CN116216781A - Method for synthesizing superfine nanowire/carbon nanotube composite film by inter-tube confinement induction - Google Patents
Method for synthesizing superfine nanowire/carbon nanotube composite film by inter-tube confinement induction Download PDFInfo
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- CN116216781A CN116216781A CN202211668945.1A CN202211668945A CN116216781A CN 116216781 A CN116216781 A CN 116216781A CN 202211668945 A CN202211668945 A CN 202211668945A CN 116216781 A CN116216781 A CN 116216781A
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- 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
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- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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Abstract
The invention relates to the controllable preparation field of carbon nano tube composite materials, in particular to a method for synthesizing an ultrafine nano wire/carbon nano tube composite film by inter-tube confinement induction. The method comprises the steps of controllably introducing defects on the tube wall of the carbon nano tube through chemical oxidation, plasma treatment and the like, introducing transition metal, noble metal, transition metal oxide and the like among the tube bundles of the carbon nano tube through chemical vapor deposition, wet chemical synthesis, solvothermal synthesis and the like, and then inducing self-assembly through rapid heat treatment and the like to form superfine nano wires limited among the tube bundles of the carbon nano tube, wherein the nano wires are directionally arranged among the tubes of the carbon nano tube to form an ordered composite film. The method can regulate the structure and components of the nanowire by changing manufacturing defects and introducing nanowire precursors, and the prepared superfine nanowire composite carbon nanotube film has a unique ordered structure and excellent performance and has wide application prospects in the fields of electrocatalytic total-decomposition water, thermal evaporation desalination of seawater, photo-thermal coupling catalysis and the like.
Description
Technical Field
The invention relates to the controllable preparation field of carbon nano tube composite materials, in particular to a method for synthesizing an ultrafine nano wire/carbon nano tube composite film by inter-tube confinement induction.
Background
Carbon nanotubes can be seen as one-dimensional hollow tubular structures of graphene curled with ultrafine nanotube cavities (0.6-2.0 nm). Since the structure of carbon nanotubes was finely resolved, its unique hollow tubular structure has attracted considerable attention from researchers. In particular, the synthesis of carbon nanotube composite structures with new structures and new properties by using single-walled carbon nanotubes as "templates" has been a research hotspot in this field.
For the controllable synthesis of carbon nanotube composite structures, researchers have proposed two types of methods: firstly, carbon is realized by adsorbing a gas phase precursor source and a liquid phase precursor source by utilizing capillary action of a nano tube cavity special for the carbon nano tubeFilling of nanotubes to prepare C 60 Carbon nanotubes, I 2 One-dimensional tubular structures such as @ carbon nanotubes, metal nanoparticles/nanowires @ carbon nanotubes, metal oxide nanoparticles/nanowires @ carbon nanotubes, chalcogenides @ carbon nanotubes, and the like, and find great application potential in the fields of nanoelectronics, photodetection, catalysis, and the like (SmithB.W.et. Carbon,2000,321,1-2,169-174; zhangJ.et. Angew.chem.int.ed.,2017,56,1850-1854; hartM., et. Inorg. Chem.2019,58, 15216-15224). Secondly, the tube wall of the carbon nano tube is used as a template, and a coaxial one-dimensional tubular heterojunction is grown through chemical vapor deposition to prepare a single-wall carbon nano tube @ h-BN and a single-wall carbon nano tube @ h-BN@MoS 2 And carbon nanotube composite structures, and are found to have excellent thermal conductivity enhancement, photoelectric properties, etc. (Xiang r., et al science,2020,367,6477,537-542).
The novel carbon nano tube composite material with excellent performance is obtained by adopting the method, but the sample quantity is usually small, and the application range of the novel carbon nano tube composite material is greatly limited. And because the curvature of the tube wall of the carbon nano tube is large, the size of the tube cavity is small, the one-dimensional composite structure of the carbon nano tube prepared by filling and cladding has the problems of poor controllability, low efficiency, poor repeatability and the like. Based on the above, the invention provides a method for efficiently and controllably synthesizing the superfine nanowire/carbon nanotube composite film by taking the limit space between the single-walled carbon nanotubes as a template.
