube network as a reactant and a carrier to construct a structure function integrated transition metal carbide/single-walled carbon nanotube self-supporting composite film, takes the single-walled carbon nanotube film with excellent mechanical property, large specific surface area and excellent conductivity as a matrix, carries transition metal oxides by different methods, carries the transition metal oxides with adjustable size and density on the functionalized single-walled carbon nanotube film by methods such as physical sputtering, chemical vapor deposition, hydrothermal synthesis and the like, and reacts the carbon nanotubes and the transition metal oxides under the conditions of low pressure and high temperature to generate carbides which are connected with the carbon nanotubes by chemical bonds, namely a structure function integrated transition metal carbide/composite film macroscopic body.
The invention has the advantages and beneficial effects that:
1. the invention provides a single-walled carbon nanotube composite film with integrated structure and function, which obtains a composite structure formed by connecting transition metal carbide and a carbon nanotube network by chemical bonds through functional component design, namely a macroscopic body of the film with integrated structure and function.
2. The invention can adopt various methods such as chemical vapor deposition, physical sputtering, hydrothermal synthesis and the like to deposit transition metal oxide on the functionalized single-walled carbon nanotube film. By changing the deposition method and deposition conditions, the size and density of the functional component transition metal carbide can be regulated and controlled, and the method has strong compatibility and controllability.
3. The method takes a single-walled carbon nanotube network with large specific surface area and high conductivity as a carrier, the single-walled carbon nanotube network and the transition metal carbide are connected by chemical bonds to form a self-supporting composite film, and the prepared transition metal carbide/single-walled carbon nanotube composite film can be directly used as a self-supporting integrated electrocatalysis hydrogen evolution electrode, thereby promoting the low-cost large-scale application of hydrogen energy. The carrier and the functional components are connected by chemical bonds to improve the electron transport capability, and the self-supporting thin film structure can avoid the loss of active sites caused by catalyst coating and improve the activity and stability of the electrocatalyst.
4. The transition metal carbide/carbon nano tube composite film prepared by the method has good application prospect in the fields of energy storage, photoelectric detection, solar interfacial water evaporation and the like.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a transition metal carbide/single-walled carbon nanotube composite film by chemical vapor deposition.
FIG. 2 is the scanning electron micrograph of the single-walled carbon nanotube film after the strong acid functionalization treatment.
FIG. 3(a) is a scanning electron micrograph of a transition metal carbide/single-walled carbon nanotube composite film prepared by chemical vapor deposition.
FIG. 3(b) is a transmission electron micrograph of the transition metal carbide/single-walled carbon nanotube composite film prepared by chemical vapor deposition.
FIG. 4 is an X-ray photoelectron spectrum representation of the transition metal carbide/single-walled carbon nanotube composite film prepared by chemical vapor deposition.
FIG. 5 shows the hydrogen evolution curve of the transition metal carbide/single-walled carbon nanotube composite film (counter electrode: graphite electrode; reference electrode: Ag/AgCl electrode; electrolyte solution: 0.5mol/L H) 2 SO 4 A solution).
FIG. 6 shows the hydrogen evolution stability test of the transition metal carbide/single-walled carbon nanotube composite film.
FIG. 7 is a schematic diagram of a process for preparing a transition metal carbide/single-walled carbon nanotube composite film by physical vapor deposition.
FIG. 8 is a transmission electron micrograph of the transition metal carbide/single-walled carbon nanotube composite film prepared by physical vapor deposition.
FIG. 9 is a schematic diagram of a hydrothermal process for preparing a transition metal carbide/single-walled carbon nanotube composite film.
FIG. 10 is a TEM image of the W/single-walled carbon nanotube composite film prepared by hydrothermal method.
FIG. 11 is a transmission electron micrograph of the transition metal carbide/single-walled carbon nanotube composite film prepared after changing the chemical vapor deposition conditions.
FIG. 12 is a transmission electron micrograph of the transition metal carbide/single-walled carbon nanotube composite film prepared after changing the carbonization conditions.
Detailed Description
In the specific implementation process, the method adopts methods such as physical sputtering, chemical vapor deposition, hydrothermal synthesis and the like to deposit transition metal oxide nanoparticles on the functionalized carbon nanotube film; and then the carbon nano tube is taken as a carbon source, and is carbonized at high temperature to generate transition metal carbide, and the carbide and the carbon nano tube are combined by chemical bonds to form the transition metal carbide/single-walled carbon nano tube composite film with integrated structure and function. The density and size of the transition metal carbide in the composite film are optimized by regulating and controlling the preparation process conditions of the transition metal oxide, and the high-performance carbon nano tube macroscopic body is obtained. The transition metal carbide/single-walled carbon nanotube composite film prepared by the method can be directly used as an electrocatalytic hydrogen evolution electrode, promotes low-cost large-scale application of hydrogen energy, and is helpful for carbon peak reaching and carbon neutralization.
