CN110562982A - Nano ditungsten carbide particles and preparation method and application thereof - Google Patents
Nano ditungsten carbide particles and preparation method and application thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 239000002159 nanocrystal Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000004570 mortar (masonry) Substances 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 239000011812 mixed powder Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 13
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 10
- 238000000227 grinding Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical class [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- -1 CH)4 Chemical compound 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MEOSMFUUJVIIKB-UHFFFAOYSA-N [W].[C] Chemical compound [W].[C] MEOSMFUUJVIIKB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OZGNYLLQHRPOBR-DHZHZOJOSA-N naftifine Chemical compound C=1C=CC2=CC=CC=C2C=1CN(C)C\C=C\C1=CC=CC=C1 OZGNYLLQHRPOBR-DHZHZOJOSA-N 0.000 description 1
- 229960004313 naftifine Drugs 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/60—
-
- 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
- C01B32/949—Tungsten or molybdenum carbides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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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
- C01P2004/20—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
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a nano-tungsten carbide particle and a preparation method and application thereof, wherein tungsten trioxide powder and urea are ground and uniformly mixed in a mortar according to a certain mass ratio, and then the mixture is transferred into a crucible; preparing nano ditungsten carbide particles: carrying out heat treatment on the uniformly mixed powder in an inert atmosphere to obtain W2and C, nano-particles. The inventionThe method has the advantages of simple process, easy control, energy conservation, uniform obtained ditungsten carbide particles, high crystallinity, no generation of other impure phases, suitability for large-scale production and good electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to nano ditungsten carbide particles and a preparation method and application thereof.
Background
Tungsten carbide (W)XC) Has high melting point, good thermal conductivity and excellent strength. The catalyst can be used as a catalyst carrier and an engineering structure material, and can stably run in a severe environment, such as a high-temperature liquid filter, a high-current density cathode material, and an ion engine of an emitter electron emission device. And has recently attracted attention as a substitute material for noble metal electrocatalysts in the production of hydrogen by electrocatalytic hydrogen evolution.
In the W-C system, the major phases are tungsten carbide (WC) and ditungsten carbide (W)2C) In that respect The advantages of using ditungsten carbide as the cathode catalyst are that it not only has catalytic property and can replace noble metals such as Pt, Pd, Ru, etc., but also is not easy to be poisoned by CO. Therefore, the ditungsten carbide catalyst can partially or to a certain extent save precious metals such as Pt, Pd, Ru and the like, and has wide application prospect.
To date, many preparative methods have been reported to obtain pure phase WC, whereas pure phase W2Methods for the preparation of C have been rarely reported, mainly because of the pure phase W2The synthesis of C is more demanding, typically by reacting a metal precursor with gaseous carbon (e.g., CH)4，C2H6Or CO) at high temperatures (> 700 ℃ C.) leads to uncontrolled sintering of the particles, resulting in very low surface areas of the material. Secondly, the introduction of excessive amounts of gaseous carbon precursor can also cause substantial coking of the catalyst surface, seriously deteriorating its catalytic performance. Thus W2The preparation method of C can only be realized in a narrow range of components and temperature, and the application of C is limited because the preparation method of ditungsten carbide is too complicated and the like, and the products contain more impurities and the like. One of the existing methods is to use WO3·xH2Placing O (x is more than or equal to 0 and less than or equal to 3) nanosheets into a reaction furnace, and introducing NH3Nitriding and then introducing CO/CO2Heating the mixed gas to 650-1000 ℃, and reacting for 1-30h under heat preservation to obtain the multistage porous carbon tungsten compound micro-nano powder. If necessary in the methodTo pure phase W2C is above 800 deg.C. WC if the product phase is obtained below 800 ℃1-X. Abbas et al, Chinese academy of sciences in 2017, use ammonia tungstate and melamine to react in the ratio of 1: 4 and then heat-treated at 800 ℃ in an argon atmosphere to obtain a W2C-NC-WN mixture with a current density of 10mA/cm in an electrochemical hydrogen evolution test in an alkaline environment2The overpotential of (a) is 145.1mv, and the gradient of the Tafel is 96.4 mv/dec.