Disclosure of Invention
The invention aims to provide a method for synthesizing an ultrafine nanowire/carbon nanotube composite film by inter-tube confinement induction, which is characterized in that defects can be controlled among carbon nanotubes, precursors are adsorbed at the defects, and the ultrafine nanowire with inter-tube confinement is formed by self-assembly or rapid thermal driving, so that the carbon nanotube composite film with uniform and ordered structure is obtained. Introducing transition metal oxide through low-pressure chemical vapor deposition, and preparing an inter-tube confinement superfine transition metal carbide/carbon nano tube composite film through high-temperature carbonization; reducing metal acetylacetonate by wet chemical method, and self-assembling between tubes to form superfine metal nanowire/carbon nanotube composite film; and decomposing the transition metal polyacid salt by adopting a solvothermal method to form metal oxide to form nuclei between tubes for growth, and carrying out heat treatment to obtain the superfine transition metal oxide nanowire/carbon nanotube composite film. The inter-tube confinement nanowire has the characteristics of monodispersion and directional arrangement, and the composite carbon nanotube film constructed by the method has wide application prospect in the field of energy storage and conversion.
The technical scheme of the invention is as follows:
the method for synthesizing superfine nanowire/carbon nanotube composite film by inter-tube confinement induction comprises controllably introducing defects on the wall of high-quality carbon nanotubes by chemical oxidation or plasma treatment, introducing transition metal, noble metal or transition metal oxide between the carbon nanotube bundles by chemical vapor deposition, wet chemical synthesis or solvothermal synthesis, and performing rapid heat treatment to induce self-assembly to form superfine nanowire of inter-carbon nanotube confinement, thereby obtaining composite film with superfine nanowire arranged between carbon nanotubes in an oriented manner; the structure and composition of the nanowires are controlled by changing the manufacturing defects and the method of introducing nanowire precursors.
According to the method for synthesizing the superfine nanowire/carbon nanotube composite film by inter-tube confinement induction, the carbon nanotube film is a high-quality single-wall carbon nanotube film, the thickness of the film is 1-2 mu m, and the film still has good mechanical properties after defects are introduced by chemical oxidation or plasma, so that a self-supporting structure can be maintained.
The method for synthesizing the superfine nanowire/carbon nanotube composite film by inter-tube confinement induction adopts a chemical oxidation method to controllably introduce defects on the wall of the carbon nanotube, and the defect density and size are regulated and controlled by using oxidants with different oxidabilities, changing the concentration of the oxidants and the oxidation time in the chemical oxidation process; wherein the oxidant is KMnO with strong oxidizing property 4 Or H 2 SO 4 H of weak oxidizing nature 2 O 2 Or an oxidizing acid HNO 3 。
The method for synthesizing the superfine nanowire/carbon nanotube composite film by inter-tube confinement induction adopts plasma treatment to controllably introduce defects on the wall of the carbon nanotube, adopts plasma sources with different chemical reactivity, changes the power for generating plasma and regulates and controls the treatment time to introduce defectsDensity and size of (3); wherein the plasma source is O with high chemical reactivity 3 Or O 2 Or moderately chemically reactive H 2 Or inert N 2 Or Ar.
The method for synthesizing the superfine nanowire/carbon nanotube composite film by inter-tube confinement induction introduces transition metal, noble metal or transition metal oxide between carbon nanotubes by chemical vapor deposition, wet chemical synthesis or solvothermal synthesis, and forms the superfine nanowire confined between the carbon nanotubes after heat treatment.
According to the method for synthesizing the superfine nanowire/carbon nanotube composite film by inter-tube confinement induction, the precursor grows by defect induction deposition, and the prepared superfine nanowire has a diameter smaller than 5nm and is directionally arranged among the tubes of the carbon nanotubes to form the carbon nanotube composite film with an ordered structure.
