CN115094432B - Preparation method of transition metal carbide/single-walled carbon nanotube composite film with integrated structure and function - Google Patents
Preparation method of transition metal carbide/single-walled carbon nanotube composite film with integrated structure and function Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B01J35/33—
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to the controllable preparation field of carbon nano tube composite macroscopic bodies, in particular to a preparation method of a transition metal carbide/single-wall carbon nano tube composite film with integrated structure and function. Depositing transition metal oxide nano particles on the functionalized carbon nano tube film by adopting methods such as physical sputtering, chemical vapor deposition, hydrothermal synthesis and the like; and then the carbon nano tube is used as a carbon source, and the transition metal carbide is generated after high-temperature carbonization treatment, and the carbide and the carbon nano tube are combined through chemical bonds to form the transition metal carbide/single-wall carbon nano tube composite film with integrated structure and function. The density and the 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, so that 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 to promote low-cost large-scale application of hydrogen energy.
Description
Technical Field
The invention relates to the controllable preparation field of carbon nano tube composite macroscopic bodies, in particular to a preparation method of a transition metal carbide/single-wall carbon nano tube composite film with integrated structure and function.
Background
Energy and environmental pollution are two major problems restricting the development of the current society, and the greenhouse gases emitted by fossil fuels cause irreversible serious damage to the earth environment. Fossil fuels are becoming scarce because they are not renewable and will also severely impact economic and social sustainable development. Hydrogen is considered one of the clean green energy carriers that can replace fossil fuels. But low cost, large scale, green hydrogen production has not been realized yet. The hydrogen production by electrolysis of water by 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 noble metals such as Pt, ir, ru and the like, and the limited reserves lead to high price, so that the large-scale application of hydrogen production by water electrolysis is limited.
The transition metal carbide is an electrocatalytic hydrogen evolution catalyst with abundant reserves, low price and platinum-like catalytic activity. As early as 1973, levy et al reported tungsten carbide (W x C) Has the activity of electrocatalytically decomposing water, and has attracted extensive attention from researchers (document 1, levy r.b., boudart m.science,1973,181,547-549). Gong et al impregnated supporting WO on multiwall carbon nanotubes 3 And carbonizing under low pressure and high temperature to obtain W 2 A C/multi-walled carbon nanotube powder electrocatalyst having high activity (low initiation potential 50 mV) and excellent dispersibility. However, the catalyst prepared by this method is in a powder form, and needs to be bonded to an electrode by coating, resulting in reduction of active sites and clogging of mass transfer channels (document 2, gong Q., wang y., hu Q., et al nature Communications,2016, 7:13216). Moreover, the transition metal carbide nanoparticles prepared by the method have large size, the interaction between the carbide and the carbon nanotube is weak, and the catalytic activity and stability are still to be improved (document 3, fan XJ., zhou hq., ACS Nano,2015,9 (5), 5125-5134).
In summary, the transition metal carbide/carbon nanotube composite material has good application prospect in the field of electrocatalytic hydrogen evolution, but still has some problems: (1) The transition metal carbide/carbon nano tube composite structure is mostly in powder form, and needs to be adhered to a conductive carrier for use, so that the activity of the catalyst is reduced. (2) The transition metal carbide is generally generated after long-time heat treatment (more than or equal to 700 ℃) at high temperature by a carbon source provided by gaseous alkane decomposition, so that carbon deposition of the catalyst covers active sites and carbide agglomeration grows. (3) The transition metal carbide is accumulated on the carbon nano tube and is easy to fall off in an acidic 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 and function integrated transition metal carbide/single-walled carbon nanotube composite film, which realizes chemical bond connection through carbonization reaction between transition metal oxide and carbon nanotubes to obtain a structure and function integrated self-supporting single-walled carbon nanotube film, and can be directly used as a catalytic hydrogen evolution film electrode.
The technical scheme of the invention is as follows:
the preparation method of the structure and function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the steps of controllably carrying transition metal oxide nano particles on a functionalized high-quality single-walled carbon nanotube film by a chemical vapor deposition, physical sputtering or hydrothermal synthesis method; the self carbon nano tube is used as a carbon source to react with transition metal oxide under low pressure and high temperature to generate transition metal carbide, and the transition metal carbide is connected with the carbon nano tube through 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 acidic conditions.
The film is a high-quality single-wall carbon nanotube film prepared by a floating catalyst chemical vapor deposition method, has good structural integrity after functionalization treatment in strong acid, and is an independent self-supporting film macroscopic body.
