CN114455586A - W-shaped steel plate2Rapid preparation method of C nanoparticles - Google Patents
W-shaped steel plate2Rapid preparation method of C nanoparticles Download PDFInfo
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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
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a W2A rapid preparation method of C nano particles. The method uses joule heat high temperature generated by electrifying a Carbon Nano Tube Film (CNTF) to evaporate tungsten powder, and loads tungsten oxide (WOx) on the surface of the film; further rapidly reducing WOx by in-situ Joule heat in a manner of consuming framework carbon to prepare W2And C, nano-particles. The invention replaces the traditional resistance type and sputtering type coating process and the W-phase method and the like with the joule heat generated by electrifying the CNTF with the characteristics of rapid temperature rise and drop2C synthesis mode, the method has the characteristics of low cost, low energy consumption and high efficiency, and can particularly realize W in a plurality of seconds2The ultra-fast preparation of the C nano-particles has important commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to an ultra-fast preparation method of ditungsten carbide nano particles.
Background
W2C has the characteristics of high melting point, good thermal conductivity, excellent mechanical property and the like. The catalyst has wide application in the fields of material processing, aerospace and catalysis. Wherein in the aspects of electrocatalytic hydrogen evolution, hydrogen production and the like, W2The catalytic yield of C being in non-noble metal catalystsSuperior ones; meanwhile, the catalyst has the advantage of being not easily poisoned by CO and the like, and shows great potential for replacing noble metal catalysts such as Pt and Ru.
In view of the above advantages, many researchers strive to explore W2The C nano-particles are synthesized by a high-efficiency method, but are generally limited to the traditional vapor deposition synthesis. For example, Xia et al reported a method for vapor deposition synthesis of Tunable carbon nanotube-tungsten carbide nanoparticle heterostructures (Xia, et al, Tunable carbon nanotubes-Tunable carbon nanoparticles by vapor deposition. Journal of Applied Physics, 2014, 115 (18)). The method firstly uses 0.5gW (CO)6The powder was loaded into the bottom of an alumina crucible and covered with 0.034g of purified alpha-CNTs, and the crucible was then covered. Prior to deposition, the furnace was vacuum cleaned and high purity hydrogen gas was introduced at a rate of 400 sccm (standard cubic centimeters per minute). The deposition temperature was raised to 400 and 900 ℃ at 5 ℃/min, respectively, and allowed to warm for 1h and then cooled to room temperature. Annealing at 2200 deg.C under argon atmosphere for 30 min to obtain W2C. Although this approach uniformly loads W on CNTs2C nano-particles, but certain impurities such as WC and the like are mixed, the time consumption is long, the energy consumption is high, the efficiency is low, hydrogen is required in an experiment, and the danger of the preparation process is increased. In addition, Takafumi et al reported a single step synthesis of W2Method for C nanoparticles (Takafumi, et al, Single-step Synthesis of W)2C nanoparticie-discrete carbon electrolytes for hydrogen evolution reactions groups on carbon images sites, ACS omega, 2016, 1 (4)). They developed the selective synthesis of W from phosphotungstic acid2C, one-step scheme of nano particles. This process compares to W before2The synthesis method of the C nano-particles is simple and convenient, but the synthesis process still needs hours of high-temperature calcination treatment, and has large energy consumption and low efficiency. In addition, the process utilizes a mechanism for selective synthesis, W2The presence of phase C is not stable.
Disclosure of Invention
The invention provides a W for solving the problem of a short plate in the prior art2A rapid preparation method of C nano-particles.
The invention solves the technical problems by the following scheme:
w2The rapid preparation method of the C nano-particles comprises the steps of carrying out WOx loading on one carbon nano-tube film by using Joule heat generated by electrifying the other carbon nano-tube film, and then rapidly reducing WOx in situ by using the Joule heat high temperature of CNTF and taking a carbon skeleton of the CNTF as a carbon source to prepare the target W nano-particles2And C, nano-particles.
Wherein the joule heat source includes but is not limited to carbon nanotube film, and may also be film or fabric of graphene, carbon nanofiber.
