CN114516636A - Method for preparing transition metal carbide nano array by using instantaneous high-temperature thermal shock carbon template - Google Patents

Method for preparing transition metal carbide nano array by using instantaneous high-temperature thermal shock carbon template Download PDF

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CN114516636A
CN114516636A CN202210237053.XA CN202210237053A CN114516636A CN 114516636 A CN114516636 A CN 114516636A CN 202210237053 A CN202210237053 A CN 202210237053A CN 114516636 A CN114516636 A CN 114516636A
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transition metal
nanosheets
nano
array
oxide film
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张永起
李晨
夏新辉
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Yangtze River Delta Research Institute of UESTC Huzhou
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/921—Titanium carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Abstract

The invention discloses a method for preparing a transition metal carbide nano array by using an instantaneous high-temperature thermal shock carbon template, which comprises the following steps of: (1) depositing Vertical Graphene (VG) nanosheets on the surface of the substrate to obtain VG nanosheets with an array structure; (2) carrying out hydrophilic treatment on the VG nanosheets with the array structures to obtain hydrophilic VG nanosheets; (3) depositing a nanometer transition metal oxide film on the surface of the hydrophilic VG nanosheet by taking a transition metal source and an oxygen source as precursors; (4) processing the transition metal oxide film loaded on the surface of the VG nanosheet by using an instantaneous high-temperature thermal shock technology to obtain a metal carbide with an array morphology; wherein the current is 0-20A, the voltage is 40-80V, and the processing time is 20-100 ms. The preparation method disclosed by the invention is extremely short in process flow, the material has unique hierarchy, higher specific surface area, controllable appearance and single component, and a large number of active sites can be exposed.