The preparation method of the structure and function integrated transition metal carbide/single-wall carbon nano tube composite film adopts a chemical vapor deposition, physical sputtering or hydrothermal synthesis method to controllably load the transition metal oxide nano particles with adjustable density and size on the single-wall carbon nano tube film.
The preparation method of the structure and function integrated transition metal carbide/single-walled carbon nanotube composite film uses the single-walled carbon nanotube as a carbon source and the transition metal oxide at low pressure of 1 multiplied by 10 -4 And (3) reacting at the high temperature of 700-1100 ℃ under the pressure of 1Pa to generate transition metal carbide, wherein the transition metal carbide is connected with the carbon nano tube in a covalent bond.
The preparation method of the structure and function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the step that transition metal carbide in a macroscopic body of the prepared composite film is connected with a carbon nanotube through a covalent bond; the film is directly used as an electrocatalytic hydrogen evolution electrode, so that active site loss caused by electrode coating is avoided, diffusion mass transfer is enhanced, and the catalytic activity and stability of the electrode are improved.
According to the preparation method of the structure-function integrated transition metal carbide/single-walled carbon nanotube composite film, the carbon nanotubes are subjected to functionalization treatment by adopting a mixed solution of 98wt% concentrated sulfuric acid, 68wt% concentrated nitric acid and 30wt% hydrogen peroxide aqueous solution, 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 self-supporting film macroscopic body is still obtained after the treatment.
The preparation method of the structure and function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the following steps of: at low pressure 1×10 -4 Under the condition of 1Pa, 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 100-300 ℃ and the time to 1-10 h; preparing transition metal carbide/single-wall carbon nano tube composite films by adopting different metal organic matters; wherein the transition metal carbide is Mo 2 C、W 2 C. TaC or Rec.
The preparation method of the structure and function integrated transition metal carbide/single-wall carbon nano tube composite film comprises the following steps of: at a vacuum ambient pressure of 1.3X10 -4 ~1×10 -1 Pa or argon pressure of 1X 10 -1 Under the pressure of 1.5Pa, the density and the size of deposited transition metal oxide particles are regulated and controlled by regulating and controlling the sputtering power to 20-70W and the deposition time to 30-1800 s, and different transition metal oxide targets 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 (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 and function integrated transition metal carbide/single-walled carbon nanotube composite film comprises the following steps of: putting a single-wall carbon nano tube film into a transition metal aerobic acid salt solution, obtaining transition metal oxide nano particles with adjustable size and density by changing the temperature of a hydrothermal reaction at 180-250 ℃ for 3-24 hours, and preparing and obtaining a transition metal carbide/single-wall carbon nano tube composite film by using different transition metal aerobic acid salts; wherein the transition metal oxyacid salt 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-wall carbon nanotube network as a reactant and a carrier to construct a structure function integrated transition metal carbide/single-wall carbon nanotube self-supporting composite film, uses a single-wall carbon nanotube film with excellent mechanical property, large specific surface area and excellent conductivity as a matrix, carries transition metal oxide by different methods, carries transition metal oxide with adjustable size and density on the functionalized single-wall carbon nanotube film by methods of physical sputtering, chemical vapor deposition, hydrothermal synthesis and the like, and reacts with the transition metal oxide under the conditions of low pressure and high temperature to generate carbide connected with the carbon nanotube by chemical bonds, namely the 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-wall carbon nano tube composite film with integrated structure and function, which is characterized in that a composite structure of transition metal carbide and a carbon nano tube network which are connected by chemical bonds is obtained through the design of functional components, 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-wall carbon nano tube film. By changing the deposition method and the deposition conditions, the size and the density of the transition metal carbide of the functional component can be regulated and controlled, and the method has strong compatibility and controllability.
3. The method takes the single-walled carbon nanotube network with large specific surface area and high conductivity as a carrier, and the carrier is connected with the transition metal carbide through chemical bonds to form the 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 electrocatalytic hydrogen evolution electrode to promote low-cost large-scale application of hydrogen energy. The carrier and the functional component are connected by chemical bonds, so that the electron transmission capacity can be improved, the self-supporting film structure can avoid the loss of active sites caused by the coating of the catalyst, and the activity and the stability of the electrocatalyst can be improved.
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 energy interface 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 a scanning electron micrograph of a strong acid functionalized single wall carbon nanotube film.
Fig. 3 (a) scanning electron microscope photograph of transition metal carbide/single-walled carbon nanotube composite film prepared by chemical vapor deposition method.
