CN115094466A - Hollow carbon dodecahedron packaged WC and W 2 C or biphase WC/W 2 Preparation method of C nano-particle electrocatalyst - Google Patents
Hollow carbon dodecahedron packaged WC and W 2 C or biphase WC/W 2 Preparation method of C nano-particle electrocatalyst Download PDFInfo
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Abstract
The invention discloses a hollow carbon dodecahedron packaged WC and W 2 C or biphase WC/W 2 A preparation method of a C nano-particle electrocatalyst belongs to the technical field of electrocatalytic hydrogen production. The invention solves the problems that the existing high-temperature compound tungsten carbide is difficult to be nano-sized and the tungsten carbide has weaker electrocatalytic activity. The invention adopts a template method to assist in preparing the hollow carbon dodecahedron packaged WC and W 2 C or biphase WC/W 2 The C nano-particle electrocatalyst has a unique hollow dodecahedron structure, so that the contact area of the catalyst and electrolyte can be increased, and the number of active sites can be increased. Two-phase WC/W packaged in hollow carbon dodecahedron simultaneously 2 W in C nano-particle electrocatalyst 2 Introduction of CCan also adjust the electronic structure of WC to improve H in the hydrogen evolution process + Thereby promoting the hydrogen evolution reaction and improving the catalytic capability of the active sites.
Description
Technical Field
The invention relates to a hollow carbon dodecahedron packaged WC and W 2 C or biphase WC/W 2 A preparation method of a C nano-particle electrocatalyst belongs to the technical field of electrocatalytic hydrogen production.
Background
Excessive exploitation and consumption of fossil energy can cause a series of resource and environmental problems such as energy exhaustion, global warming, air pollution and the like. The development of new, green renewable energy sources is an important direction of current research.
The hydrogen energy is a green and efficient renewable energy source, and the advantages of no toxicity, water generation of a combustion product, wide source range and the like are considered as an optimal energy carrier. The hydrogen produced by the electrolysis water hydrogen production technology has high purity and zero carbon emission, and is the most efficient and environment-friendly hydrogen production mode. In the electrolytic cell, Hydrogen Evolution Reaction (HER) occurs at the cathode, and Oxygen Evolution Reaction (OER) occurs at the anode. The main problem restricting the development is that the hydrogen production cost is increased due to the large energy loss accompanying the overhigh electrode voltage, which is mainly reflected in the relatively high overpotential of the hydrogen evolution and oxygen evolution reactions. Therefore, it is important to reduce the overpotential of the catalytic reaction and promote the progress of the catalytic reaction.
At present, commercial catalytic electrode materials generally adopt noble metal platinum group elements, but the hydrogen production cost is improved due to the lack of earth reserves, high price and excessive loss, so that the large-scale industrial application is limited. In order to reduce the cost of hydrogen production by electrolyzing water, a non-noble metal electrocatalyst with low price needs to be greatly developed to replace a noble metal catalyst so as to achieve the purpose of industrial application.
The Transition Metal Carbides (TMCs) have good chemical and structural stability, can be kept stable in an acidic or alkaline system without chemical reaction with the Transition metal carbides, and can be used as an active electrode material for a long timeImmersed in an acidic (or alkaline) electrolyte environment. Wherein, tungsten carbide (WC) has a platinum-like surface electronic structure and catalytic performance, and the arrangement of nuclear electrons is most similar to that of noble metal platinum, so that the tungsten carbide is a non-noble metal material which has the most potential to replace Pt in the field of electrocatalytic hydrogen production. Although WC has good electrochemical stability and catalytic activity, WC still has catalytic activity comparable to Pt. This is mainly due to the electronic structure of WC to H + So that the adsorption energy of (2) is too high that H is generated during the hydrogen evolution process + Difficult to desorb, shielding the active site, resulting in a decrease in catalytic activity. Meanwhile, WC is a typical high-melting-point compound, and high-temperature sintering often causes excessive growth of WC crystals and coarsening of crystal grains, so that the specific surface area of the WC is inevitably reduced, the surface active sites of the WC are greatly reduced, and the catalytic performance of the WC cannot be fully exerted. Therefore, it is necessary to provide a novel electrocatalyst and a preparation method thereof to solve the problems that high-temperature compound tungsten carbide is difficult to be nano-sized and the tungsten carbide has weak electrocatalytic activity.