Description

Method for preparing transition metal carbide nano array by using instantaneous high-temperature thermal shock carbon template
Technical Field
The invention relates to preparation of a transition metal carbide nano material, in particular to a method for preparing a transition metal carbide nano array by using an instantaneous high-temperature thermal shock carbon template.
Background
Transition metal carbides are a class of materials that have high mechanical strength and hardness and are commonly used as cutting tools and drilling tools. This class of materials is an intermetallic packing compound formed by the insertion of carbon atoms into the crystal lattice of transition metals. The compound has the characteristics of covalent solid, ionic crystal and transition metal. Due to their unique physical, chemical and structural properties, transition metal carbides have been widely used in the fields of optics, electronics, and magnetics. In recent years, the high catalytic activity and selectivity of transition metal carbides have attracted much attention.
The catalytic reaction requires that the catalyst has higher specific surface area (more active sites are exposed) and proper micro morphology (product diffusion and transportation are facilitated), and the nano-array structure has the characteristics of unique hierarchy, high specific surface area, a large number of active sites, convenience in electron transfer and mass transfer, close interface contact and the like, and shows excellent catalytic activity, but the preparation of the transition metal carbide nano-array is a difficult point.
At present, the preparation method of the transition metal carbide nano material mainly comprises the following steps:
(1) traditional temperature programmed reduction-carbothermic process
The reaction mechanism is to directly carbonize the metal or metal oxide or metal salt. The method has the advantages of high reaction temperature, long heat treatment time, overhigh process energy consumption and difficult control of the shape and the size of the carbide.
(2) Template method
Researchers not only adopt artificially synthesized templates (such as carbon nanofibers, carbon nanotubes, graphene and carbon microspheres), but also adopt natural biomass templates (such as cotton, bamboo and other plants) and precursors of metal salts to carbonize in a high-temperature inert environment. The method can effectively control the structure size and the micro-morphology of the metal carbide, but still adopts the traditional high-temperature heat treatment mode, and the whole process needs longer time.
(3) Sol-gel process
The sol-gel method is mainly characterized in that a liquid chemical reagent or an inorganic substance (metal alkoxide) is used as a precursor, the precursor is uniformly mixed in a liquid phase, a stable and transparent sol system is formed through hydrolysis and condensation chemical reaction, the sol is aged and slowly polymerized to form gel with a three-dimensional structure, and the gel is finally dried and sintered to prepare the nano or sub-nano structure material. The method has the problems of high raw material cost, harmful organic solvent, short growth period and the like.
(4) Chemical vapor deposition method
The conventional chemical vapor deposition methods for preparing metal carbide include two methods, one is to use a carbon material as a substrate (e.g., carbon cloth) and a target metal oxide as a gas source and obtain the metal carbide by a chemical vapor deposition technique in a high temperature tube furnace, and the other is to use an oxide as a deposition substrate and a gas containing carbon elements (e.g., methane or acetone) as a gas source and obtain the metal carbide by a high temperature chemical vapor deposition reaction. The method has the disadvantages of high energy consumption due to the adoption of a high-temperature means.
Disclosure of Invention
Aiming at the prior art, the invention provides a method for preparing a transition metal carbide nano array by using an instantaneous high-temperature thermal impact carbon template, so as to solve the problems of long time, difficult control of material morphology, high cost and the like of the conventional preparation method.
In order to achieve the purpose, the invention adopts the technical scheme that: the method for preparing the transition metal carbide nano array by using the instantaneous high-temperature thermal shock carbon template comprises the following steps of:
(1) depositing vertical graphene nanosheets on the surface of the substrate to obtain VG nanosheets with an array structure;
(2) carrying out hydrophilic treatment on the VG nanosheets with the array structures to obtain hydrophilic VG nanosheets;
(3) Depositing a nanometer transition metal oxide film on the surface of the hydrophilic VG nanosheet by taking a transition metal source and an oxygen source as precursors;
(4) processing the transition metal oxide film loaded on the surface of the VG nanosheet by using an instantaneous high-temperature thermal shock technology to obtain a metal carbide with an array morphology; wherein the current is 0-20A, the voltage is 40-80V, and the processing time is 20-100 ms.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the deposition method in the step (1) is a plasma-assisted chemical vapor deposition method, and the process parameters are as follows: ar, H2And CH4The flow rates of the plasma deposition device are respectively 10-30, 5-15 and 1-13 sccm, the deposition time is 5-20 min, the temperature is 400-800 ℃, and the power of the plasma device is 300-900W.
Further, the hydrophilic treatment method in the step (2) is a plasma-assisted method, the treatment atmosphere is an air atmosphere, the treatment power is 15-50W, and the treatment time is 5-20 s.
Further, the oxygen source is deionized water.
Further, the nanometer transition metal oxide film is nanometer TiO2A film deposited by the steps of:
titanium tetraisopropoxide or titanium tetrachloride is used as a titanium source, deionized water is used as an oxygen source, the atomic layer deposition technology is utilized to deposit on VG nanosheets to obtain the nanometer titanium dioxide thin films, and the number of deposition cycles is 50-700.
Further, the nanometer transition metal oxide film is a nanometer molybdenum oxide film which is obtained by deposition through the following steps:
depositing on VG nanosheets by using molybdenum hexacarbonyl as a molybdenum source and deionized water as an oxygen source by utilizing an atomic layer deposition technology to obtain nano MoO3The number of deposition cycles used for the thin film is 50 to 700.
Further, the nanometer transition metal oxide film is a nanometer tungsten oxide film which is obtained by deposition through the following steps:
depositing the VG nanosheets by using the atomic layer deposition technology to obtain nano WO by using tungsten hexacarbonyl as a tungsten source and deionized water as an oxygen source3The number of deposition cycles used for the thin film is 50 to 700.
The invention has the beneficial effects that:
according to the method, firstly, a vertical graphene nanosheet with an open array structure is rapidly prepared by using a Plasma Enhanced Chemical Vapor Deposition (PECVD) technology, then, a nano oxide film with the thickness capable of being accurately regulated and controlled and excellent shape retention is deposited on the surface of the nanosheet by using an Atomic Layer Deposition (ALD) technology, and finally, the oxide and the graphene react by using an instantaneous high-temperature thermal shock technology to prepare the carbide material with the nanosheet array morphology.
The invention can control the height of the VG nanosheet by adjusting the growth process of VG, such as adjusting the deposition time, thereby controlling the morphology of the carbide. The transition metal carbide nano array is composed of nano sheets, the nano sheets are obvious in orientation and independent in structure, and an open pore structure is formed between the nano sheets, so that exposure of active sites is facilitated.
