CN117568759A - Method for preparing superfine metal nanocrystalline/nano carbon composite film in rapid and controllable manner - Google Patents
Method for preparing superfine metal nanocrystalline/nano carbon composite film in rapid and controllable manner Download PDFInfo
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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
- Y02E60/50—Fuel cells
Abstract
The invention relates to the controllable preparation field of nano materials, in particular to a method for rapidly and controllably preparing an ultrafine metal nanocrystalline/nano carbon composite film. Carrying metal nano particles on a nano carbon film by adopting physical deposition methods such as ion beam sputtering or magnetron sputtering, and the like, and rapidly heating and cooling (the temperature rise and fall rate is 100-300 ℃/s) in an inert atmosphere with positive pressure (0.01-0.2 MPa higher than standard atmospheric pressure) and trace oxygen (0.001-0.2% of oxygen volume fraction) to ensure that the metal nano particles form nano crystals with specific orientation, so as to obtain superfine (diameter < 3 nm) metal nano crystals (purity > 95%) which are monodisperse on the composite film of the nano carbon. The metal nanocrystalline with adjustable diameter and dispersity is obtained by adjusting the deposition condition and the temperature rising and falling rate of rapid heating and adjusting the dispersity and the size of the metal nano particles. Particularly on a single-wall carbon nano tube film, the nano crystal can form metal nano crystal with large length-diameter ratio by tube bundle induction.
Description
Technical Field
The invention relates to the controllable preparation field of nano materials, in particular to a method for rapidly and controllably preparing an ultrafine metal nanocrystalline/nano carbon composite film.
Background
The metal nanocrystals have nanoscale in which metal atoms are periodically arranged to form specific crystal planes. Nanocrystals of different structures have excellent optical, magnetic, mechanical, and electrical properties in their unique orientations. The crystal face size of the metal nanocrystalline is in the nanoscale, and the exposed specific orientation crystal face can be selectively adsorbed to different molecules, so that the metal nanocrystalline has great application prospects in the aspects of catalysis, sensing, bacteriostasis and the like.
In order to realize the controllable preparation of the metal nanocrystalline, researchers invented two main methods: (1) The physical method from top to bottom mainly comprises physical sputtering deposition, evaporation, ball milling, milling and the like. The method is to crush the block metal material into tiny particles, and then form metal nanocrystalline in the heat treatment process. (literature one: dhandc.; dwivedi, n.; loh, x.j.; jieYing, a.n.; verma, n.k.; beuerman, r.w.; lakshmarrayanan, r.; ramakrishana, s.rsc advance 2015,5 (127), 105003.; literature two: gonzalez-Martinez, i.g.; bachmateik, a.; bezugly, v.; kunstmann, j.; gemming, t.; liu, z.; cuniberti, g.; rummeli, m.h. Nanoscaled, 8 (22), 11340) the method can regulate the size and dispersion of the nanoparticles by varying the process parameters, has the advantages of strong controllability, good reproducibility, high uniformity, high efficiency, etc., but is not generally regular in the preparation of nanocrystals. (2) The chemical method from bottom to top mainly comprises electrochemical deposition, solvothermal synthesis, coprecipitation, sol-gel and the like. The method uses heat or electricity as driving force and uses a surfactant as a template to self-assemble metal ions or atoms to form metal nanocrystals. (literature three: tsung, c.k.; kuhn, j.n.; huang, w.y.; aliga, c.; hung, l.i.; somorjai, g.a.; yang, p.d. journal ofthe American Chemical Society, 131 (16), 5816.; literature four: xia, y.; gilroy, k.d.; peng, h.; c.; xia, x.angelwatte Chemie International Edition 2017,56 (1), 60.) this type of process allows for the control of crystal planes, sizes, and dispersion of metal nanocrystals by varying surfactant, reducing agent, heating temperature, metal precursor salt concentration, with very strong adjustability and compatibility. However, the method generally takes a long time, the size of the prepared nanocrystalline is larger (more than 10 nm), the structural uniformity of the nanocrystalline is poor, the surface of the nanocrystalline is coated by a surfactant, and the nanocrystalline in the solution needs to be dispersed on a carrier for use.