Disclosure of Invention
The invention provides a hollow carbon dodecahedron packaged WC and W to solve the problems that the existing high-temperature compound tungsten carbide is difficult to nanocrystallize and the tungsten carbide has weak electrocatalytic activity 2 C or biphase WC/W 2 C nano-particle electro-catalyst and a preparation method thereof.
The technical scheme of the invention is as follows:
one of the purposes of the invention is to provide a hollow carbon dodecahedron packaged biphase WC/W 2 A method of preparing a C nanoparticle electrocatalyst, the method comprising the steps of:
s1, mixing a phosphotungstic acid aqueous solution and a potassium chloride aqueous solution to obtain a hydrothermal reaction mixed solution, placing the hydrothermal reaction mixed solution in a high-pressure hydrothermal kettle for hydrothermal reaction, centrifuging after the reaction is finished, and repeatedly cleaning precipitates for several times by using deionized water and an ethanol solution in sequence to obtain white potassium phosphotungstate dodecahedron powder;
s2, adding potassium phosphotungstate dodecahedron powder into deionized water, adding dopamine hydrochloride after ultrasonic dispersion is uniform, stirring uniformly at room temperature, adjusting the pH to 13 by using ammonia water, continuing stirring for reaction for 0.5-6 h, centrifuging to obtain black brown powder, repeatedly cleaning for several times by using deionized water and ethanol solution in sequence, and drying in vacuum to obtain hollow W-polydopamine dodecahedron powder;
s3, carrying out high-temperature carbonization treatment on the hollow W-polydopamine dodecahedron powder in an inert atmosphere to obtain the hollow carbon dodecahedron packaged biphase WC/W 2 And C, nano-particles.
Further limiting, in S1, the concentration of the phosphotungstic acid aqueous solution and the concentration of the potassium chloride aqueous solution are both 0.5-1.5%, the volume of the phosphotungstic acid aqueous solution is 10-20 ml, and the volume of the potassium chloride aqueous solution is 5-10 ml.
Further limiting, the mass ratio of phosphotungstic acid to potassium chloride in the hydrothermal reaction solution in S1 is (1-5): 1.
further limiting the temperature of the water in the S1 to be 100-130 ℃ for 1-24 h.
Further limited, the mass ratio of the dodecahedral powder of potassium phosphotungstate to dopamine hydrochloride in S2 is 1: 1.
Further limiting, the volume of the ammonia water added in S2 is 0.1-2 ml.
Further, the ammonia water concentration in S2 is 28-30%.
Further, the inert atmosphere in S3 is nitrogen, helium, neon, argon, krypton, xenon, or radon.
Further limiting the temperature of high-temperature carbonization in S3 to 700-1000 ℃ for 1-12 h.
The invention also aims to provide a hollow carbon dodecahedron encapsulated WC nanoparticle electrocatalyst and a preparation method thereof, wherein the method comprises the following steps:
s1, mixing a phosphotungstic acid aqueous solution and a potassium chloride aqueous solution to obtain a hydrothermal reaction solution, placing the hydrothermal reaction solution in a high-pressure hydrothermal kettle for hydrothermal reaction, centrifuging after the reaction is finished, and repeatedly cleaning precipitates for several times by using deionized water and an ethanol solution in sequence to obtain white potassium phosphotungstate dodecahedron powder;
s2, adding potassium phosphotungstate dodecahedron powder into deionized water, adding dopamine hydrochloride after uniform ultrasonic dispersion, uniformly stirring at room temperature, adjusting the pH to 13 by using ammonia water, continuously stirring for reaction for 0.5-6 h, centrifuging to obtain black brown powder, repeatedly cleaning for several times by using deionized water and ethanol solution in sequence, and performing vacuum drying treatment to obtain hollow W-polydopamine dodecahedron powder;
s3, carrying out high-temperature carbonization treatment on the hollow W-polydopamine dodecahedron powder under a vacuum condition to obtain the hollow carbon dodecahedron encapsulated WC nano-particles.