The method for synthesizing the superfine nanowire/carbon nanotube composite film by the inter-tube confinement induction adopts a low-pressure chemical vapor deposition method to synthesize superfine transition metal carbide nanowires of the inter-tube confinement, takes metal organic matters as a precursor source under the negative pressure condition, deposits transition metal oxide clusters on the wall of the carbon nanotube containing defects at the temperature lower than the decomposition temperature of the precursor source, rapidly heats to 700-1700 ℃ at the heating rate of 50-500 ℃/s, and introduces CH 4 Carbonizing the nano-wires for 1 to 5 minutes by using a carbon source, and agglomerating the nano-wires in a limited space between the tubes to form ultrafine transition metal carbide nano-wires; wherein the transition metal carbide is Mo 2 C、W 2 C. One or more than two of TaC or Rec, the transition metal carbide/single-walled carbon nanotube composite film of the inter-tube confinement has excellent electrocatalytic hydrogen evolution performance.
The method for synthesizing the superfine nanowire/carbon nanotube composite film by the inter-tube confinement induction adopts a wet chemical method to synthesize the superfine metal nanowire of the inter-tube confinement, takes acetylacetone metal salt as a precursor, adds a surfactant and heats in 130-220 ℃ oleylamine for 1-300 min, and generates the superfine metal nanowire among the bundles of the carbon nanotube film; wherein the metal is one or more than two of Pt, pd, fe, co, ni, mo, ru, rh; the surfactant is one or more than two of didodecyl dimethyl ammonium bromide, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide and behenyl dimethyl ammonium bromide, and the inter-tube confinement superfine metal nanowire/single-wall carbon nanotube composite film has excellent interfacial water evaporation performance.
The method for synthesizing the superfine nanowire/carbon nanotube composite film by the inter-tube confinement induction has the advantages that the superfine nanowire confinement is arranged among the carbon nanotubes in a directional manner, has specific structural orientation, and is widely applied to the fields of electrocatalytic total decomposition of water, thermal evaporation desalination of sea water, photo-thermal coupling catalysis or solar interface water evaporation.
The design idea of the invention is as follows:
the invention utilizes the groove between the single-wall carbon nanotubes as the confined space to controllably synthesize the self-supporting superfine nanowire/carbon nanotube composite film. The method is characterized in that single-wall carbon nanotubes have the characteristic of superfine tube diameter, a micro-confined space is formed between the tubes, defects can be controlled on the tube walls of the carbon nanotubes, and then precursor self-assembly is introduced into the defects of the carbon nanotubes by methods such as solvothermal reaction, chemical vapor deposition, wet chemical synthesis and the like to form superfine nanowires. The inter-tube confinement monodisperse superfine nanowire has consistent orientation, and the composite film has excellent performance.
The invention has the advantages and beneficial effects that:
1. the invention provides a preparation method of an inter-tube confinement superfine nanowire/carbon nanotube composite film, which utilizes the inter-tube confinement effect of carbon nanotubes to control preparation of a monodisperse superfine nanowire which is arranged in a directional manner.
2. The invention can adopt various methods such as chemical vapor deposition, solvothermal reaction, wet chemical synthesis and the like to introduce transition metal, metal oxide, metal carbide and the like among the carbon nano tubes, and can realize the regulation and control of the structure and the performance of the composite film by changing the method and the process condition for introducing the nano wires, thereby having strong compatibility and controllability.
3. The method takes the carbon nano tube network with large specific surface area and high conductivity as a carrier, and the inter-tube confinement ensures that the superfine nano wire and the carbon nano tube have better contact, thereby improving the stability and having excellent performance in the aspects of enhancing electron and phonon transmission.
4. The transition metal carbide superfine nano wire/carbon nano tube composite film and the metal superfine nano wire carbon nano tube composite film prepared by the method have good application prospects in the fields of electrocatalytic total decomposition water, photo-thermal conversion, solar energy interface water evaporation and the like.
Drawings
FIG. 1 is a schematic illustration of the chemical vapor deposition process for preparing a composite film of inter-tube confinement ultra-fine transition metal carbide nanowires/carbon nanotubes.
FIG. 2 inter-tube confinement ultra-fine W 2 Scanning transmission electron microscope photograph of the C nano wire/carbon nano tube composite film.
FIG. 3 inter-tube confinement superfine W 2 Hydrogen evolution curve of C nano wire/carbon nano tube composite film (counter electrode: graphite electrode; reference electrode: ag/AgCl electrode; electrolyte solution: 0.5 mol/LH) 2 SO 4 A solution).