Disclosure of Invention
The invention aims to solve the technical problems of providing a nano-ditungsten carbide particle and a preparation method and application thereof aiming at the defects in the prior art, wherein urea is used as a carbon source and tungsten trioxide powder is used as a tungsten source, the process is simple and easy to control, energy sources are saved, the product phase is single, no other phase exists, the obtained ditungsten carbide particle is uniform, the electrochemical performance is good, and the expansion of the process for preparing ditungsten carbide and the optimization of the electrochemical hydrogen evolution performance are realized.
The invention adopts the following technical scheme:
A process for preparing the particles of nano-class ditungsten carbide includes such steps as grinding tungsten trioxide powder and urea, mixing, calcining in low-temp tubular furnace, natural cooling to obtain W2And C, nano-particles.
specifically, the mass ratio of the tungsten trioxide powder to the urea is 1 (1-3).
Specifically, the inert atmosphere is N2An atmosphere.
Specifically, the temperature of the calcination treatment is 600-800 ℃, and the heating rate is 1-8 ℃/min.
5. The preparation method of claim 1, wherein the calcination treatment is performed for 1-4 hours, and then the product is naturally cooled.
In another aspect of the present invention, a nano-tungsten carbide particle, W2The C nano crystal is in a particle or sheet structure.
Specifically, W2The particle size of the C nano-particles is 30-300 nm.
The other scheme of the invention is the application of the nano-ditungsten carbide particles in electrocatalysis, and the nano-ditungsten carbide particles can carry out electrocatalysis hydrogen evolution under an acidic condition.
Compared with the prior art, the invention has at least the following beneficial effects:
The invention relates to a preparation method of nano-tungsten carbide particles, which is characterized in that W prepared by controlling the mass ratio of tungsten trioxide to urea and calcining the tungsten trioxide and urea by a one-step method2The C nano crystal has uniform size, high crystallization degree and no impurities, and the whole preparation process has simple steps and simple and convenient operation.
Further, the amount of urea used is W2The phase composition of C has an important adjusting function, and the solid carbon source is adopted in the carbonization process, so that the carbon deposition generated in the carbonization process can be reduced, and the increase of the active surface area of the catalyst is facilitated. To some extent, the size of the nanoparticle size also affects the effective path for catalytic activity.
Furthermore, the gas raw material of the invention is inert gas N for common experiments2The inert gas is used as a protective atmosphere in the experiment, so that the introduction of impurities and the generation of oxides can be avoided, and the purity of the product is high.
Compared with the prior art, the nano-tungsten carbide particles have relatively low temperature and greatly reduce energy consumption.
Further, W2The diameter of the C nano crystal is 30-300 nm, the size is uniform, and the crystallization degree is high
The application of nano ditungsten carbide particle in electrocatalytic hydrogen evolution is to prepare ditungsten carbide nano particles which have high electrocatalytic hydrogen evolution activity, low onset potential, high current density, small Tafel slope, electrocatalytic hydrogen evolution effect under acidic conditions and stable performance.
In conclusion, the tungsten source and the carbon source adopted by the invention have low cost, the preparation process is simple, easy to control, energy-saving and environment-friendly, the product does not generate other impurity phases, the obtained ditungsten carbide particles are uniform, and the method is suitable for large-scale production.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is an SEM image of nano-tungsten carbide prepared in example 1;
FIG. 2 is an XRD pattern of nano-tungsten carbide obtained from the preparation of example 1;
FIG. 3 is the HER performance of the Nanotungsten carbide sample of example 1 in a 0.5M H2SO4 solution;
FIG. 4 is the Tafel slope of the nano-tungsten carbide sample in 0.5M H2SO4 solution in example 1;
Fig. 5 is a stability test chart of the nano tungsten carbide sample prepared in example 1 in a 0.5M H2SO4 solution.