Further limiting, the mass ratio of phosphotungstic acid to potassium chloride in the hydrothermal reaction solution in S1 is (1-5): 1.
further limiting the temperature of the water in the S1 to be 100-130 ℃ for 1-24 h.
Further limiting, the mass ratio of the dodecahedral powder of potassium phosphotungstate to dopamine hydrochloride in S2 is 1: 1.
Further limiting, the volume of the ammonia water added in S2 is 0.1-2 ml.
Further limiting, the ammonia water concentration in S2 is 28-30%.
Further limiting, the carbon source in S3 is dicyandiamide or melamine.
More specifically, the carbon source in S3 is melamine.
Further limiting the mass ratio of the carbon source to the hollow W-polydopamine dodecahedral powder in S3 to be (1-6): 1.
further limiting, the high-temperature carbonization temperature in S3 is 700-1000 ℃, and the time is 1-12 h.
The third purpose of the invention is to provide a hollow carbon dodecahedron packaged W 2 A method of preparing a C nanoparticle electrocatalyst, the method comprising the steps of:
s1, mixing a phosphotungstic acid aqueous solution and a potassium chloride aqueous solution to obtain a hydrothermal reaction solution, placing the hydrothermal reaction solution in a high-pressure hydrothermal kettle for hydrothermal reaction, centrifuging after the reaction is finished, and repeatedly cleaning precipitates for several times by using deionized water and an ethanol solution in sequence to obtain white potassium phosphotungstate dodecahedron powder;
s2, adding potassium phosphotungstate dodecahedron powder into deionized water, adding dopamine hydrochloride after ultrasonic dispersion is uniform, stirring uniformly at room temperature, adjusting the pH to 13 by using ammonia water, continuing stirring for reaction for 0.5-6 h, centrifuging to obtain black brown powder, repeatedly cleaning for several times by using deionized water and ethanol solution in sequence, and drying in vacuum to obtain hollow W-polydopamine dodecahedron powder;
s3, carrying out high-temperature carbonization treatment on the hollow W-polydopamine dodecahedron powder under the vacuum condition to obtain hollow carbon dodecahedron packaged W 2 And C, nano-particles.
Further limiting, in S1, the concentration of the phosphotungstic acid aqueous solution and the concentration of the potassium chloride aqueous solution are both 0.5-1.5%, the volume of the phosphotungstic acid aqueous solution is 10-20 ml, and the volume of the potassium chloride aqueous solution is 5-10 ml.
Further limiting, the mass ratio of phosphotungstic acid to potassium chloride in the hydrothermal reaction solution in S1 is (1-5): 1.
further limiting the temperature of the water in the S1 to be 100-130 ℃ for 1-24 h.
Further limiting, the mass ratio of the dodecahedral powder of potassium phosphotungstate to dopamine hydrochloride in S2 is 1: 1.
Further limiting, the volume of the ammonia water added in S2 is 0.1-2 ml.
Further, the ammonia water concentration in S2 is 28-30%.
Further limiting the temperature of high-temperature carbonization in S3 to 700-1000 ℃ for 1-12 h.