W2The rapid preparation method of the C nano-particles comprises the following steps:
(1) pretreatment of the carbon nanotube film: cutting a carbon nanotube film with a thickness of 20 μm and a specification of 2 × 4cm, and soaking with concentrated hydrochloric acid for 6h to remove metal impurities such as catalyst;
(2) loading of WOx particles: uniformly dispersing tungsten powder in absolute ethyl alcohol, and then performing suction filtration on the carbon nanotube film to obtain CNTF deposited with a tungsten powder layer; and then the tungsten-containing powder of the CNTF is faced upwards, two ends of the CNTF are stuck on a sample frame in a joule heating furnace by utilizing conductive silver adhesive, and another CNTF with the same thickness specification is placed on the CNTF at intervals. Further pumping the furnace chamber to a certain vacuum degree and connecting a direct current power supply. By controlling the voltage and the electrifying time, the tungsten powder on the upper surface of the lower CNTF is partially evaporated and oxidized and is deposited on the lower surface of the upper CNTF.
（3）W2Rapid joule heating preparation of C nanoparticles: coating a layer of PVP solution on the surface of the CNTF loaded with the WOx particles, drying in a forced air drying oven, and taking out; the two ends of the sample holder are adhered to a sample holder in a joule heating furnace by using conductive silver adhesive, and the furnace chamber is pumped to a certain vacuum degree. By controlling the voltage and the power-on time, the target W is prepared by quickly reducing WOx by utilizing the Joule heat of the CNTF2And C, nano-particles.
Wherein, the oxidation and evaporation temperature in the step (2) is 700-1000 ℃.
As a preferred techniqueThe scheme is that the specific flow of the step (2) is as follows: uniformly dispersing 0.2g of tungsten powder in 20ml of absolute ethyl alcohol, performing ultrasonic treatment for 10 minutes, taking 2ml of the solution, and performing suction filtration on a carbon nanotube film to obtain CNTF uniformly coated with the tungsten powder; and then, the surface of the CNTF containing tungsten powder faces upwards, two ends of the CNTF are stuck on a sample frame in a joule heating furnace by utilizing conductive silver adhesive, and a CNTF with the same thickness specification is placed on the CNTF at a position 5mm away from the CNTF. Further evacuating the oven cavity to 10-1Pa vacuum degree, and connecting a direct current power supply to two ends of the CNTF. At a constant pressure of 13V, the CNTF surface reached 800 ℃. The tungsten powder on the upper surface of the lower layer CNTF is partially oxidized by maintaining the constant pressure for 1s, and WOx particles are rapidly evaporated to the lower surface of the upper layer CNTF.
As a preferred technical scheme, the specific flow of the step (2) is as follows: uniformly dispersing 0.2g of tungsten powder in 20ml of absolute ethyl alcohol, performing ultrasonic treatment for 10 minutes, taking 2ml of the solution, and performing suction filtration on a carbon nanotube film to obtain CNTF uniformly coated with the tungsten powder; and then, the surface of the CNTF containing tungsten powder faces upwards, two ends of the CNTF are stuck on a sample frame in a joule heating furnace by utilizing conductive silver adhesive, and a CNTF with the same thickness specification is placed on the CNTF at a position 5mm away from the CNTF. Further evacuating the oven cavity to 10-1Pa vacuum degree, and connecting a direct current power supply to two ends of the CNTF. At a constant pressure of 14V, the CNTF surface reached 850 ℃. The tungsten powder on the upper surface of the lower layer CNTF is partially oxidized by keeping the constant pressure for 1s, and WOx particles are uniformly evaporated on the lower surface of the upper layer CNTF.
Wherein, the specific flow of the step (3) is as follows: 0.2g of PVP was added to 20ml of ethanol, dissolved by ultrasound and dispersed for 1 h. The surface of the CNTF loaded with WOx is uniformly coated with 1ml of the PVP-ethanol solution, and then dried in a forced air drying oven at 60 ℃ for 0.5 h. Further adhering two ends of the film to a sample holder in a Joule heating furnace by using conductive silver adhesive, and pumping the furnace chamber to 10 deg.C-2Pa vacuum degree and connecting a direct current power supply. At a constant pressure of 35V, the surface of CNTF reaches 1100 ℃. At the moment, the skeleton carbon and PVP of the CNTF synergistically reduce WOx to obtain target W uniformly distributed on the surface of the CNTF2And C, nano-particles.