Detailed Description
The invention relates to a preparation method of nano ditungsten carbide particles, which comprises the following steps:
S1, grinding tungsten trioxide powder and urea in a mortar according to the mass ratio of 1 (1-3) and uniformly mixing to obtain a mixture;
Wherein, the requirements of the grinding treatment are certain;
S2, placing the mixture in a crucible, heating to 600-800 ℃ in a low-temperature tube furnace at a heating rate of 1-8 ℃/min, then preserving heat for 1-4 h, and naturally cooling to room temperature to obtain W2And C, nano-particles.
The low-temperature tube furnace is filled with N2An atmosphere.
Prepared W2The C nano crystal is in a particle or sheet structure, and the particle size of the crystal is 30-300 nm.
In the electrochemical test, in order to detect the electrochemical catalytic performance of the nano tungsten carbide prepared by the method, the electrochemical evaluation is carried out on the nano tungsten carbide. In order to detect the electrochemical catalytic performance of the nano tungsten carbide prepared by the method, the electrochemical evaluation is carried out on the nano tungsten carbide. Electrochemical performance test an electrochemical analyzer (shanghai chenhua instruments CHI760B) was used. In the test process, a three-electrode electrolytic cell is adopted, a working electrode is a glassy carbon electrode, an auxiliary electrode is a graphite electrode, a reference electrode is a saturated silver chloride electrode, and an electrolyte solution is as follows: 0.5M H2SO4(pH 0). The test method adopts cyclic voltammetryThe experiments were performed at room temperature.
The preparation method of the working electrode comprises the following steps:
(1) 5mg of the catalyst was weighed out and dissolved in 300. mu.l of isopropanol and sonicated for at least 30 min.
(2) then 10. mu.l of naftifine was added to the sonicated solution and sonication continued for 30 min.
(3) And dripping 10 mul of the catalyst dispersion liquid mixed solution on a glassy carbon electrode with the diameter of 3mm, and carrying out electrochemical test after the solvent in the catalyst is evaporated.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing urea and tungsten trioxide powder in a mass ratio of 2: 1 grinding and uniformly mixing in a mortar, and transferring the mixture into a crucible; placing the mixture in a crucible, and flowing N in a cryotube furnace2Protecting, heating to 700 deg.C at 1 deg.C/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain W of 30nm2And C, nano-particles. W is2C nanoparticles are shown in FIG. 1; and has good crystallinity, d value and relative intensity of diffraction peak and W2The values of d and relative intensities listed in the PDF standard card of C (35-0776) are consistent as shown in FIGS. 1 and 2.
Example 2
Mixing urea with tungsten trioxideThe powder is prepared from the following components in a mass ratio of 1: 1 grinding and uniformly mixing in a mortar, and transferring the mixture into a crucible; placing the mixture in a crucible, and flowing N in a cryotube furnace2protecting, heating to 600 deg.C at 2 deg.C/min, keeping the temperature for 4h, and naturally cooling to room temperature to obtain diffraction peak d and relative intensity and W2The d values listed in the PDF standard cards (35-0776) of C are consistent with the relative intensity and are 80nm W2And C, nano-particles.
Example 3
Mixing urea and tungsten trioxide powder in a mass ratio of 3: 1 grinding and uniformly mixing in a mortar, and transferring the mixture into a crucible; placing the mixture in a crucible, and flowing N in a cryotube furnace2Protecting, heating to 800 deg.C at 3 deg.C/min, maintaining for 1h, and naturally cooling to room temperature to obtain diffraction peak d and relative intensity and W2The d values listed in the PDF standard cards (35-0776) of C are consistent with the relative intensity and are 100nm W2And C, nano-particles.
Example 4
Mixing urea and tungsten trioxide powder in a mass ratio of 2.5: 1 grinding and uniformly mixing in a mortar, and transferring the mixture into a crucible; placing the mixture in a crucible, and flowing N in a cryotube furnace2Protecting, heating to 700 deg.C at 5 deg.C/min, maintaining for 2 hr, and naturally cooling to room temperature to obtain diffraction peak d and relative intensity and W2the values of d and relative intensity listed in the PDF standard card of C (35-0776) are consistent and 150nm W2And C, nano-particles.
example 5
Mixing urea and tungsten trioxide powder in a mass ratio of 2.75: 1 grinding and uniformly mixing in a mortar, and transferring the mixture into a crucible; placing the mixture in a crucible, and flowing N in a cryotube furnace2Protecting, heating to 800 deg.C at 7 deg.C/min, keeping the temperature for 3h, and naturally cooling to room temperature to obtain diffraction peak d and relative intensity and W2The values of d and relative intensity listed in the PDF standard card of C (35-0776) are consistent and are 250nm W2And C, nano-particles.