The present invention will be described in more detail below with reference to examples.
Example 1
As shown in fig. 1, the chemical vapor deposition method for preparing the transition metal carbide/single-walled carbon nanotube film comprises the following specific experimental steps:
(1) functionalization of carbon nanotube films
Placing the single-walled carbon nanotube film prepared by the floating catalyst chemical vapor deposition method in a strong acid solution, wherein the strong acid solution is a mixed solution of concentrated sulfuric acid with the concentration of 98 wt%, concentrated nitric acid with the concentration of 68 wt% and hydrogen peroxide aqueous solution with the concentration of 30 wt%, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide aqueous solution is 4:1:1, heating to 60 ℃, and stirring for 24 hours to obtain the functionalized single-walled carbon nanotube film, wherein a scanning electron microscope photo of the functionalized single-walled carbon nanotube film is shown in figure 2, so that the obtained film still maintains a complete network structure.
(2) Deposition of transition metal oxides
Placing the single-walled carbon nanotube film obtained in the step (1) and 5mg of tricarbonyl trimethylbenzene tungsten into a quartz tube (the diameter is 25mm, the length is 10cm), and vacuumizing until the pressure in the tube is 4 multiplied by 10 -3 And Pa, then placing the mixture in a constant temperature area of a tube furnace, heating the mixture to 200 ℃ at the heating rate of 10 ℃/min, and preserving the heat for 6 hours to obtain the tungsten oxide/single-walled carbon nanotube composite film consisting of the transition metal oxide particles and the single-walled carbon nanotubes.
(3) Carbonization (carburization) of transition metal oxides
Taking the composite film obtained in the step (2), and sealing the composite film into a vacuum quartz tubeIn the vacuum chamber, and vacuumizing to 5X 10 -3 Pa, heating to 900 ℃ at the heating rate of 10 ℃/min in a tube furnace, preserving the heat for 1h, and then cooling to room temperature along with the furnace to obtain the tungsten carbide/single-walled carbon nanotube composite film consisting of the transition metal carbide particles and the single-walled carbon nanotubes.
(4) Structural characterization of composite films
And (4) respectively carrying out scanning electron microscope (figure 3a), transmission electron microscope (figure 3b) and X-ray photoelectron spectroscopy characterization on the sample obtained in the step (3) (figure 4). The diameter distribution of the tungsten carbide particles is 5-10nm, and the tungsten carbide particles are uniformly distributed on the wall of the single-walled carbon nanotube. The peak positions at 33.5eV and 31.4eV in the X-ray photoelectron spectrum are characteristic peaks of W-C bond, which proves that a large amount of W exists in the composite film x And C, particles.
(5) Electrocatalytic hydrogen evolution performance test of composite film
Testing the electro-catalysis hydrogen evolution performance of the tungsten carbide/single-walled carbon nanotube composite film obtained in the step (3), and placing the film in a three-electrode electrochemical workstation (a working electrode: a rotating disc electrode; a counter electrode: a graphite electrode; a reference electrode: an Ag/AgCl electrode; and an electrolyte solution: 0.5mol/L H) 2 SO 4 Solution) was scanned linearly at a scan rate of 0.005V/s. The test result is shown in figure 5, and the initial potential of the composite membrane for electrocatalytic hydrogen evolution is 64mV and 10mA/cm 2 The overpotential at the current density was 152 mV.
And (4) testing the electrocatalytic hydrogen evolution stability of the tungsten carbide/single-walled carbon nanotube composite film obtained in the step (3), wherein the used electrochemical system is the same as that in the step (5). The constant potential of the stability test is 152mV, the test time is 24h, and the result is shown in FIG. 6, which shows that the composite film has good hydrogen evolution stability within 24 h.
Example 2
As shown in fig. 7, the transition metal carbide/single-walled carbon nanotube film is prepared by a physical sputtering method, and the specific experimental steps are as follows:
(1) same as example 1, step (1), except that: in the strong acid solution, concentrated sulfuric acid, concentrated nitric acid and aqueous hydrogen peroxide solution are heated and stirred for 30 hours at 70 ℃ according to the volume ratio of 6:1: 1.