In conclusion, the metal nanocrystalline has excellent physicochemical properties and wide application prospect in the fields of sensing and catalysis, but the controllable preparation of the metal nanocrystalline still has a plurality of problems, such as: (1) The structural uniformity of the metal nanocrystals is poor and the surface is coated with a surfactant. (2) The size of the metal nanocrystalline is bigger and is not easy to regulate and control, and the nanocrystalline with the diameter smaller than 3nm is very difficult to prepare. (3) The preparation of the nanocrystalline is long in time consumption and low in synthesis efficiency, and the nanocrystalline still needs to be dispersed on a carrier in the subsequent use.
Disclosure of Invention
The invention aims to provide a method for preparing an ultrafine metal nanocrystalline/nano carbon composite film in a rapid controllable way, wherein monodisperse metal nano particles are deposited on a nano carbon carrier by a physical sputtering method, and the nano particles are reconstructed into monodisperse, small-size (less than 3 nm), high-structure uniformity (more than 95 percent) and clean-surface metal nanocrystalline through rapid temperature rise and fall. In particular, single-walled carbon nanotube films are used as substrates, and bundles of carbon nanotubes can induce metal nanocrystals to form ultrafine nanowires. The nano carbon film supported metal nano crystal composite film has high conductivity, large specific surface area and excellent mechanical property, and has wide application prospect in the fields of electrochemistry and the like.
The technical scheme of the invention is as follows:
a method for preparing ultra-fine metal nanocrystalline/nano carbon composite film rapidly and controllably, deposit metal nano particles on the nano carbon film by ion beam sputtering or magnetron sputtering of physical deposition method, rapidly heat and cool the nano particles in inert atmosphere containing trace oxygen with 0.01-0.2 MPa positive pressure and 0.001-0.2% oxygen volume fraction higher than standard atmospheric pressure, and the temperature rise and fall rate is 100-300 ℃/s, so that the metal nano particles form high-purity ultra-fine nanocrystalline with clean surface, and the composite film of the metal nano crystals monodisperse on the nano carbon film is obtained; the metal nano particles with adjustable density and size are obtained by regulating and controlling physical deposition conditions, so that the size and dispersity of the nano crystals are adjustable within a certain range.
The method for preparing the superfine metal nanocrystalline/nano carbon composite film can be controlled rapidly, and the nano carbon is carbon nano tube, graphene, graphite alkyne, nano carbon fiber, graphite or fullerene, and has good electric conduction, thermal conductivity and large specific surface area.
The method for preparing the superfine metal nanocrystalline/nano carbon composite film is characterized in that the used carbon nanotube film is composed of a high-crystallinity carbon nanotube network with G/D more than 50, and the carbon nanotubes are single-wall, double-wall or few-wall carbon nanotubes.
According to the method for preparing the superfine metal nanocrystalline/nano carbon composite film in a rapid controllable manner, metal nanocrystalline growth is induced on a single-wall carbon nanotube film by using a single-wall carbon nanotube bundle to form a superfine nanowire with a large length-diameter ratio, so that the metal nanocrystalline/nano carbon composite film with a unique structure is obtained; wherein, the length-diameter ratio of the superfine nanowire ranges from 1:1 to 5:1, and the diameter is less than 3nm.
According to the method for preparing the superfine metal nanocrystalline/nano carbon composite film, the nano carbon film carrying the metal nano particles can realize rapid temperature rise and fall, and the temperature rise rate and the temperature fall rate are both greater than 100 ℃/s.
The method for preparing the ultra-fine metal nanocrystalline/nano carbon composite film is characterized in that magnetron sputtering is adopted to deposit metal nano particles on the nano carbon film, the sputtering power is 1-50W, the deposition time is 10-500 s, the rapid heating temperature is 700-2200 ℃, the temperature rise and fall rate is 100-300 ℃/s, and the monodisperse metal nanocrystalline with adjustable size in the range of 2-10 nm is prepared, and the purity of the nanocrystalline is higher than 95%.