The beneficial techniques that can be realized by the present invention include at least: the Joule is generated by electrifying the CNTF with the characteristics of rapid temperature rise and dropHeat replaces the traditional resistance type, sputtering type coating process, liquid phase method and other W2C synthesis mode, the method has the characteristics of low cost, low energy consumption and high efficiency, and can particularly realize W in a plurality of seconds2The ultra-fast preparation of the C nano-particles has important commercial application prospect.
Drawings
FIG. 1 is a diagram illustrating the preparation of nano-W on the surface of a carbon nanotube film by using ultra-fast Joule thermal temperature response in the present invention2And C, a process schematic diagram.
FIG. 2 shows the nano-W produced on the surface of the carbon nanotube film in example 1 of the present invention2C scanning electron micrograph.
FIG. 3 shows the nano-W produced on the surface of the carbon nanotube film in example 1 of the present invention2C scanning electron micrograph.
FIG. 4 shows the nano-W produced on the surface of the carbon nanotube film in example 1 of the present invention2X-ray diffraction pattern of C.
FIG. 5 shows the nano-W produced on the surface of the carbon nanotube film in example 1 of the present invention2And (3) transmission electron microscope images of the C particles.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is obvious that the described embodiments are only a few examples of the invention, not all examples. Other embodiments, which can be obtained by one skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
W2The method for rapidly preparing the C nano-particles comprises the steps of firstly utilizing Joule heat generated by electrifying the carbon nano-tube film to load the WOx on the carbon nano-tube film, continuously utilizing the Joule heat high temperature of the film to rapidly reduce the WOx in situ, and then preparing a target W on the surface of the carbon nano-tube film2And C, nano-particles.
W2The rapid preparation method of the C nano-particles specifically comprises the following steps:
a carbon nanotube film with a thickness of 20 μm and a size of 2 × 4cm is cut, and immersed in concentrated hydrochloric acid for 6h to remove metal impurities such as contained catalyst.
Further, 0.2g of tungsten powder is uniformly dispersed in 20ml of absolute ethyl alcohol, ultrasonic treatment is carried out for 10 minutes, 2ml of the solution is taken and filtered onto a carbon nano tube film, and the CNTF uniformly coated with the tungsten powder is obtained; and then, the surface of the CNTF containing tungsten powder faces upwards, two ends of the CNTF are stuck on a sample frame in a joule heating furnace by utilizing conductive silver adhesive, and a CNTF with the same thickness specification is placed on the CNTF at a position 5mm away from the CNTF. Further evacuating the oven cavity to 10-1Pa vacuum degree, and connecting a direct current power supply to two ends of the CNTF. At a constant pressure of 12V, the CNTF surface reached 750 ℃. The tungsten powder on the upper surface of the lower layer CNTF is partially oxidized by keeping the constant pressure for 1s, and WOx particles are uniformly evaporated on the lower surface of the upper layer CNTF.
Further, 0.2g of pvp was added to 20ml of ethanol, dissolved with ultrasound and dispersed for 1 hour. The surface of the CNTF loaded with WOx is uniformly coated with 1ml of the PVP-ethanol solution, and then dried in a forced air drying oven at 60 ℃ for 0.5 h. Further adhering two ends of the film to a sample holder in a Joule heating furnace by using conductive silver adhesive, and pumping the furnace chamber to 10 deg.C-2Pa vacuum degree and connecting a direct current power supply. Under the constant pressure of 32V, the surface of the CNTF reaches 1000 ℃, at the moment, the skeleton carbon and PVP of the CNTF are subjected to co-reduction of WOx, and the target W uniformly distributed on the surface of the CNTF is obtained2And C, nano-particles.
Example 2
W2The method for rapidly preparing the C nano-particles comprises the steps of firstly utilizing Joule heat generated by electrifying the carbon nano-tube film to load the WOx on the carbon nano-tube film, continuously utilizing the Joule heat high temperature of the film to rapidly reduce the WOx in situ, and then preparing a target W on the surface of the carbon nano-tube film2And C, nano-particles.
W2The rapid preparation method of the C nano-particles specifically comprises the following steps:
a carbon nanotube film with a thickness of 20 μm and a size of 2 × 4cm is cut, and immersed in concentrated hydrochloric acid for 6h to remove metal impurities such as contained catalyst.