The preparation method of the invention has the advantages of short process flow, controllable material appearance and single component. The transition metal carbide nano array prepared by the invention has unique hierarchy and higher specific surface area, can expose a large number of active sites, and is often used as a catalyst.
Drawings
FIG. 1 is an XRD plot of TiC obtained in inventive example 1;
FIG. 2 is a diagram showing the morphology of a TiC nanosheet array obtained in example 1 of the present invention;
FIG. 3 shows ORR performance of TiC nanosheets obtained in example 1 of the present invention when used as a fuel cell;
FIG. 4 shows Mo obtained in example 3 of the present invention2C, the morphology of the nanosheet array;
FIG. 5 shows Mo obtained in example 3 of the present invention2The hydrogen evolution performance of the C nanosheet;
FIG. 6 shows the morphology of the WC nanosheet array obtained in example 4 of the present invention;
fig. 7 shows hydrogen evolution performance of the WC nanoplates obtained in example 4 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings.
Example 1
A method for preparing a titanium carbide nano array by using an instantaneous high-temperature thermal shock carbon template comprises the following steps:
(1) depositing vertical graphene nanosheets on the surface of the clean carbon cloth by using a plasma-assisted chemical vapor deposition method to obtain VG nanosheets with an array structure; the technological parameters are as follows: ar, H 2And CH4The flow rates of the deposition solution are respectively 20, 10 and 7sccm, the deposition time is 13min, the used temperature is 600 ℃, and the power of a plasma device is 600W;
(2) placing the VG nanosheets with the array structure in a quartz tube of plasma equipment for hydrophilic treatment, wherein the plasma treatment atmosphere is an air atmosphere, the treatment power is 30W, and the treatment time is 13s, so that hydrophilic VG nanosheets are obtained;
(3) with titanium tetraisopropoxide (Ti { OCH (CH))3)2) Depositing nano TiO on the surface of the hydrophilic VG nanosheet by using an atomic layer deposition technology and using deionized water as an oxygen source2A film, with a deposition cycle number of 350;
(4) processing nanometer TiO loaded on VG nanosheet surface by utilizing instantaneous high-temperature thermal shock technology2A film is formed to obtain titanium carbide with an array appearance; wherein the current is 10A, the voltage is 60V, and the processing time is 60 ms.
Example 2
A method for preparing a titanium carbide nano array by using an instantaneous high-temperature thermal shock carbon template comprises the following steps:
(1) depositing vertical graphene nanosheets on the surface of the clean carbon cloth by using a plasma-assisted chemical vapor deposition method to obtain VG nanosheets with an array structure; the technological parameters are as follows: ar, H2And CH4The flow rates of the deposition solution are respectively 15 sccm, 7sccm and 5sccm, the deposition time is 10min, the used temperature is 650 ℃, and the power of the plasma equipment is 700W;
(2) Placing VG nanosheets with array structures in a quartz tube of plasma equipment for hydrophilic treatment, wherein the plasma treatment atmosphere is air atmosphere, the treatment power is 20w, and the treatment time is 17s, so that hydrophilic VG nanosheets are obtained;
(3) with titanium tetrachloride (TiCl)4) Uses a titanium source and deionized water as oxygen sources, and utilizes an atomic layer deposition technology to deposit nano TiO on the surface of the hydrophilic VG nano-sheet2Film, cycle number of deposition used is 150;
(4) processing nanometer TiO loaded on VG nanosheet surface by utilizing instantaneous high-temperature thermal shock technology2A film is formed to obtain titanium carbide with an array appearance; whereinThe current was 5A, the voltage was 70V, and the treatment time was 80 ms.
Example 3
A method for preparing a molybdenum carbide nano array by using an instantaneous high-temperature thermal shock carbon template comprises the following steps:
(1) depositing vertical graphene nanosheets on the surface of the clean carbon cloth by using a plasma-assisted chemical vapor deposition method to obtain VG nanosheets with an array structure; the technological parameters are as follows: ar, H2And CH4The flow rates of the deposition solution are respectively 10 sccm, 10 sccm and 5sccm, the deposition time is 20min, the used temperature is 400 ℃, and the power of the plasma equipment is 300W;
(2) placing the VG nanosheets with the array structure in a quartz tube of plasma equipment for hydrophilic treatment, wherein the plasma treatment atmosphere is an air atmosphere, the treatment power is 15W, and the treatment time is 20s, so that hydrophilic VG nanosheets are obtained;
(3) By molybdenum hexacarbonyl (Mo (CO)6) Depositing nano MoO on the surface of the hydrophilic VG nanosheet by using an atomic layer deposition technology and using deionized water as an oxygen source3A film, deposited for a cycle number of 50;
(4) processing nanometer MoO loaded on VG nanosheet surface by utilizing instantaneous high-temperature thermal shock technology3A film is formed to obtain molybdenum carbide with an array appearance; wherein the current is 1A, the voltage is 80V, and the processing time is 100 ms.
Example 4
A method for preparing a tungsten carbide nano array by using a carbon template with instantaneous high temperature thermal shock comprises the following steps:
(1) depositing vertical graphene nanosheets on the surface of the clean carbon cloth by using a plasma-assisted chemical vapor deposition method to obtain VG nanosheets with an array structure; the technological parameters are as follows: ar, H2And CH4The flow rates of the deposition solution are respectively 30 sccm, 15 sccm and 13sccm, the deposition time is 5min, the used temperature is 800 ℃, and the power of a plasma device is 900W;
(2) placing the VG nanosheets with the array structure in a quartz tube of plasma equipment for hydrophilic treatment, wherein the plasma treatment atmosphere is air atmosphere, the treatment power is 50W, and the treatment time is 5s, so that hydrophilic VG nanosheets are obtained;
(3) with tungsten hexacarbonyl (W (CO)6) Depositing nano WO on the surface of the hydrophilic VG nanosheet by using an atomic layer deposition technology and taking tungsten source and deionized water as oxygen sources 3A film, the number of cycles of deposition used was 700;
(4) nano WO (WO) for processing VG nanosheet surface load by utilizing instantaneous high-temperature thermal shock technology3Forming a film to obtain tungsten carbide with an array appearance; wherein the current is 20A, the voltage is 40V, and the processing time is 20 ms.
As shown in fig. 1, the XRD profile of the sample obtained in example 1 shows that the obtained material has characteristic peaks typical of titanium carbide.
As shown in fig. 2, after the instantaneous high-temperature treatment, the original nanosheet structure of the graphene is not damaged, and the titanium carbide nanosheet array is successfully prepared.
As shown in fig. 4, after molybdenum oxide is deposited on the surface of the vertical graphene nanosheet, the molybdenum carbide obtained through joule heating treatment still maintains the morphology of the vertical nanosheet.
As shown in FIG. 5, when molybdenum carbide having an array structure was used in the hydrogen evolution reaction, the current density was 10mA/cm2The overpotential was 128 mV.
As shown in fig. 6, after tungsten oxide is deposited on the surface of the vertical graphene nanosheet, the tungsten carbide is obtained through joule heating treatment, and the tungsten carbide array is also composed of the vertical nanosheets.
As shown in FIG. 7, when tungsten carbide having an array structure was used in the hydrogen evolution reaction, the current density was 10mA/cm2The overpotential was 131 mV.
While the embodiments of the invention have been described in detail in connection with the drawings, the invention should not be construed as limited to the scope of the patent. Various modifications and changes may be made by those skilled in the art without inventive work within the scope of the appended claims.