Example 6
Mixing urea and tungsten trioxide powder in a mass ratio of 1.75: 1 grinding and uniformly mixing in a mortar, and transferring the mixture into a crucible; placing the mixture in a crucible, and flowing N in a cryotube furnace2Protecting, heating to 600 deg.C at 8 deg.C/min, keeping the temperature for 4h, and naturally cooling to room temperature to obtain diffraction peak d and relative intensity and W2The values of d and relative intensity listed in the PDF standard card of C (35-0776) are consistent and 300nm W2And C, nano-particles.
In order to detect the electrochemical catalytic performance of the nano tungsten carbide prepared by the method, the electrochemical evaluation is carried out on the nano tungsten carbide. Electrochemical performance test an electrochemical analyzer (shanghai chenhua instruments CHI760B) was used.
In the test process, a three-electrode electrolytic cell is adopted, a working electrode is a glassy carbon electrode, an auxiliary electrode is a graphite electrode, a reference electrode is a saturated silver chloride electrode, and an electrolyte solution is as follows: 0.5M H2SO4(PH 0), the test method was cyclic voltammetry, and the experiment was performed at room temperature.
referring to FIGS. 3 and 4, the catalyst provided in example 1 is 0.5M H2SO4The polarization curve and its Tafel curve in solution (PH 0) show high current density, low onset potential (onset potential) and Tafel slope of 72.08mV dec-1Compared with the similar hydrogen evolution materials reported at present, the material has certain competitiveness. Catalyst exhibiting good hydrogen evolution catalytic activity under acidic conditions figure 5 provides the catalyst of example 1 at 0.5M H respectively2SO4Stability testing of the solution (PH 0) showed that the catalyst remained stable well under acid conditions after 360000s of cycling.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (8)
1. A method for preparing nano ditungsten carbide particles is characterized in thatGrinding tungsten trioxide powder and urea, mixing to obtain a mixture, calcining the mixture in a low-temperature tubular furnace in an inert atmosphere, and naturally cooling to obtain W2and C, nano-particles.
2. The method according to claim 1, wherein the mass ratio of the tungsten trioxide powder to the urea is 1 (1-3).
3. The method according to claim 1, wherein the inert atmosphere is N2An atmosphere.
4. The method according to claim 1, wherein the calcination treatment temperature is 600 to 800 ℃ and the temperature increase rate is 1 to 8 ℃/min.
5. the preparation method of claim 1, wherein the calcination treatment is performed for 1-4 hours, and then the product is naturally cooled.
6. Nano-ditungsten carbide particles prepared according to the method of claim 1, wherein W is2the C nano crystal is in a particle or sheet structure.
7. The nano-ditungsten carbide particles of claim 6, wherein W is2The particle size of the C nano-particles is 30-300 nm.
8. The use of the nano-ditungsten carbide particles in electrocatalysis according to claim 6, wherein the nano-ditungsten carbide particles are capable of electrocatalytic hydrogen evolution under acidic conditions.
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| CN201910985022.0A CN110562982B (en) | 2019-10-16 | 2019-10-16 | Nano ditungsten carbide particles and preparation method and application thereof |
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| CN114988411A (en) * | 2022-06-02 | 2022-09-02 | 浙江工业大学 | Pure phase W with high specific surface area 2 C nano material and preparation method and application thereof |
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| CN115094466A (en) * | 2022-06-06 | 2022-09-23 | 哈尔滨工业大学（深圳） | Hollow carbon dodecahedron packaged WC and W 2 C or biphase WC/W 2 Preparation method of C nano-particle electrocatalyst |
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