The method for preparing the ultra-fine metal nanocrystalline/nano carbon composite film can be controlled rapidly, improves the structural uniformity of nanocrystalline by one or more than two lifting heat treatments in positive pressure inert atmosphere, and has short time consumption and good controllability, and the inert atmosphere is high-purity Ar, he or N 2 。
The method for preparing the ultra-fine metal nanocrystalline/nano carbon composite film can be controlled rapidly, and the size and the dispersion degree of the nano particles are controlled by adjusting the physical deposition conditions of ion beam sputtering or magnetron sputtering, so that the preparation of the ultra-fine metal nanocrystalline with single dispersion and adjustable size is realized.
The method for preparing the superfine metal nanocrystalline/nano carbon composite film can be controlled rapidly, the prepared metal nanocrystalline and carbon have poor wettability and chemical reactivity, and the metal material is Au, ag, pt, pd or Ir.
The method for preparing the superfine metal nanocrystalline/nano carbon composite film is fast and controllable, the Pt cubic nanocrystalline/single-wall carbon nano tube composite film prepared by the method has excellent electrocatalytic performance, and the fully exposed (100) crystal face of the Pt cubic nanocrystalline shows excellent oxygen reduction and ammonia oxidation performance in an alkaline environment.
The design idea of the invention is as follows:
according to the invention, metal nano-particles are carried on the nano-carbon film through physical deposition, metal nano-crystals with specific morphology are formed through rapid heat treatment, the metal nano-crystals are directly dispersed on the nano-carbon film, the metal nano-particles are carried on the nano-carbon film through a top-down method, and the nano-particles are formed into nano-crystals with regular morphology by rapid temperature rise and drop, so that the nano-carbon composite film carrying superfine metal nano-crystals is obtained.
In addition, the metal nanocrystalline with adjustable diameter and dispersity is obtained by adjusting the deposition condition and the temperature rising and falling rate of rapid heating and adjusting the dispersity and the size of the metal nano particles. The single-wall carbon nanotube film is used as a substrate, and the tube bundles can induce the metal nanocrystalline to form nanowires with a certain length-diameter ratio.
The invention has the advantages and beneficial effects that:
1. the invention provides a method for preparing an ultrafine metal nanocrystalline/nano carbon composite film in a rapid controllable way, which is characterized in that after metal nano particles are loaded on the nano carbon film, the metal nanocrystalline with regular morphology is formed by rapid temperature rise and fall, the whole process can be completed within 1 minute, and the formed nanocrystalline has small size (less than 3 nm), high dispersity and clean surface.
2. The invention can regulate and control the components, the dispersity and the size of the nanocrystalline through a top-down physical deposition method, namely, the size and the dispersity of the prepared metal nanocrystalline are regulated and controlled through changing deposition conditions, and different kinds of metal nanocrystalline are obtained through adopting different component targets. The single-wall carbon nanotube film is used as a substrate, and the tube bundles can induce the metal nanocrystalline to form nanowires with a certain length-diameter ratio.
3. The method uses the nano carbon film with large specific surface area and high conductivity as a carrier, and the prepared metal nano crystal has high structural consistency (more than 95 percent) and can be directly used as a self-supporting electrocatalytic film electrode.
Drawings
FIG. 1 is a transmission electron microscope photograph of a Pt nanocrystalline/single-walled carbon nanotube composite film after magnetron sputtering.
FIG. 2 is a histogram of dimension statistics of (a) transmission electron micrographs and (b) Pt cubic nanocrystals of Pt cubic nanocrystalline/single-walled carbon nanotube composite films; (b) In the figure, the Particle size is the Particle size (nm) on the abscissa and Counts on the ordinate.
FIG. 3 is a graph showing that the composite film is 1 mol.L -1 Linear sweep voltammogram in KOH solution. In the figure, square represents Pt cubic nanocrystalline/single-walled carbon nanotube composite film, and circle represents Pt nanocrystalline/single-walled carbon nanotube composite film. The abscissa Potential represents the Potential (V ver. Rhe),the ordinate Current density represents the Current density (mA cm) -2 ). The scanning range is 0.2V-1.0V.