Claims (7)

1. A method for preparing a transition metal carbide nano array by using a carbon template with instantaneous high-temperature thermal shock is characterized by comprising the following steps:
(1) depositing vertical graphene nanosheets on the surface of the substrate to obtain VG nanosheets with an array structure;
(2) carrying out hydrophilic treatment on the VG nanosheets with the array structures to obtain hydrophilic VG nanosheets;
(3) depositing a nanometer transition metal oxide film on the surface of the hydrophilic VG nanosheet by taking a transition metal source and an oxygen source as precursors;
(4) processing the transition metal oxide film loaded on the surface of the VG nanosheet by using an instantaneous high-temperature thermal shock technology to obtain a metal carbide with an array morphology; wherein the current is 0-20A, the voltage is 40-80V, and the processing time is 20-100 ms.
2. The method of claim 1, wherein: the deposition method in the step (1) is a plasma-assisted chemical vapor deposition method, and the process parameters are as follows: ar, H 2And CH4The flow rates of the plasma equipment are respectively 10-30, 5-15 and 1-13 sccm, the deposition time is 5-20 min, the used temperature is 400-800 ℃, and the power of the plasma equipment is 300-900W.
3. The method of claim 1, wherein: the hydrophilic treatment method in the step (2) is a plasma-assisted method, the treatment atmosphere is an air atmosphere, the treatment power is 15-50W, and the treatment time is 5-20 s.
4. The method of claim 1, wherein: the oxygen source is deionized water.
5. The method of claim 4, wherein the nano transition metal oxide thin film is nano TiO2A film deposited by the steps of:
titanium tetraisopropoxide or titanium tetrachloride is used as a titanium source, deionized water is used as an oxygen source, the atomic layer deposition technology is utilized to deposit on VG nanosheets to obtain the nanometer titanium dioxide thin films, and the number of deposition cycles is 50-700.
6. The method of claim 4, wherein the nano transition metal oxide film is a nano molybdenum oxide film deposited by the steps of:
depositing the nanometer MoO on the VG nanosheet by using the atomic layer deposition technology by using molybdenum hexacarbonyl as a molybdenum source and deionized water as an oxygen source 3The number of deposition cycles used for the thin film is 50 to 700.
7. The method of claim 4, wherein the nano transition metal oxide film is a nano tungsten oxide film deposited by the steps of:
depositing the VG nanosheets by using the atomic layer deposition technology to obtain nano WO by using tungsten hexacarbonyl as a tungsten source and deionized water as an oxygen source3The number of deposition cycles used for the thin film is 50 to 700.
CN202210237053.XA 2022-03-11 2022-03-11 Method for preparing transition metal carbide nano array by using instantaneous high-temperature thermal shock carbon template Pending CN114516636A (en)

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