Fig. 3 (b) transmission electron microscope photograph of transition metal carbide/single-walled carbon nanotube composite film prepared by chemical vapor deposition method.
FIG. 4X-ray photoelectron spectroscopy characterization of the transition metal carbide/single-wall carbon nanotube composite film prepared by chemical vapor deposition.
FIG. 5 Hydrogen evolution curve of 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. Hydrogen evolution stability test of transition metal carbide/single wall carbon nanotube composite films.
FIG. 7 is a schematic illustration 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 microscope photograph of a transition metal carbide/single-walled carbon nanotube composite film prepared by a physical vapor deposition method.
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 transmission electron microscope photograph of a tungsten carbide/single-walled carbon nanotube composite film prepared by a hydrothermal method.
FIG. 11 is a transmission electron microscope photograph of a transition metal carbide/single-walled carbon nanotube composite film prepared by changing the chemical vapor deposition conditions.
FIG. 12 is a transmission electron micrograph of a transition metal carbide/single-walled carbon nanotube composite film prepared after varying carbonization conditions.
Detailed Description
In the specific implementation process, transition metal oxide nano particles are deposited on the functionalized carbon nano tube film by adopting methods such as physical sputtering, chemical vapor deposition, hydrothermal synthesis and the like; and then the carbon nano tube is used as a carbon source, and the transition metal carbide is generated after high-temperature carbonization treatment, and the carbide and the carbon nano tube are combined through chemical bonds to form the transition metal carbide/single-wall carbon nano tube composite film with integrated structure and function. The density and the 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, so that 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 helps carbon peak and carbon neutralization.
The invention is further illustrated by the following 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
The single-walled carbon nanotube film prepared by the floating catalyst chemical vapor deposition method is placed in a strong acid solution, the strong acid solution adopts a mixed solution of 98wt% concentrated sulfuric acid, 68wt% concentrated nitric acid and 30wt% hydrogen peroxide water solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide water solution is 4:1:1, the mixture is heated to 60 ℃ and stirred for 24 hours, and the functionalized single-walled carbon nanotube film is obtained, and a scanning electron microscope photo of the functionalized single-walled carbon nanotube film is shown as a 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 trimethyltungsten into a quartz tube (diameter 25mm, length 10 cm), and vacuumizing to 4×10 pressure in the tube -3 Pa, then placing the film in a constant temperature area of a tube furnace, heating to 200 ℃ at a heating rate of 10 ℃/min, and preserving heat for 6 hours to obtain the tungsten oxide/single-walled carbon nanotube composite film consisting of transition metal oxide particles and single-walled carbon nanotubes.
(3) Carbonization (carburizing) of transition metal oxides
Taking the composite film obtained in the step (2), sealing the composite film in a vacuum quartz tube, and vacuumizing to 5 multiplied by 10 -3 Pa, heating to 900 ℃ in a tube furnace at a heating rate of 10 ℃/min, preserving heat for 1h, and cooling to room temperature along with the furnace to obtain the tungsten carbide/single-walled carbon nanotube composite film consisting of transition metal carbide particles and single-walled carbon nanotubes.
(4) Characterization of the Structure of composite films
And (3) respectively carrying out scanning electron microscopy (figure 3 a), transmission electron microscopy (figure 3 b) and X-ray photoelectron spectroscopy characterization (figure 4) on the sample obtained in the step (3). The diameter distribution of the tungsten carbide particles is 5-10nm, and the tungsten carbide particles are uniformDistributed on the wall of the single-wall carbon nano tube. The characteristic peaks of the X-ray photoelectron spectrum at 33.5eV and 31.4eV are W-C bond characteristic peaks, 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 electrocatalytic hydrogen evolution performance of the tungsten carbide/single-walled carbon nanotube composite film obtained in the step (3), and in a three-electrode electrochemical workstation (working electrode: rotary disk electrode; counter electrode: graphite electrode; reference electrode: ag/AgCl electrode; electrolyte solution: 0.5mol/L H) 2 SO 4 Solution), a linear scan is performed at a scan rate of 0.005V/s. The test result is shown in FIG. 5, and the initial potential of the electrocatalytic hydrogen evolution of the composite film is 64mV and 10mA/cm 2 The overpotential at current density was 152mV.
Testing the electrocatalytic hydrogen evolution stability of the tungsten carbide/single-walled carbon nanotube composite film obtained in the step (3), wherein an electrochemical system is used in the same step (5). The constant potential of the stability test is 152mV, the test time is 24h, and the result is shown in FIG. 6, and the composite film has good hydrogen evolution stability within 24 h.