FIG. 4 is a transmission electron micrograph of a Pt ultrafine nanocrystalline/single-walled carbon nanotube composite film with a large aspect ratio.
FIG. 5 is a schematic view of a composite film containing 0.1 mol.L -1 NH 3 And 1 mol.L -1 Cyclic voltammogram in KOH mixed solution. In the figure, square represents Pd cubic nanocrystalline/carbon nanofiber composite film, and circle represents Pd nanocrystalline/carbon nanofiber composite film. The abscissa Potential represents the Potential (V ver. RHE), and the ordinate Current density represents the Current density (mA cm) -2 ). Scanning range is-1.0V-0V.
FIG. 6 composite film at 1 mol.L -1 Linear sweep voltammogram in KOH solution. In the figure, square represents Pt cubic nanocrystalline/graphite alkyne composite film, and circle represents Pt nanocrystalline/graphite alkyne composite film. The abscissa Potential represents the Potential (V ver. RHE), and the ordinate Current density represents the Current density (mA cm) -2 ). Scanning range is-1.4V-0V.
Fig. 7 is a transmission electron microscope photograph of a Pt nanoparticle/single-walled carbon nanotube composite film prepared by ordinary temperature ramp-down.
FIG. 8 is a transmission electron micrograph of a Pt nanoparticle/SiN composite film.
Detailed Description
In the specific implementation process, the invention adopts physical deposition methods such as magnetron sputtering or ion beam sputtering and the like to deposit metal nano particles on the nano carbon film; different metal targets are bombarded by magnetron/ion beam sputtering, and metal nano particles with different sizes and densities are prepared by regulating and controlling sputtering power and deposition time. Under the conditions of rapid heating and cooling (the temperature rising and falling rate is 100-300 ℃/s) in an inert atmosphere with positive pressure (0.01-0.2 MPa higher than standard atmospheric pressure) and trace oxygen (the oxygen volume fraction is 0.001-0.2%), the metal nano-particles form nano-crystals with specific morphology and specific orientation, and the metal nano-crystal/nano-carbon composite film is obtained. The structure of the composite film is characterized and the performances of oxygen reduction, electrochemical ammoxidation and the like are tested.
The invention is further illustrated by the following examples.
Example 1
In this embodiment, the preparation of the Pt cubic nanocrystalline/single-walled carbon nanotube composite film comprises the following specific experimental steps:
(1) Deposition of metal nanoparticles
Placing the single-wall carbon nanotube film in a magnetron sputtering cavity, and vacuumizing to the air pressure of 1.0×10 -5 Pa, heating to 100deg.C, sputtering Pt, igniting at 20Torr, rotating at 10rpm, coating at 5Torr with power of 10W, coating for 500s, placing the thin film (figure 1) after sputter depositing metal in a rapid thermal device, mixing with 0.1% O at 0.13MPa positive pressure and 99.9% He gas volume fraction 2 In the inert atmosphere, the temperature is increased and decreased to 950 ℃ within 20 seconds, and the Pt cubic nano-crystal/single-wall carbon nano-tube composite film is obtained.
(2) Characterization of the Structure of composite films
Placing the Pt cubic nano-crystal/single-wall carbon nano-tube composite film prepared in the step (1) into absolute ethyl alcohol, carrying out ultrasonic treatment for 10min, then using a liquid-transferring gun to drop the absolute ethyl alcohol with the Pt cubic nano-crystal/single-wall carbon nano-tube onto a micro grid, drying, and observing under a transmission electron microscope, wherein the appearance and the size distribution condition are shown as figure 2, the appearance of the Pt cubic nano-crystal is rectangular or square, and the radial size of the short side is smaller than 3nm.