Further, 0.2g of tungsten powder was addedUniformly dispersing in 20ml of absolute ethyl alcohol, performing ultrasonic treatment for 10 minutes, taking 2ml of the solution, and performing suction filtration on the solution to obtain CNTF uniformly coated with tungsten powder; and then, the surface of the CNTF containing tungsten powder faces upwards, two ends of the CNTF are stuck on a sample frame in a joule heating furnace by utilizing conductive silver adhesive, and a CNTF with the same thickness specification is placed on the CNTF at a position 5mm away from the CNTF. Further evacuating the oven cavity to 10-1Pa vacuum degree, and connecting a direct current power supply to two ends of the CNTF. At a constant pressure of 13V, the CNTF surface reached 800 ℃. The tungsten powder on the upper surface of the lower layer CNTF is partially oxidized by maintaining the constant pressure for 1s, and WOx particles are rapidly evaporated to the lower surface of the upper layer CNTF.
Further, 0.2g of pvp was added to 20ml of ethanol, dissolved with ultrasound and dispersed for 1 hour. The surface of the CNTF loaded with WOx is uniformly coated with 1ml of the PVP-ethanol solution, and then dried in a forced air drying oven at 60 ℃ for 0.5 h. Further using conductive silver adhesive to stick the two ends of the film on the sample rack in the joule heating furnace, pumping the furnace chamber to 10-2Pa vacuum degree and connecting a direct current power supply. At a constant pressure of 35V, the surface of CNTF reaches 1100 ℃. At the moment, the skeleton carbon and PVP of the CNTF are reduced to WOx together to obtain the target W uniformly distributed on the surface of the CNTF2And C, nano-particles.
Example 3
W2A rapid preparation method of C nano-particles. The method utilizes joule heat generated by electrifying the carbon nanotube film to load the WOx on the carbon nanotube film, continues to utilize the joule heat high temperature of the film to quickly reduce the WOx in situ, and then prepares a target W on the surface of the carbon nanotube film2And C, nano-particles.
W2The rapid preparation method of the C nano-particles specifically comprises the following steps:
a carbon nanotube film with a thickness of 20 μm and a size of 2 × 4cm is cut, and immersed in concentrated hydrochloric acid for 6h to remove metal impurities such as contained catalyst.
Further, 0.2g of tungsten powder is uniformly dispersed in 20ml of absolute ethyl alcohol, ultrasonic treatment is carried out for 10 minutes, 2ml of the solution is taken and filtered onto a carbon nano tube film, and the CNTF uniformly coated with the tungsten powder is obtained; then the surface of the CNTF containing tungsten powder faces upwards, and conductive silver is utilizedThe glue was glued at both ends to a sample holder in a joule oven and a piece of CNTF of the same thickness gauge was placed thereon at a distance of 5 mm. Further evacuating the oven cavity to 10-1Pa vacuum degree, and connecting a direct current power supply to two ends of the CNTF. At a constant pressure of 14V, the CNTF surface reached 850 ℃. The tungsten powder on the upper surface of the lower layer CNTF is partially oxidized by maintaining the constant pressure for 1s, and WOx particles are rapidly evaporated to the lower surface of the upper layer CNTF.
Further, 0.2g of pvp was added to 20ml of ethanol, dissolved with ultrasound and dispersed for 1 hour. The surface of the CNTF loaded with WOx is uniformly coated with 1ml of the PVP-ethanol solution, and then dried in a forced air drying oven at 60 ℃ for 0.5 h. Further adhering two ends of the film to a sample holder in a Joule heating furnace by using conductive silver adhesive, and pumping the furnace chamber to 10 deg.C-2Pa vacuum degree and connecting a direct current power supply. At a constant pressure of 46V, the surface of CNTF reached 1300 ℃. At the moment, the skeleton carbon and PVP of the CNTF are reduced to WOx together to obtain the target W uniformly distributed on the surface of the CNTF2And C, nano-particles.
Relative to the other W2C nano-particle preparation method, W of the invention2The rapid preparation method of the C nano-particles replaces the traditional resistance type and sputtering type coating processes, the liquid phase method and other W processes with the CNTF with the characteristics of rapid temperature rise and drop to generate joule heat2C synthesis mode, the method has the characteristics of low cost, low energy consumption and high efficiency, and can particularly realize W in a plurality of seconds2The ultra-fast preparation of the C nano-particles has important commercial application prospect.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. W2The rapid preparation method of the C nano-particles is characterized by comprising the following steps: the W is2The C nanoparticles are made by consuming the skeletal carbon in CNTF and reducing WOx in situ at high temperatures in joule heating.
