CN110562982B - Nano ditungsten carbide particles and preparation method and application thereof - Google Patents

Nano ditungsten carbide particles and preparation method and application thereof Download PDF

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CN110562982B
CN110562982B CN201910985022.0A CN201910985022A CN110562982B CN 110562982 B CN110562982 B CN 110562982B CN 201910985022 A CN201910985022 A CN 201910985022A CN 110562982 B CN110562982 B CN 110562982B
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tungsten
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CN110562982A (en
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原晓艳
黄文瑞
黄圣琰
沙爱明
王晓飞
郭守武
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Shaanxi University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20Carbon compounds
    • B01J27/22Carbides
    • B01J35/33
    • B01J35/40
    • B01J35/60
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/914Carbides of single elements
    • C01B32/949Tungsten or molybdenum carbides
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057Electrodes 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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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/20Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • YGENERAL 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
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process 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 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

Nano ditungsten carbide particles and preparation method and application thereof
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.
So far, it has been reportedMany preparation methods have been described for obtaining 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 plus 1000 ℃, and reacting for 1-30h under heat preservation to obtain the multistage porous carbon tungsten compound micro-nano powder. In this process, if a pure phase W is to be obtained2C 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:
preparation method of nano ditungsten carbide particlesGrinding tungsten trioxide powder and urea, mixing the ground tungsten trioxide powder and urea to prepare a mixture, then putting the mixture into a low-temperature tubular furnace for calcining in an inert atmosphere, and naturally 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 oxides can be avoidedThe product has high purity.
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, mixing the mixturePlacing the mixture into a crucible, heating the mixture to 600-800 ℃ in a low-temperature tube furnace at a heating rate of 1-8 ℃/min, then preserving the heat for 1-4 hours, and naturally cooling the mixture 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 voltammetry, and the experiment is carried out 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 and tungsten trioxide powder 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 in a mortar anduniformly mixing, 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 (2)

1. A preparation method of nano-tungsten carbide particles is characterized in that tungsten trioxide powder and urea are ground and mixed to prepare a mixture, the mass ratio of the tungsten trioxide powder to the urea is 1:1.75, and then the mixture is added with N2Calcining the mixture in a low-temperature tubular furnace at 600 deg.C and 8 deg.C/min under natural cooling to obtain W in the form of granule or sheet2C nanoparticles, W2The particle size of the C nanoparticles is 300 nm.
2. Use of nano-ditungsten carbide particles prepared according to the method of claim 1 in electrocatalytic hydrogen evolution under acidic conditions.
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