(3) Performance test of composite films
Placing the Pt cubic nanocrystalline/single-walled carbon nanotube composite film prepared in the step (1) into an electrode clamp to serve as a working electrode, wherein a carbon rod serves as a counter electrode, and a silver/silver chloride electrode serves as a reference electrode and is placed in a range of 1 mol.L -1 Testing of Linear sweep voltammograms in Mixed solution of KOH (sweep Rate 5 mV.s -1 ) Oxygen is firstly introduced into the electrolyte for 10min, the reduction capacity of the oxygen is shown as figure 3, and the half-wave potential of the Pt cubic nano-crystal/single-wall carbon nano-tube composite film is 153mV higher than that of the Pt nano-particle/single-wall carbon nano-tube composite film.
Example 2
In this embodiment, the preparation of the Pt ultrafine nanowire/single-walled carbon nanotube composite film comprises the following specific experimental steps:
(1) Deposition of metal nanoparticles
Unlike step (1) of example 1, the thin film after sputter deposition of the metal was placed in a rapid thermal apparatus, and mixed with 0.1% O by a positive pressure of 0.2MPa and a volume fraction of 99.9% He gas 2 In the inert atmosphere of (2), 5 times of 1000 ℃ temperature rise and fall are completed within 30 seconds, and the Pt superfine nanowire/single-walled carbon nanotube composite film is obtained; wherein, the length-diameter ratio of the superfine nanowire ranges from 1:1 to 5:1, and the diameter is less than 3nm.
(2) Characterization of the Structure of composite films
Placing the Pt superfine nanowire/single-walled carbon nanotube composite film prepared in the step (1) into absolute ethyl alcohol, carrying out ultrasonic treatment for 10min, then using a pipette gun to drop the absolute ethyl alcohol with the Pt cubic nanowire/single-walled carbon nanotube onto a micro grid, drying, and observing under a transmission electron microscope, wherein the appearance and the size distribution situation are shown in figure 4, the appearance of the Pt cubic nanowire is rectangular, and the short side size is smaller than 3nm.
(3) Performance test of composite films
The same as in step (3) of example 1. The half-wave potential of the Pt superfine nanowire/single-wall carbon nanotube composite film is improved by 10mV compared with that of the Pt cubic nanocrystal/single-wall carbon nanotube composite film.
Example 3
In this embodiment, the preparation of the Pd cubic nanocrystalline/carbon nanofiber composite film comprises the following specific experimental steps:
(1) Deposition of metal nanoparticles
The carbon nanofiber film is placed in an ion beam sputtering coating machine, the ion beam pressure is set to 1250V, the ion beam current is 600mA, the acceleration voltage is 300V, E/B is 125%, the argon flow of an ion source is 18sccm, the argon flow of a neutralizer is 8sccm, the oxygen flow is 30sccm, and the substrate temperature is 200 ℃. Putting the sputtered film into a quick heating device, and mixing 0.001% O with Ar gas with volume fraction of 99.999% under positive pressure of 0.12MPa 2 The temperature is increased and decreased by 1025 ℃ in 20s under the inert atmosphere, and the Pd nanocrystalline/carbon nanofiber composite film is obtained.
(2) Characterization of the structure of the composite film.
The Pd cubic nanocrystals obtained were all regular rectangles with short side radial dimensions of 3nm, as in step (2) of example 1.
(3) Performance test of composite films
Placing the Pd cubic nanocrystalline/carbon nanofiber composite film prepared in the step (1) into an electrode clamp to serve as a working electrode, wherein a Pt electrode serves as a counter electrode, and a saturated calomel electrode serves as a reference electrode and is placed in a range of 0.2 mol.L -1 NH 3 And 1 mol.L -1 Cyclic voltammetric scans (scan rate 5 mV.s) were performed in a mixed solution of KOH -1 ) The electrocatalytic oxidation activity of the test sample on ammonia in alkaline medium (figure 5) is improved by 5.2 times compared with the anodic oxidation peak of the Pd cubic nanocrystalline/nano carbon fiber composite film.