The invention adopts a template method to assist in preparing the hollow carbon dodecahedron packaged biphase WC/W 2 The C nano-particle electrocatalyst has a unique hollow dodecahedron structure, so that the contact area of the catalyst and electrolyte can be increased, and the number of active sites can be increased. While W 2 The introduction of C can also adjust the electronic structure of WC, improve H in the hydrogen evolution process + The adsorption energy of the hydrogen-separating catalyst can promote the hydrogen-separating reaction, improve the catalytic capability of the active sites and enable the hydrogen-separating catalyst to have excellent electro-catalytic hydrogen-separating performance, such as typical parameters, overpotential, stability and the like. The synthesis method provided by the invention can reduce the synthesis temperature of WC, has low cost, has nontoxic and environment-friendly reactants and products, and can be used for popularizing the synthesis of other tungsten-based compounds, such as carbon hollow dodecahedron encapsulated WC or W 2 C nanoparticlesAnd (4) granulating. Compared with the prior art, the application also has the following beneficial effects:
(1) the method takes potassium phosphotungstate dodecahedron as a template and a tungsten source, and utilizes the good coating characteristic of dopamine hydrochloride in an alkaline solution to uniformly coat the potassium phosphotungstate dodecahedron; meanwhile, potassium phosphotungstate can be dissolved in an alkaline environment and forms a W-polypopamine organic framework with dopamine hydrochloride, W atoms are uniformly wrapped by dopamine hydrochloride organisms, the dopamine hydrochloride is used as a carbon source during high-temperature carbonization, and meanwhile, the organic framework can inhibit excessive growth of tungsten carbide grains and prevent agglomeration during the high-temperature carbonization.
(2) The invention utilizes the diffusion gradient existing in the difference of the diffusion rates of carbon in the high-temperature carbonization process of macromolecular organic dopamine hydrochloride, thereby obtaining the hollow carbon dodecahedron packaged biphase WC/W 2 C nano-particle electrocatalyst. Aiming at the influence of the carbon diffusion rate on the phase growth characteristic of WC, the method respectively adopts the modes of melamine-assisted carbonization and vacuum carbonization to respectively obtain the hollow carbon dodecahedron-packaged WC nanoparticle electrocatalyst and the hollow carbon dodecahedron-packaged W 2 C nanoparticle electrocatalyst.
(3) All the raw materials are non-noble metals, so the cost is low; the synthetic method is simple and easy to implement, green, pollution-free and environment-friendly; the method has strong universality and has effects on Mo and W-based carbide.
(4) The hollow carbon dodecahedron prepared by the invention encapsulates WC and W 2 C or biphase WC/W 2 The hollow structure of the C nano-particle electrocatalyst can increase the contact area of the catalyst and electrolyte in the catalysis process, and expose more active sites; and the carbon hollow dodecahedron structure has good conductivity, and enhances the electron/charge transmission in the catalysis process.
Drawings
FIG. 1 is a schematic view of a hollow carbon dodecahedron encapsulated WC, W prepared in accordance with the examples 2 C or biphase WC/W 2 C, a synthetic schematic diagram of the nano-particles;
FIG. 2 shows the hollow carbon dodecahedral encapsulated WC, W prepared in each example 2 C and biphaseWC/W 2 An X-ray diffraction pattern of the C nanoparticles;
FIG. 3 is a hollow carbon dodecahedral encapsulated two-phase WC/W prepared in example 1 2 C transmission electron microscope picture of nano-particles;
fig. 4 is a transmission electron micrograph of hollow-carbon dodecahedral encapsulated WC nanoparticles prepared in example 2;
FIG. 5 is a hollow-carbon dodecahedral package W prepared in example 3 2 C transmission electron microscope picture of nano-particles;
FIG. 6 shows the hollow carbon dodecahedral encapsulated WC, W prepared in each example 2 C and biphase WC/W 2 And C nano particles and commercial platinum carbon electrolyzed water hydrogen evolution performance are compared.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
Example 1:
as shown in FIG. 1, the present embodiment provides a two-phase WC/W 2 The C nano particles are encapsulated in the carbon hollow dodecahedron to obtain the hollow carbon dodecahedron encapsulated biphase WC/W 2 The method for preparing the C nano-particle electrocatalyst specifically comprises the following steps:
step 1: accurately weighing 200mg of phosphotungstic acid and 80mg of potassium chloride by using an electronic balance, respectively dissolving the phosphotungstic acid and the potassium chloride in 20ml of deionized water and 10ml of deionized water, stirring the solution at room temperature for 30min until the solid is completely dissolved, and then transferring the phosphotungstic acid solution and the potassium chloride solution into a 40ml of polytetrafluoroethylene lining to form a mixed solution. Sealing the polytetrafluoroethylene lining into a stainless steel hydrothermal kettle, heating to 105 ℃, and carrying out heat preservation reaction for 12 hours. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, repeatedly washing the precipitate by using ionized water and absolute ethyl alcohol through a centrifugal method, and drying at 70 ℃ under a vacuum condition to obtain white potassium phosphotungstate dodecahedral powder.