Example 2
As shown in fig. 7, the physical sputtering method for preparing the transition metal carbide/single-walled carbon nanotube film comprises the following specific experimental steps:
(1) Step (1) is the same as in example 1 except that: in the strong acid solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide water solution is 6:1:1, and the mixture is heated and stirred for 30 hours at 70 ℃.
(2) Deposition of transition metal oxide particles
Transferring the single-walled carbon nanotube film obtained in the step (1) onto a suspended metal frame and placing the suspended metal frame into a cavity of a magnetron sputtering device, wherein the high-purity tungsten oxide is used as (purity)>99.98 wt%) target at low pressure (1X 10) -3 Pa), depositing tungsten oxide particles with sputtering power of 20W for 500s to obtain the tungsten oxide/single-wall carbon nano tube composite film.
(3) Carburizing of transition metal tungsten oxide was performed 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 the carbonization were 1X 10, respectively -4 Pa and 700 ℃.
(4) Characterization of the Structure of composite films
And (3) carrying out 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 1.5nm.
(5) The electrocatalytic hydrogen evolution performance test step is the same as the 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 24h hydrogen evolution performance test process, so that the electrocatalytic hydrogen evolution catalyst 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 implementation steps:
(1) Step (1) is the same as in example 1 except that: in the strong acid solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide water solution is 2:1:1, and the mixture is heated and stirred for 15 hours at 80 ℃.
(2) Deposition of transition metal oxide particles
0.1g of tungstic acid (H) 2 WO 4 ) Dissolved in 20mL of hydrogen peroxide solution (mass fraction 12%), heated to 90 ℃ and stirred for 3h. 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). The reaction kettle is placed into a muffle furnace to be heated to 180 ℃, kept warm for 6 hours, naturally cooled, and repeatedly washed with deionized water until the pH value is 7.
(3) The transition metal oxide particles were carburized at high temperature to obtain transition metal carbide particles, as in step (3) of example 1, except that the degree of vacuum and the temperature during the carbonization were 0.6Pa and 1000 ℃.
(4) Characterization of the Structure of composite films
Transmission electron microscopy (as in fig. 10) showed a uniform distribution of tungsten carbide particles on the wall of the single-walled carbon nanotubes.
(5) The electrocatalytic hydrogen evolution performance test step is the same as the 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 24h hydrogen evolution performance test process, so that the electrocatalytic hydrogen evolution catalyst has good catalytic activity and stability.
Example 4
Changing the technological condition of chemical vapor deposition transition metal oxide, regulating and controlling the structure of transition metal carbide/single-wall carbon nanotube composite film, and the specific steps are as follows:
(1) Step (1) is the same as in example 1 except that: in the strong acid solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide water solution is 8:1:1, and the mixture is heated and stirred for 36 hours at 50 ℃.
(2) Deposition of transition metal oxides
Placing the single-walled carbon nanotube film obtained in the step (1) and 5mg of tricarbonyl trimethyltungsten into a quartz tube (diameter 25mm, length 10 cm), and vacuumizing to 4×10 pressure in the tube -3 Pa, then placing the film in a constant temperature area of a tube furnace, heating to 165 ℃ at a heating rate of 10 ℃/min, and preserving heat for 6 hours to obtain the tungsten carbide/single-walled carbon nanotube composite film.
(3) The vacuum degree and the temperature of the different carbonization processes are respectively 4×10 as in the step (3) of the example 1 -4 Pa and 700 ℃.
(4) Characterization of the Structure of composite films
The composite film obtained in the step (3) is subjected to transmission electron microscope characterization, and as shown in fig. 11, tungsten carbide particles uniformly dispersed on the wall of the single-wall carbon nanotube can be seen.
(5) The electrocatalytic hydrogen evolution performance test step is the same as the 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 24h hydrogen evolution performance test process, so that the electrocatalytic hydrogen evolution catalyst has good catalytic activity and stability.
Example 5
The structure of the transition metal carbide/single-walled carbon nanotube composite film is regulated and controlled by changing carbonization conditions, and the specific steps are as follows:
(1) Step (1) is the same as in example 1 except that: in the strong acid solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide water solution is 8:1:1, and the mixture is heated and stirred for 20 hours at 60 ℃.