FIG. 4 is a schematic illustration of the wet chemical process for preparing the transition metal ultra-fine nanowires/carbon nanotubes composite film.
FIG. 5 is a transmission electron micrograph of an inter-tube confinement transition metal ultrafine nanowire/carbon nanotube composite film.
FIG. 6 shows the full water solubility of the transition metal ultrafine nanowire/carbon nanotube composite film with a limited area between the tubes (electrolyte solution: 1mol/L KOH aqueous solution).
FIG. 7 shows the performance of the transition metal superfine nano wire/carbon nano tube composite film in the light-heat interface water evaporation to desalinate sea water.
FIG. 8 is a transmission electron micrograph of a transition metal carbide particle/carbon nanotube composite film.
Detailed Description
In the specific implementation process, defects are controllably introduced on the tube wall of the carbon nano tube through chemical oxidation, plasma treatment and the like, then precursors such as transition metal, noble metal, transition metal oxide and the like are introduced among the carbon nano tube by adopting methods such as low-pressure chemical vapor deposition, wet chemical synthesis, solvothermal synthesis and the like, and self-assembly is induced through heat treatment and the like to form superfine nano wires limited among the tube bundles of the carbon nano tube, and the nano wires are directionally arranged among the tubes of the carbon nano tube to obtain the superfine nano wire/carbon nano tube ordered composite film. The method is characterized in that the inter-tube confinement metal/metal oxide/transition metal carbide superfine nanowire/carbon nano tube composite film is prepared by introducing defects into the tube wall of the carbon nano tube, regulating and controlling the technological conditions of the precursor introduction process, changing the types of precursor sources and the like.
The invention is further described below by way of examples and figures.
Example 1
As shown in fig. 1, the process for preparing the inter-tube confinement transition metal carbide superfine nanowire/carbon nanotube composite film by chemical vapor deposition comprises the following specific experimental steps:
(1) Controllable defect on carbon nano tube wall
The volume ratio of the preparation is V Sulfuric acid ：V Nitric acid =5: 1, placing the single-wall carbon nano tube grown by the floating catalytic chemical vapor deposition method in 10-30 ml of the mixed acid solution and heating to 70 ℃ for 20h. Washing with deionized water to neutrality, vacuum filtering to obtain single-wall carbon nanotube film with defect in the wall of 2-3 microns and mixed acid to form great number of defect sites on the wall of carbon nanotube.
(2) Low pressure chemical vapor deposition of transition metal oxides
Taking acid treated single-wall carbon nanotube film with size of 1×1cm, adding 30mg tricarbonyl trimethylbenzene tungsten powder into quartz tube, vacuum sealing tube, and vacuum reducing the pressure in quartz tube to 1×10 -4 ～1×10 -1 And (3) sealing after Pa, and placing the sealed quartz tube into a muffle furnace for heat treatment at 300 ℃ for 10 hours to obtain the single-walled carbon nanotube composite film with tungsten oxide nano particles dispersed among the tubes.
(3) Carbonization assembly of transition metal oxides to form nanowires
Putting the film obtained in the step (2) into a tube furnace, and introducing mixed gas (methane 2%, hydrogen 10% and argon 88% by volume percent) into the tube furnace at 500 DEG CHeating to 1500 ℃ at a heating rate of/min, heat-treating for 5min, cooling with a furnace, and forming W in a limiting region between pipes 2 C nanowire to obtain superfine W 2 C nano wire/carbon nano tube composite film.
(4) Characterization of the Structure of composite films
As shown in FIG. 2, the composite film was ultrasonically dispersed and then dropped onto a copper mesh micro-grid, and ultra-fine W was observed by a transmission electron microscope 2 Microstructure of C nanowire/carbon nanotube composite film, superfine W 2 The C nano wires are monodisperse among bundles of carbon nano tubes, have the diameter of 1-1.5 nm and the average length of 10nm, and have consistent orientation.