Step 2: 50mg of white potassium phosphotungstate dodecahedron powder is accurately weighed by an electronic balance, dispersed into 20ml of deionized water, and stirred at room temperature until the white potassium phosphotungstate dodecahedron powder is uniformly dispersed in the solution. Then 50mg of dopamine hydrochloride is accurately weighed and added into the solution, 20ml of absolute ethyl alcohol is added, and the mixture is stirred continuously for 30min to be mixed evenly. And then, absorbing an ammonia water solution with the concentration of 28-30% by using an injector, slowly dropwise adding the ammonia water solution into the mixed solution at the speed of 0.075ml/min until the pH value of the mixed solution is 13, and continuously stirring and reacting for 1h after the dropwise adding is finished. And finally, obtaining a black-brown precipitate by a centrifugal method, repeatedly cleaning the black-brown precipitate by deionized water and absolute ethyl alcohol, and drying the black-brown precipitate under the vacuum condition at 70 ℃ to obtain black-brown hollow W-polydopamine dodecahedral powder.
And 3, step 3: transferring the hollow W-polydopamine dodecahedron powder obtained in the step (2) into a tube furnace, heating to 900 ℃ at the heating rate of 20 ℃/min in the argon atmosphere, preserving heat for 1h, cooling, and obtaining the biphase WC/W after the temperature is reduced to room temperature 2 The C nanoparticles are encapsulated in a carbon hollow dodecahedral electrocatalyst.
Example 2:
as shown in fig. 1, the present embodiment provides a method for obtaining a hollow carbon dodecahedron encapsulated WC nanoparticle electrocatalyst by encapsulating WC nanoparticles in a carbon hollow dodecahedron, which specifically comprises the following steps:
step 1: accurately weighing 200mg of phosphotungstic acid and 80mg of potassium chloride by using an electronic balance, respectively dissolving the phosphotungstic acid and the potassium chloride in 20ml of deionized water and 10ml of deionized water, stirring the mixture at room temperature for 30min until the solids are completely dissolved, and transferring the phosphotungstic acid solution and the potassium chloride solution into 40ml of polytetrafluoroethylene lining to form a mixed solution. Sealing the polytetrafluoroethylene lining into a stainless steel hydrothermal kettle, heating to 105 ℃, and carrying out heat preservation reaction for 12 hours. And after the hydrothermal kettle is cooled to room temperature, repeatedly washing the hydrothermal kettle by using ionized water and absolute ethyl alcohol by a centrifugal method, and drying the hydrothermal kettle at 70 ℃ under a vacuum condition to obtain white potassium phosphotungstate dodecahedron powder.
And 2, step: 50mg of white potassium phosphotungstate dodecahedron powder is accurately weighed by an electronic balance, dispersed into 20ml of deionized water, and stirred at room temperature to be uniformly dispersed in the solution. Then 50mg of dopamine hydrochloride is accurately weighed and added into the solution, 20ml of absolute ethyl alcohol is added, and the mixture is stirred continuously for 30min to be mixed evenly. And then sucking the ammonia water solution with the concentration of 28-30% by using an injector, slowly dropwise adding the ammonia water solution at the speed of 0.075ml/min until the pH value of the mixed solution is 13, and continuously stirring and reacting for 1h after the dropwise adding is finished. And finally, obtaining a black-brown precipitate by a centrifugal method, repeatedly cleaning the black-brown precipitate by deionized water and absolute ethyl alcohol, and drying the black-brown precipitate under the vacuum condition at 70 ℃ to obtain black-brown hollow W-polydopamine dodecahedral powder.