(2) Step (2) is the same as in example 1, except that chemical vapor depositionThe vacuum degree and the temperature of the process are respectively 2 multiplied by 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 enabling the vacuum degree to be 5 multiplied by 10 -3 Pa, heating to 1000 ℃ in a tube furnace at a heating rate of 10 ℃/min, preserving heat for 1h, and cooling to room temperature along with the furnace to obtain the tungsten carbide/single-walled carbon nanotube composite film.
(4) Characterization of the Structure of composite films
And (3) carrying out transmission electron microscope characterization on the composite film obtained in the step (3), wherein the result is that as shown in fig. 12, due to the fact that the carbonization temperature is increased, part of tungsten carbide particles are agglomerated, so that the particles become large, and the uniformity is poor.
(5) The electrocatalytic hydrogen evolution performance test step is the same as the 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 24h hydrogen evolution performance test process, so that the electrocatalytic hydrogen evolution catalyst has good catalytic activity and stability.
Example 6
The transition metal carbide/single-wall carbon nano tube composite film with different compositions is prepared by changing metal sources, and the specific steps are as follows:
(1) Step (1) is the same as in example 1 except that: in the strong acid solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide water solution is 1:1:1, and the mixture is heated and stirred for 12 hours at 80 ℃.
(2) Deposition of transition metal oxides
Placing the single-walled carbon nanotubes obtained in the step (1) in a cavity of a magnetron sputtering device, and performing sputtering under low pressure (1.3X10) -1 Pa), depositing molybdenum oxide particles on the single-walled carbon nanotube film, wherein the deposition power is 20W, the deposition time is 500s, and the argon pressure is 1.33Pa, so as to finally obtain the molybdenum oxide/single-walled carbon nanotube composite film.
(3) Step (3) was performed as in example 1, except that the vacuum degree and the 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 step is the same as the 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 24h hydrogen evolution performance test process, so that the electrocatalytic hydrogen evolution catalyst has good catalytic activity and stability.
Comparative example 1
The transition metal carbide/single-walled carbon nanotube composite film is prepared by adding a carbon source, and the specific steps are as follows:
(1) Step (1) in the same manner as in example 1
(2) Step (2) in the same manner as in example 1
(3) Carbonization of transition metal oxides
And (3) taking the tungsten oxide/single-walled carbon nanotube composite film obtained in the step (2), placing the film into a tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the atmosphere of 120sccm argon and 80sccm methane, and preserving the heat for 1h.
(4) The prepared composite film structure is characterized by a transmission electron microscope, tungsten carbide nano particles with uneven sizes are supported on a carbon nano tube network, and part of the nano particles are coated by a carbon layer.
(5) The electrocatalytic hydrogen evolution performance test step is the same as that of the embodiment step 5, and the test result shows that the initial potential of hydrogen evolution is 200mV, and the current density decay is obvious in the 24h hydrogen evolution performance test process, which shows that the catalytic 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 electrocatalytic hydrogen evolution performance, and the invention has the greatest characteristics compared with the prior art that: the carbide particles and the single-wall carbon nanotube film are connected by chemical bonds, so that the catalyst has higher particle density, higher hydrogen evolution activity and stability, and fully plays the advantage of the macroscopic body of the single-wall carbon nanotube film.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (6)
1. The preparation method of the structure and function integrated transition metal carbide/single-walled carbon nanotube composite film is characterized in that transition metal oxide nano particles are controllably supported on the functionalized high-quality single-walled carbon nanotube film by chemical vapor deposition, physical sputtering or hydrothermal synthesis; the self carbon nano tube is used as a carbon source to react with transition metal oxide under low pressure and high temperature to generate transition metal carbide, and the transition metal carbide is connected with the carbon nano tube through covalent bonds to form a composite film macroscopic body with integrated structure and function; the film is directly used as an electrocatalytic hydrogen evolution electrode, and shows excellent catalytic activity and stability under an acidic condition;
the film is a high-quality single-wall carbon nanotube film prepared by a floating catalyst chemical vapor deposition method, has good structural integrity after being functionalized in strong acid, and is an independent self-supporting film macroscopic body;
1 x 10 low pressure transition metal oxide with single-wall carbon nanotube as carbon source -4 Reacting at the high temperature of 700-1100 ℃ under the pressure of 1Pa to generate transition metal carbide, wherein the transition metal carbide is connected with the carbon nano tube through covalent bonds;
the transition metal carbide in the prepared composite film macroscopic body is connected with the carbon nano tube by covalent bond; the film is directly used as an electrocatalytic hydrogen evolution electrode, so that active site loss caused by electrode coating is avoided, diffusion mass transfer is enhanced, and the catalytic activity and stability of the electrode are improved.