(5) Electrocatalytic hydrogen evolution performance test of composite film
Testing the superfine W obtained in the step (3) 2 Electrocatalytic hydrogen evolution performance of C nanowire/single-walled carbon nanotube film in three-electrode electrochemical workstation (working electrode: rotating disk electrode; counter electrode: graphite electrode; reference electrode: ag/AgCl electrode; electrolyte solution: 0.5 mol/LH) 2 SO 4 Solution), a linear scan was performed at a scan rate of 5 mV/s. As shown in FIG. 3, the test result shows that the initial potential of the electrocatalytic hydrogen evolution of the composite film is 42mV,10mA/cm 2 The overpotential at current density was 72mV.
Example 2
As shown in fig. 4, the wet chemical method for preparing the inter-tube confinement ultra-fine transition metal nanowire/carbon nanotube composite film comprises the following specific experimental steps:
(1) Controllable defect on carbon nano tube wall
The single-wall carbon nano tube film which is directly collected after the floating catalytic chemical vapor deposition method is grown is placed in a plasma cleaning machine, the treatment power of the plasma is 7W, the treatment time is 1min, the defects are manufactured on the wall of the carbon nano tube by utilizing the plasma, the single-wall carbon nano tube film with the wall rich in defects is obtained, the thickness of the single-wall carbon nano tube film is 1-2 mu m, and the defects loaded on the wall of the single-wall carbon nano tube are mainly carbon vacancies, point defects and the like.
(2) Wet chemical deposition of transition metals
A certain amount of platinum acetylacetonate, iron acetylacetonate, molybdenum acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate (20 mg each) and 50mg of cetyltrimethylammonium bromide, and 80mg of anhydrous glucose were taken, placed in 5ml of an oleylamine solvent, subjected to ultrasonic dispersion and dissolution to form a uniform solution, and a carbon nanotube film rich in defects was placed in the solution, and heated in an oil bath at 160 ℃ for 60 minutes. And after the reaction is finished, taking out the film, and washing with absolute ethyl alcohol to remove the surfactant, thereby obtaining the superfine PtFeCoNiMo nanowire/single-walled carbon nanotube composite film.
(3) Characterization of the Structure of composite films
Step (4) was performed as in example 1. As shown in fig. 5, the composite film was ultrasonically dispersed and then dropped onto a copper mesh micro-grid, and the microstructure of the ultra-fine PtFeCoNiMo nanowire/single-walled carbon nanotube composite film, which was monodisperse between bundles of carbon nanotubes, had an average diameter of 1.56nm, an average length of 20nm, and had a uniform orientation, was observed using a transmission electron microscope.
(4) Electrocatalytic full-decomposition water performance test of composite film
And (3) testing the electrocatalytic full water decomposition performance of the superfine PtFeCoNiMo nanowire/single-walled carbon nanotube composite film obtained in the step (2), and performing linear scanning at a scanning rate of 5mV/s by using a 1mol/LKOH aqueous solution as an electrolyte. As shown in FIG. 6, the test result shows that the composite film can reach 10mA cm under the voltage of 1.667V -2 High-efficiency full water dissolution of current density.
Example 3
As shown in fig. 4, the wet chemical method for preparing the inter-tube confinement transition metal ultrafine nanowire/carbon nanotube composite film comprises the following specific experimental steps:
(1) Controllable defect on carbon nano tube wall
Step (1) was performed as in example 1.
(2) Wet chemical deposition of multiple transition metals
Step (2) was performed as in example 2.
(3) Characterization of the Structure of composite films
Step (4) was performed as in example 1. The composite film is dropped onto a copper mesh micro-grid after ultrasonic dispersion, and a transmission electron microscope is used for observing the microstructure of the ultra-fine PtFeCoNiMo nanowire/single-wall carbon nano tube composite film, wherein the ultra-fine PtFeCoNiMo nanowire is monodisperse among bundles of carbon nano tubes, has an average diameter of 1.44nm and an average length of 10.3nm, and has consistent orientation.
(4) Interfacial thermal evaporation performance test of composite film
Putting the composite film prepared in the step (2) into thermal evaporation performance testing equipment, taking wood pulp fiber as a water channel to absorb water and transmitting the water to the upper composite film, taking polytetrafluoroethylene as a structural support die, and separating the composite film from seawater to prevent heat loss. As shown in FIG. 7, the thermal evaporation performance of the transition metal ultrafine nanowire carbon nanotube composite film under the irradiation of sunlight is obtained after testing for 6 hours, and the evaporation efficiency is 1.2 kg.m -2 ·h -1 。
Example 4
Method for preparing inter-tube confinement superfine WO (WO) by solvothermal method 3 The nanowire/carbon nanotube composite film comprises the following specific experimental steps:
(1) Controllable defect on carbon nano tube wall
Step (1) was performed as in example 2.