(2) Depositing transition metal oxide particles
Transferring the single-walled carbon nanotube film obtained in the step (1) to a suspended metal frame and placing the suspended metal frame in a cavity of magnetron sputtering equipment, wherein the high-purity tungsten oxide is used as the material with high purity>99.98 wt%) target at low pressure (1X 10) -3 Pa), depositing tungsten oxide particles with the sputtering power of 20W for 500s to obtain the tungsten oxide/single-walled carbon nanotube composite film.
(3) Carburization of tungsten oxide as a transition metal was carried out in the same manner as in the step (3) of example 1 except that the degree of vacuum and the temperature at the time of carburization were 1X 10 -4 Pa and 700 ℃.
(4) Structural characterization of composite films
And (4) performing transmission electron microscope characterization on the tungsten carbide/single-walled carbon nanotube composite film obtained in the step (3) (figure 8). It can be seen that the tungsten carbide particles are uniformly dispersed on the wall of the single-walled carbon nanotube, and the average diameter of the particles is 1.5 nm.
(5) The steps of the electrocatalytic hydrogen evolution performance test are the same as those in step 5 of the embodiment 1, and the test result shows that the initial potential of hydrogen evolution is 82mV, and the current density is not attenuated in the process of the hydrogen evolution performance test for 24h, which shows that the electrocatalytic hydrogen evolution performance test has good catalytic activity and stability.
Example 3
As shown in fig. 9, the hydrothermal synthesis method for preparing the transition metal carbide/single-walled carbon nanotube composite film comprises the following specific steps:
(1) same as example 1, step (1), except that: in the strong acid solution, concentrated sulfuric acid, concentrated nitric acid and aqueous hydrogen peroxide solution are heated and stirred for 15 hours at 80 ℃ according to the volume ratio of 2:1: 1.
(2) Depositing transition metal oxide particles
0.1g of tungstic acid (H) 2 WO 4 ) Dissolved in 20mL of hydrogen peroxide solution (12% by mass), heated to 90 ℃ and stirred for 3 h. And (3) placing the obtained tungstic acid solution and the single-walled carbon nanotube film obtained in the step (1) into a reaction kettle (with the volume of 40 mL). And putting the reaction kettle into a muffle furnace, heating to 180 ℃, preserving heat for 6 hours, naturally cooling, and repeatedly washing with deionized water until the pH value is 7.
(3) Transition metal carbide particles were obtained by high-temperature carburization of the transition metal oxide particles, similar to step (3) of example 1, except that the degree of vacuum and the temperature in the carbonization process were 0.6Pa and 1000 ℃.
(4) Structural characterization of composite films
Transmission electron microscopy (see FIG. 10) shows that there are tungsten carbide particles uniformly distributed on the wall of the single-walled carbon nanotube.
(5) The electrocatalytic hydrogen evolution performance test steps are the same as those in step 5 of the embodiment 1, and the test result shows that the initial potential of hydrogen evolution is 65mV, and the current density is not attenuated in the process of 24h hydrogen evolution performance test, which indicates that the electrocatalytic hydrogen evolution performance test has good catalytic activity and stability.
Example 4
Changing the process conditions of chemical vapor deposition of transition metal oxide, and regulating and controlling the structure of the transition metal carbide/single-walled carbon nanotube composite film, the method comprises the following steps:
(1) same as example 1, step (1), except that: in the strong acid solution, concentrated sulfuric acid, concentrated nitric acid and aqueous hydrogen peroxide solution are heated and stirred for 36 hours at 50 ℃ according to the volume ratio of 8:1: 1.
(2) Deposition of transition metal oxides
Placing the single-walled carbon nanotube film obtained in the step (1) and 5mg of tricarbonyl trimethylbenzene tungsten into a quartz tube (the diameter is 25mm, the length is 10cm), and vacuumizing until the pressure in the tube is 4 multiplied by 10 -3 And Pa, then placing the film in a constant temperature area of a tube furnace, heating the film to 165 ℃ at the heating rate of 10 ℃/min, and preserving heat for 6 hours to obtain the tungsten carbide/single-walled carbon nanotube composite film.
(3) In the same manner as in step (3) of example 1, the vacuum degree and temperature in the different carbonization processes were respectively 4X 10 -4 Pa and 700 ℃.
(4) Structural characterization of composite films
And (4) performing transmission electron microscope characterization on the composite film obtained in the step (3), wherein the result is shown in fig. 11, and the tungsten carbide particles uniformly dispersed on the wall of the single-walled carbon nanotube can be seen.
(5) The steps of the electrocatalytic hydrogen evolution performance test are the same as those in step 5 of the embodiment 1, and the test result shows that the initial potential of hydrogen evolution is 55mV, and the current density is not attenuated in the process of the hydrogen evolution performance test for 24h, which indicates that the electrocatalytic hydrogen evolution performance test has good catalytic activity and stability.