Example 4
In this embodiment, the preparation of Pt cubic nanocrystalline/graphite alkyne composite films with different sizes comprises the following specific experimental steps:
(1) Deposition of metal nanoparticles
Placing graphite alkyne film in ion beam sputtering equipment, vacuumizing to air pressure of 3×10 -4 At Pa, the current was set to 20A and the voltage to 15V, and Pt nanoparticle sputtering was performed. Putting the film sputtered by the ion beam into a quick heating device, and keeping the volume fraction of the film to be 99.9% N under the positive pressure of 0.17MPa 2 Gas mixing 0.1% O 2 The temperature is raised and lowered at 1750 ℃ within 20 seconds under the inert atmosphere, and the process is repeated for 10 times, so that the Pt cubic nanocrystalline/graphite alkyne composite film is obtained.
(2) Characterization of the Structure of composite films
The Pt cubic nanocrystals were obtained in the same shape as in step (2) of example 1, with regular rectangles or squares, and with a short side radial dimension of 3nm.
(3) Performance test of composite films
Placing the Pt cubic nanocrystalline/graphite alkyne composite film prepared in the step (1) into an electrode clamp, wherein the electrode clamp is a working electrode, a carbon rod is a counter electrode, and a silver/silver chloride electrode is a reference electrode and is placed in 1 mol.L -1 Testing of linear sweep voltammograms (sweeps) in a mixed solution of KOHAt a rate of 5 mV.s -1 ) To characterize the ability of the samples to evolve hydrogen in alkaline medium (FIG. 6), current density 200mA cm -2 When the Pt cubic nanocrystalline/graphite alkyne composite film is used, the overpotential is-649 mV, which is smaller than the overpotential-694 mV of the Pt nanoparticle/graphite alkyne composite film.
Comparative example 1
The Pt nano particle/single-wall carbon nano tube composite film is prepared by common lifting heat treatment, and the specific experimental steps are as follows:
(1) Deposition of metal nanoparticles
Unlike step (1) in example 1, the thin film after the sputtering was put into a common tube furnace, and placed in an inert atmosphere to complete the temperature rise and fall of 1100 ℃ within 1 hour, thereby obtaining the Pt nanoparticle/single-walled carbon nanotube composite thin film.
(2) Characterization of the Structure of composite films
As in step (2) of example 1, the transmission electron microscope showed that its structure is as shown in FIG. 7, the nanoparticle size is significantly larger, and there is no regular morphology.
(3) Performance test of composite films
The same as in step (3) of example 1. The initial potential of the Pt nano particle/single-wall carbon nano tube composite film is obviously higher than that of the Pt cubic nano crystal/single-wall carbon nano tube composite film, and the half-wave potential is improved by a plurality of times.
Comparative example 2
The preparation method of the Pt nano particle/SiN composite film by taking SiN as a carrier comprises the following specific steps:
(1) Deposition of metal nanoparticles
Unlike step (1) in example 1, the substrate was a SiN film.
(2) Characterization of the Structure of composite films
As in step (2) of example 1, the structure is as shown in fig. 8, the nanoparticle size is significantly larger, and there is no regular morphology.
(3) Performance test of composite films
As in step (3) in example 1, the Pt nanoparticle/SiN composite film onset potential became significantly higher, and the half-wave potential was increased several times.
The results of examples and comparative examples show that metal nanocrystals prepared on nanocarbon films at rapid elevated temperatures have smaller dimensions, higher densities and higher structural uniformity. Compared with the prior art, the invention has the greatest characteristics that: the metal nano-particles loaded on the nano-carbon network are rapidly heated and cooled (the temperature rising and falling rate is 100-300 ℃/s) in an inert atmosphere with positive pressure (0.1-0.2 MPa higher than standard atmospheric pressure) and trace oxygen (0.001-0.2% of oxygen volume fraction) to form the metal nano-crystal composite film with regular morphology, and the preparation of the nano-carbon film loaded metal nano-crystal composite film is rapidly controllable. The metal nanocrystalline prepared by the method has high orientation consistency (purity is more than 95 percent), clean surface and wide application prospect in the fields of photo-thermal catalysis, energy storage and conversion, sensing and monitoring and the like, and is directly supported on a nano carbon film with high specific surface area, high electric conductivity and high heat conduction.