(2) Solvothermal synthesis of ultrafine WO 3 Nanowire
First, 0.1g of tungstic acid (WO 3 ·H 2 O), dissolving in 20mL of 20% hydrogen peroxide aqueous solution, taking the single-walled carbon nanotube film in (1), putting the single-walled carbon nanotube film and the solution into a 40mL reaction kettle, heating to 110 ℃ in a muffle furnace at a heating rate of 10 ℃/min, preserving heat for 3h, and cooling to room temperature along with the furnace. Taking out the film and repeatedly cleaning with deionized water to obtain superfine WO 3 A nanowire/carbon nanotube composite film.
(3) Characterization of the Structure of composite films
Step (4) was performed as in example 1. Dispersing the composite film ultrasonically, dripping the dispersed composite film onto a copper mesh micro grid, and observing superfine WO (WO) by using a transmission electron microscope 3 Microstructure of nano wire/carbon nano tube composite film, superfine WO 3 The nanowires are monodisperse among bundles of carbon nanotubes, have a diameter of 1-2 nm, an average length of about 5nm, and have a uniform orientation.
Comparative example 1
The transition metal carbide nanoparticle/carbon nanotube composite film comprises the following specific steps:
(1) Collecting single-wall carbon nanotube film by floating catalytic chemical vapor deposition, shearing 1×1cm, adding 20mg tungsten hexacarbonyl powder into quartz tube, vacuum sealing tube, and vacuum reducing the pressure in quartz tube to 1×10 -4 ～1×10 -1 And (5) sealing after Pa, and placing the sealed quartz tube into a muffle furnace at 230 ℃ for heat treatment for 5 hours.
(2) Step (3) in the same manner as in example 1
(3) In example 1, step (4), the transmission electron microscope characterization result is shown in fig. 8, and it is clear from the graph that no ultra-fine nanowires are formed, and the average diameter of the nano-particle particles with wide size distribution and obvious agglomeration carried on the carbon nano-tube reaches 10nm. Meanwhile, the small-size oxide particles are agglomerated, so that the dispersibility and uniformity of the nano particles in the composite film are poor.
The results of the examples and comparative examples show that single-walled carbon nanotubes that are not defective in tube wall construction are larger in size by chemical vapor deposition and that larger sized particles are more prone to agglomeration into larger sized particles during subsequent heat treatment. Therefore, the structure and the components of the nanowire can be regulated and controlled by changing the manufacturing defects and the method for introducing nanowire precursors, and the step of introducing defects by pretreatment of the single-wall carbon nanotube has the promotion effect on the growth of the nanowire in the inter-tube confinement. The superfine nanowire composite carbon nanotube film prepared by the method has a unique ordered structure and excellent performance, and has wide application prospects in the fields of electrocatalytic total decomposition of water, thermal evaporation desalination of seawater, photo-thermal coupling catalysis, interfacial water evaporation and other energy storage and conversion.
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 (9)
1. A method for synthesizing an ultrafine nanowire/carbon nanotube composite film by inter-tube confinement induction is characterized in that defects are controllably introduced on the wall of a high-quality carbon nanotube by a chemical oxidation or plasma treatment method, transition metal, noble metal or transition metal oxide is introduced among the bundles of the carbon nanotube by a chemical vapor deposition, wet chemical synthesis or solvothermal synthesis method, and self-assembly is induced by rapid heat treatment to form an ultrafine nanowire of the inter-carbon nanotube confinement, so that the composite film with the ultrafine nanowire arranged among the carbon nanotubes in an oriented manner is obtained; the structure and composition of the nanowires are controlled by changing the manufacturing defects and the method of introducing nanowire precursors.