Example 5
The method changes the carbonization condition to regulate and control the structure of the transition metal carbide/single-walled carbon nanotube composite film, and comprises the following specific steps:
(1) same as example 1, step (1), except that: in the strong acid solution, concentrated sulfuric acid, concentrated nitric acid and aqueous hydrogen peroxide solution are heated and stirred for 20 hours at the temperature of 60 ℃ according to the volume ratio of 8:1: 1.
(2) Same as the step (2) of example 1, except that the vacuum degree and the temperature of the chemical vapor deposition process were 2X 10 -3 Pa and 200 ℃.
(3) Taking the composite film obtained in the step (2), sealing the composite film in a vacuum quartz tube, and ensuring that the vacuum degree is 5 x 10 -3 And Pa, heating to 1000 ℃ at the heating rate of 10 ℃/min in a tube furnace, preserving the heat for 1h, and then cooling to room temperature along with the furnace to obtain the tungsten carbide/single-walled carbon nanotube composite film.
(4) Structural characterization of composite films
And (3) performing transmission electron microscope characterization on the composite film obtained in the step (3), wherein the result is shown in fig. 12, as the carbonization temperature is increased, part of tungsten carbide particles are agglomerated, so that the particles are enlarged and the uniformity is poor.
(5) The steps of the electrocatalytic hydrogen evolution performance test are the same as those in step 5 of the embodiment 1, and the test result shows that the initial potential of hydrogen evolution is 50mV, and the current density is not attenuated in the process of the hydrogen evolution performance test for 24h, which shows that the electrocatalytic hydrogen evolution performance test has good catalytic activity and stability.
Example 6
The method for preparing the transition metal carbide/single-walled carbon nanotube composite film with different compositions by changing a metal source comprises the following specific steps:
(1) same as example 1, step (1), except that: in the strong acid solution, concentrated sulfuric acid, concentrated nitric acid and aqueous hydrogen peroxide solution are heated and stirred for 12 hours at the temperature of 80 ℃ according to the volume ratio of 1:1: 1.
(2) Deposition of transition metal oxides
Placing the single-walled carbon nanotube obtained in the step (1) in a cavity of a magnetron sputtering device at low pressure (1.3 multiplied by 10) -1 Pa) at the single wallAnd depositing molybdenum oxide particles on the carbon nano tube film, wherein the deposition power is 20W, the deposition time is 500s, and the argon pressure is 1.33Pa, so that the molybdenum oxide/single-walled carbon nano tube composite film is finally obtained.
(3) The same procedure as in step (3) of example 1, except that the vacuum degree and temperature at the time of carbonization were 1Pa and 1100 ℃ respectively.
(4) The obtained composite film structure is characterized by a transmission electron microscope, the size distribution of the composite film structure is 3-10nm, and the composite film structure has good dispersibility.
(5) The electrocatalytic hydrogen evolution performance test steps are the same as those in step 5 of the embodiment 1, and the test result shows that the initial potential of hydrogen evolution is 70mV, and the current density is not attenuated in the process of 24h hydrogen evolution performance test, which indicates that the electrocatalytic hydrogen evolution performance test has good catalytic activity and stability.
Comparative example 1
The method for preparing the transition metal carbide/single-walled carbon nanotube composite film by adding a carbon source comprises the following specific steps:
(1) same as example 1 step (1)
(2) Same as example 1, step (2)
(3) Carbonization of transition metal oxides
And (3) taking the tungsten oxide/single-walled carbon nanotube composite film obtained in the step (2), putting the tungsten oxide/single-walled carbon nanotube composite film into a tubular furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the atmosphere of 120sccm argon and 80sccm methane, and preserving heat for 1 h.
(4) The transmission electron microscope representation of the prepared composite film structure shows that tungsten carbide nano-particles with uneven sizes are loaded on the carbon nano-tube network, and part of the nano-particles are coated by the carbon layer.
(5) The electrocatalytic hydrogen evolution performance test steps are the same as the step 5 of the embodiment, and the test result shows that the initial potential of hydrogen evolution is 200mV, and the current density attenuation is obvious in the process of 24-hour hydrogen evolution performance test, which indicates that the electrocatalytic activity and the stability are poor.
The results of the examples and the comparative examples show that the transition metal carbide/single-walled carbon nanotube composite film prepared by taking the carbon nanotube network as a support carrier and a carbon source has excellent electro-catalytic hydrogen evolution performance, and compared with the prior art, the invention has the greatest characteristics that: the carbide particles and the single-walled carbon nanotube film are connected by chemical bonds, so that the carbon nanotube film has higher particle density, higher hydrogen evolution activity and stability, and fully exerts the advantages of a macroscopic body of the single-walled carbon nanotube film.