2. The method for preparing a structure and function integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1, wherein the transition metal oxide nanoparticles with adjustable density and size are controllably supported on the single-walled carbon nanotube film by chemical vapor deposition, physical sputtering or hydrothermal synthesis.
3. The method for preparing the structure-function-integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1, wherein the carbon nanotubes are functionalized by adopting a mixed solution of 98wt% concentrated sulfuric acid, 68wt% concentrated nitric acid and 30wt% hydrogen peroxide aqueous solution, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid to the hydrogen peroxide aqueous solution is 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 macroscopical bodies.
4. The method for preparing a structural-functional integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1 or 2, wherein the chemical vapor deposition process is as follows: at low pressure 1×10 -4 Under the condition of 1Pa, 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 100-300 ℃ and the time to 1-10 h; preparing transition metal carbide/single-wall carbon nano tube composite films by adopting different metal organic matters; wherein the transition metal carbide is Mo 2 C、W 2 C. TaC or Rec.
5. The method for preparing a structural-functional integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1 or 2, wherein the physical sputtering process is as follows: at a vacuum ambient pressure of 1.3X10 -4 ~1×10 -1 Pa or argon pressure of 1X 10 -1 Under the pressure of 1.5Pa, the density and the size of deposited transition metal oxide particles are regulated and controlled by regulating and controlling the sputtering power to 20-70W and the deposition time to 30-1800 s, and different transition metal oxide targets 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 (Re) 2 O 7 The corresponding transition metal carbide is Mo 2 C、W 2 C. TaC or Rec.
6. The method for preparing a structural-functional integrated transition metal carbide/single-walled carbon nanotube composite film according to claim 1 or 2, wherein the hydrothermal synthesis process is as follows: single sheetThe wall carbon nano tube film is placed in a transition metal aerobic acid salt solution, the transition metal oxide nano particles with adjustable size and density are obtained by changing the temperature of the hydrothermal reaction at 180-250 ℃ for 3-24 hours, and different transition metal aerobic acid salts are used for preparing and obtaining the transition metal carbide/single-wall carbon nano tube composite film; wherein the transition metal oxyacid salt 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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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102557029A (en) * | 2012-01-04 | 2012-07-11 | 南昌大学 | Synthetic method of fibrous nano-tungsten carbide |
CN102643638A (en) * | 2012-04-28 | 2012-08-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Tungsten trioxide carbon nano tube composite film, production process and applications thereof |
CN105948128A (en) * | 2016-06-10 | 2016-09-21 | 江西理工大学 | Method for adjusting length of tungsten oxide nano-rod by means of oxygen |
CN111769298A (en) * | 2020-06-19 | 2020-10-13 | 中国科学院金属研究所 | Method for preparing single-atom cluster Fe-N co-doped single-walled carbon nanotube electrocatalytic film electrode |
CN112701268A (en) * | 2021-01-30 | 2021-04-23 | 江西理工大学 | Flexible integrated carbon-coated tungsten oxide/carbon nanotube film composite electrode and preparation method thereof |
-
2022
- 2022-05-12 CN CN202210520829.9A patent/CN115094432B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102557029A (en) * | 2012-01-04 | 2012-07-11 | 南昌大学 | Synthetic method of fibrous nano-tungsten carbide |
CN102643638A (en) * | 2012-04-28 | 2012-08-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Tungsten trioxide carbon nano tube composite film, production process and applications thereof |
CN105948128A (en) * | 2016-06-10 | 2016-09-21 | 江西理工大学 | Method for adjusting length of tungsten oxide nano-rod by means of oxygen |
CN111769298A (en) * | 2020-06-19 | 2020-10-13 | 中国科学院金属研究所 | Method for preparing single-atom cluster Fe-N co-doped single-walled carbon nanotube electrocatalytic film electrode |
CN112701268A (en) * | 2021-01-30 | 2021-04-23 | 江西理工大学 | Flexible integrated carbon-coated tungsten oxide/carbon nanotube film composite electrode and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
Synthesis of multi-walled carbon nanotube–tungsten carbide composites by the reduction and carbonization process;X. Shi 等;Carbon;第45卷;1735-1742 * |
Ultrasmall and phase-pure W2C nanoparticles for efficient electrocatalytic and photoelectrochemical hydrogen evolution;Qiufang Gong等;NATURE COMMUNICATIONS;1-8 * |
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