2. The method for synthesizing the superfine nanowire/carbon nanotube composite film by the inter-tube confinement induction according to claim 1, wherein the used carbon nanotube film is a high-quality single-wall carbon nanotube film, the thickness of the film is 1-2 mu m, and the film still has good mechanical properties after chemical oxidation or plasma introduction of defects and can maintain a self-supporting structure.
3. The method for synthesizing the superfine nanowire/carbon nanotube composite film by inter-tube confinement induction according to claim 1 or 2, wherein defects are controllably introduced on the wall of the carbon nanotube by adopting a chemical oxidation method, and the defect density and size are regulated and controlled by using oxidants with different oxidabilities, changing the concentration of the oxidants and the oxidation time in the chemical oxidation process; wherein the oxidant is KMnO with strong oxidizing property 4 Or H 2 SO 4 H of weak oxidizing nature 2 O 2 Or an oxidizing acid HNO 3 。
4. The method for synthesizing ultrafine nanowire/carbon nanotube composite film by inter-tube confinement induction according to claim 1 or 2, wherein defects are controllably introduced on the carbon nanotube walls by plasma treatment, plasma sources with different chemical reactivity are used, and power and treatment for generating plasma are changedThe time control introduces the density and size of the defect; wherein the plasma source is O with high chemical reactivity 3 Or O 2 Or moderately chemically reactive H 2 Or inert N 2 Or Ar.
5. The method for synthesizing the superfine nanowire/carbon nanotube composite film by inter-tube confinement induction according to claim 1, wherein transition metal, noble metal or transition metal oxide is introduced between carbon nanotubes by a chemical vapor deposition, wet chemical synthesis or solvothermal synthesis method, and the superfine nanowire confined between the carbon nanotubes is formed after heat treatment.
6. The method for synthesizing the superfine nanowire/carbon nanotube composite film by the inter-tube confinement induction according to claim 1 or 5, wherein the precursor grows by defect-induced deposition, and the prepared superfine nanowire has a diameter smaller than 5nm and is directionally arranged among the tubes of the carbon nanotubes to form the carbon nanotube composite film with an ordered structure.
7. The method for synthesizing superfine nanowire/carbon nanotube composite film by inter-tube confinement induction according to claim 1 or 5, wherein the method is characterized in that a low-pressure chemical vapor deposition method is adopted to synthesize superfine transition metal carbide nanowire of the inter-tube confinement, a metal organic matter is used as a precursor source under the negative pressure condition, a transition metal oxide cluster is deposited on the wall of the carbon nanotube containing defects at the decomposition temperature lower than the precursor source, the temperature is quickly increased to 700-1700 ℃ at the heating rate of 50-500 ℃/s, and CH is introduced 4 Carbonizing the nano-wires for 1 to 5 minutes by using a carbon source, and agglomerating the nano-wires in a limited space between the tubes to form ultrafine transition metal carbide nano-wires; wherein the transition metal carbide is Mo 2 C、W 2 C. One or more than two of TaC or Rec, the transition metal carbide/single-walled carbon nanotube composite film of the inter-tube confinement has excellent electrocatalytic hydrogen evolution performance.
8. The method for synthesizing the superfine nanowire/carbon nanotube composite film by the inter-tube confinement induction according to claim 1 or 5, which is characterized in that the superfine metal nanowire of the inter-tube confinement is synthesized by adopting a wet chemical method, acetylacetone metal salt is used as a precursor, a surfactant is added into oleylamine at 130-220 ℃ and heated for 1-300 min, and the superfine metal nanowire is generated among bundles of the carbon nanotube film; wherein the metal is one or more than two of Pt, pd, fe, co, ni, mo, ru, rh; the surfactant is one or more than two of didodecyl dimethyl ammonium bromide, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide and behenyl dimethyl ammonium bromide, and the inter-tube confinement superfine metal nanowire/single-wall carbon nanotube composite film has excellent interfacial water evaporation performance.
9. The method for synthesizing the superfine nanowire/carbon nanotube composite film by inter-tube confinement induction according to claim 1, wherein the superfine nanowire confinement is arranged among carbon nanotubes in a specific structural orientation and is widely applied to the fields of electrocatalytic total decomposition of water, thermal evaporation desalination of seawater, photo-thermal coupling catalysis or solar interfacial water evaporation.
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