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 (10)
1. A method for preparing an ultrafine metal nanocrystalline/nano carbon composite film in a rapid controllable manner is characterized in that metal nano particles are deposited on the nano carbon film by ion beam sputtering or magnetron sputtering of a physical deposition method, and are rapidly heated and cooled in an inert atmosphere which is 0.01-0.2 MPa positive pressure and 0.001-0.2% oxygen volume fraction and contains trace oxygen above standard atmospheric pressure, wherein the lifting temperature rate is 100-300 ℃/s, so that the metal nano particles form high-purity ultrafine surface clean nanocrystalline, and the composite film of the metal nano crystals which are monodisperse on the nano carbon film is obtained; the metal nano particles with adjustable density and size are obtained by regulating and controlling physical deposition conditions, so that the size and dispersity of the nano crystals are adjustable within a certain range.
2. The method for preparing the ultra-fine metal nanocrystalline/nano carbon composite film according to claim 1, wherein the nano carbon is carbon nanotube, graphene, graphite alkyne, nano carbon fiber, graphite or fullerene, and has good electric conduction, thermal conductivity and large specific surface area.
3. The method for preparing the ultra-fine metal nanocrystalline/carbon nano composite film according to claim 2, wherein the carbon nanotube film is composed of a network of high crystalline carbon nanotubes with G/D > 50, and the carbon nanotubes are single-walled, double-walled or few-walled carbon nanotubes.
4. The method for preparing the superfine metal nanocrystalline/nano carbon composite film in a rapid and controllable manner according to claim 3, wherein the metal nanocrystalline is induced to grow by a single-wall carbon nanotube bundle on the single-wall carbon nanotube film to form a superfine nanowire with a large length-diameter ratio, so as to obtain the metal nanocrystalline/nano carbon composite film with a unique structure; wherein, the length-diameter ratio of the superfine nanowire ranges from 1:1 to 5:1, and the diameter is less than 3nm.
5. The method for preparing the ultra-fine metal nanocrystalline/nano carbon composite film according to claim 1, wherein the nano carbon film carrying the metal nano particles realizes rapid temperature rise and fall, and the temperature rise rate and the temperature fall rate are both more than 100 ℃/s.
6. The method for preparing the ultra-fine metal nanocrystalline/nano carbon composite film according to claim 1, wherein the metal nano particles are deposited on the nano carbon film by magnetron sputtering, the sputtering power is 1-50W, the deposition time is 10-500 s, the rapid heating temperature is 700-2200 ℃, the temperature rise and fall rate is 100-300 ℃/s, the monodisperse metal nanocrystalline with adjustable size in the range of 2-10 nm is prepared, and the purity of the nanocrystalline is higher than 95%.
7. According to claim 1 or 6The method for preparing the superfine metal nanocrystalline/nano carbon composite film is characterized in that the structural uniformity of nanocrystalline is improved through one or more than two lifting heat treatments in a positive pressure inert atmosphere, the time consumption is short, the controllability is good, and the inert atmosphere is high-purity Ar, he or N 2 。
8. The method for preparing the ultra-fine metal nanocrystalline/carbon composite film according to claim 1, wherein the size and the dispersion degree of the nano particles are controlled by adjusting the physical deposition conditions of ion beam sputtering or magnetron sputtering, so as to realize the preparation of the ultra-fine metal nanocrystalline with single dispersion and adjustable size.
9. A method for the rapid and controllable preparation of ultra-fine metallic nanocrystalline/nanocarbon composite films according to claim 1 or 3, characterized in that the metallic nanocrystalline prepared has poor wettability and chemical reactivity with carbon, and the metallic material thereof is Au, ag, pt, pd or Ir.
10. The method for preparing the superfine metal nanocrystalline/nano carbon composite film in a rapid and controllable manner according to claim 1 or 3, wherein the Pt cubic nanocrystalline/single-walled carbon nanotube composite film prepared by the method has excellent electrocatalytic performance, and the (100) crystal face of the Pt cubic nanocrystalline is fully exposed so as to show excellent oxygen reduction and ammoxidation performances in an alkaline environment.
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