While the invention has been described in detail with respect to the general description and the specific embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. A method for preparing a structure-function integrated transition metal carbide/single-walled carbon nanotube composite film is characterized in that transition metal oxide nanoparticles are controllably supported on a functionalized high-quality single-walled carbon nanotube film by a chemical vapor deposition, physical sputtering or hydrothermal synthesis method; the carbon nano tube is used as a carbon source to react with transition metal oxide at low pressure and high temperature to generate transition metal carbide, and the transition metal carbide and the carbon nano tube are connected by covalent bonds to form a composite film macroscopic body with integrated structure and function; the self-supporting film is directly used as an electrocatalytic hydrogen evolution electrode and shows excellent catalytic activity and stability under an acidic condition.
2. The method for preparing the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1, wherein the used film is a high-quality single-walled carbon nanotube film prepared by a floating catalyst chemical vapor deposition method, which has good structural integrity after functionalization treatment in strong acid and is an independent self-supporting film macroscopic body.
3. The method for preparing the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1, characterized in that the controllable loading density and size of the transition metal oxide nanoparticles on the single-walled carbon nanotube film are adjustable by chemical vapor deposition, physical sputtering or hydrothermal synthesis.
4. The method for preparing the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1, wherein the single-walled carbon nanotube itself is used as a carbon source and is mixed with the transition metal oxide at a low pressure of 1X 10 -4 Reacting at 1Pa and high temperature of 700-1100 ℃ to generate transition metal carbide, wherein the transition metal carbide is connected with the carbon nano tube by covalent bonds.
5. The method for preparing the structure-function integrated transition metal carbide/single-wall carbon nanotube composite film according to claim 1, wherein transition metal carbide in the prepared composite film macrosome is connected with carbon nanotubes by covalent bonds; the film is directly used as an electrocatalytic hydrogen evolution electrode, avoids active site loss caused by electrode coating, enhances diffusion mass transfer, and improves the catalytic activity and stability of the electrode.
6. The preparation method of the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1 or 2, characterized in that a mixed solution of concentrated sulfuric acid with a concentration of 98 wt%, concentrated nitric acid with a concentration of 68 wt% and aqueous hydrogen peroxide with a concentration of 30 wt% is used for functionalizing the carbon nanotubes, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the aqueous hydrogen peroxide is 1:1: 1-8: 1:1, the treatment temperature is 50-80 ℃, the treatment time is 12-36 h, and the carbon nanotubes are still self-supporting film macrostructures after treatment.
7. The method for preparing the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1 or 3, wherein the chemical vapor deposition process comprises: at low pressure 1X 10 -4 Under the condition of-1 Pa, taking metal organic matters as a precursor source, and controlling the size and the dispersity of the transition metal oxide by regulating and controlling the heating temperature to be 100-300 ℃ and the time to be 1-10 h; preparing a transition metal carbide/single-walled carbon nanotube composite film by adopting different metal organics; wherein the transition metal carbide is Mo 2 C、W 2 C. TaC or ReC.
8. The method for preparing the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1 or 3, characterized in that the physical sputtering process comprises the following steps: in vacuum environment, the pressure is 1.3 multiplied by 10 -4 ～1×10 -1 Pa or argon pressure of 1X 10 -1 Under the pressure of-1.5 Pa, the density and the size of the deposited transition metal oxide particles are regulated and controlled by regulating and controlling the sputtering power to be 20-70W and the deposition time to be 30-1800 s, and different transition metal oxide target materials are used for preparing the transition metal carbide single-walled carbon nanotube composite film; wherein the transition metal oxide is MoO 2 、WO 3 、Ta 2 O 5 Or Re 2 O 7 The corresponding transition metal carbide is Mo 2 C、W 2 C. TaC or ReC.
9. The method for preparing the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1 or 3, characterized in that the hydrothermal synthesis process comprises the following steps: placing the single-walled carbon nanotube film in a transition metal oxometallate solution, obtaining transition metal oxide nanoparticles with adjustable size and density by changing the temperature of hydrothermal reaction to 180-250 ℃ and the time to 3-24 h, and preparing the transition metal carbide/single-walled carbon nanotube composite film by using different transition metal oxometallate; wherein the transition metal oxosalt is Na 2 MoO 4 、Na 2 WO 4 、NaTaO 3 Or NaReO 4 The corresponding transition metal carbide is Mo 2 C、W 2 C. TaC or ReC.
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