2. A W according to claim 12The rapid preparation method of the C nano-particles is characterized by comprising the following steps: the high-temperature preparation process based on the ultra-fast joule heat response is realized by electrifying two ends of the CNTF and quickly reducing WOx on the surface of the CNTF in situ by using joule heat generated by the self resistance of the film.
3. A W according to claim 12A rapid preparation method of C nano-particles, the W2The joule heat source used in the preparation process of the C nanoparticles includes, but is not limited to, carbon nanotube films, and films or fabrics of graphene and carbon nanofibers.
4. A W according to claim 12The rapid preparation method of the C nano-particles mainly comprises the following steps:
(1) pretreatment of the carbon nanotube film: cutting a carbon nanotube film with a thickness of 20 μm and a specification of 2 × 4cm, and soaking with concentrated hydrochloric acid for 6h to remove metal impurities such as catalyst;
(2) loading of WOx particles: uniformly dispersing tungsten powder in absolute ethyl alcohol, and then performing suction filtration on the carbon nanotube film to obtain CNTF deposited with a tungsten powder layer; then the tungsten powder surface of the CNTF is upward, two ends of the CNTF are stuck on a sample frame in a joule heating furnace by utilizing conductive silver adhesive, another CNTF with the same thickness specification is placed on the CNTF at an interval, a furnace chamber is further pumped to a certain vacuum degree and is connected with a direct current power supply, and the tungsten powder on the upper surface of the lower CNTF is partially evaporated and oxidized by controlling the voltage and the electrifying time and is deposited on the lower surface of the upper CNTF;
（3）W2rapid joule heating preparation of C nanoparticles: coating a layer of PVP solution on the surface of the CNTF loaded with the WOx particles, drying in a forced air drying oven, and taking out; adhering two ends of the sample to a sample holder in a Joule heating furnace by using conductive silver adhesive, pumping the furnace chamber to a certain vacuum degree, and rapidly reducing WOx by using Joule heat of CNTF (carbon nano tube) at high temperature by controlling voltage and electrifying time to obtain a target W2And C, nano-particles.
5. A W according to claim 42The rapid preparation method of the C nano-particles is characterized by comprising the following steps: the temperature of the evaporation and oxidation process in the step (2) is 700-1000 ℃.
6. A W according to claim 42The rapid preparation method of the C nano-particles is characterized in that the preparation method specifically comprises the following steps (2): uniformly dispersing 0.2g of tungsten powder in 20ml of absolute ethyl alcohol, performing ultrasonic treatment for 10 minutes, taking 2ml of the solution, and performing suction filtration on a carbon nanotube film to obtain CNTF uniformly coated with the tungsten powder; then the surface of CNTF containing tungsten powder is upward, its two ends are stuck on the sample frame in the joule heating furnace by using conductive silver adhesive, and a CNTF with same thickness specification is placed on the position 5mm away from it, and the furnace cavity is further evacuated to 10 deg.C-1Pa vacuum degree, connecting direct current power supplies at two ends of the CNTF, keeping the surface of the CNTF at 800 ℃ for 1s under the constant voltage of 13V, oxidizing the tungsten powder on the upper surface of the lower CNTF layer, and quickly evaporating WOx particles to the lower surface of the upper CNTF layer.
7. A W according to claim 42The rapid preparation method of the C nano-particles is characterized in that the preparation method specifically comprises the following steps (3): adding 0.2g of PVP into 20ml of ethanol, ultrasonically dissolving and dispersing for 1h, uniformly coating 1ml of PVP-ethanol solution on the surface of the CNTF loaded with WOx, drying in a blast drying oven at 60 ℃ for 0.5h, further adhering two ends of a film on a sample frame in a joule heating furnace by using conductive silver adhesive, and pumping the furnace chamber to 10 DEG C-2Pa vacuum degree and connecting a direct-current power supply, the surface of the CNTF reaches 1100 ℃ under the constant voltage of 35V, at the moment, the framework carbon and PVP of the CNTF synergistically reduce WOx, and the target W uniformly distributed on the surface of the CNTF is obtained2And C, nano-particles.
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