And 3, step 3: 50mg of hollow W-polypopamine dodecahedron powder and 200mg of melamine powder are accurately weighed by an electronic balance, the hollow W-polypopamine dodecahedron powder and the melamine powder are separately placed on two sides of a magnetic boat, and one side of melamine is placed on the upper wind of a tube furnace. Heating to 900 ℃ at the heating rate of 20 ℃/min under the argon atmosphere, preserving heat for 2h, cooling, and obtaining the WC nano-particles encapsulated in the carbon hollow dodecahedron electrocatalyst when the temperature is reduced to room temperature.
Example 3:
as shown in FIG. 1, the present embodiment provides W 2 C nano particles are encapsulated in the carbon hollow dodecahedron to obtain hollow carbon dodecahedron encapsulated W 2 The method for preparing the C nano-particle electrocatalyst specifically comprises the following steps:
step 1: accurately weighing 200mg of phosphotungstic acid and 80mg of potassium chloride by using an electronic balance, respectively dissolving the phosphotungstic acid and the potassium chloride in 20ml of deionized water and 10ml of deionized water, stirring the mixture at room temperature for 30min until the solids are completely dissolved, and transferring the phosphotungstic acid solution and the potassium chloride solution into 40ml of polytetrafluoroethylene lining to form a mixed solution. Sealing the polytetrafluoroethylene lining into a stainless steel hydrothermal kettle, heating to 105 ℃, and carrying out heat preservation reaction for 12 hours. After the reaction is finished and the hydrothermal kettle is cooled to room temperature, repeatedly washing the reaction product by using ionized water and absolute ethyl alcohol through a centrifugal method, and drying the reaction product at 70 ℃ under a vacuum condition to obtain white potassium phosphotungstate dodecahedral powder.
Step 2: 50mg of white potassium phosphotungstate dodecahedron powder is accurately weighed by an electronic balance, dispersed into 20ml of deionized water, and stirred at room temperature to be uniformly dispersed in the solution. Then, 50mg of dopamine hydrochloride is accurately weighed and added into the solution, 20ml of absolute ethyl alcohol is added, and the mixture is stirred continuously for 30min to be mixed uniformly. And (3) sucking an ammonia water solution with the concentration of 28-30% by using an injector, slowly dropwise adding the ammonia water solution at the speed of 0.075ml/min until the pH value of the solution is 13, and continuously stirring and reacting for 1h after the dropwise adding is finished. And finally, obtaining a black-brown precipitate by a centrifugal method, repeatedly cleaning the black-brown precipitate by deionized water and absolute ethyl alcohol, and drying the black-brown precipitate under the vacuum condition at 70 ℃ to obtain black-brown hollow W-polydopamine dodecahedral powder.
And step 3: the resulting hollow W-polydopamine dodecahedral powder was vacuum-sealed in a quartz tube. Transferring into a tube furnace, heating to 900 deg.C at a heating rate of 20 deg.C/min, maintaining for 1 hr, cooling, and cooling to room temperature to obtain W 2 The C nanoparticles are encapsulated in a carbon hollow dodecahedral electrocatalyst.
Example of effects:
the hollow-carbon dodecahedral packages WC and W obtained in examples 1 to 3 2 C or biphase WC/W 2 The microstructure and properties of the C nanoparticle electrocatalyst were characterized, with the results as follows:
(1) FIG. 2 is a hollow carbon dodecahedron packaged two-phase WC/W 2 C nanoparticles, hollow-carbon dodecahedral-encapsulated WC nanoparticles, and hollow-carbon dodecahedral-encapsulated W 2 As is clear from FIG. 2, the X-ray diffraction pattern of the C nanoparticles revealed that XRD diffraction peaks of the obtained product corresponded to WC (JCPDS no 51-0939) in the hexagonal system and W in the orthorhombic system 2 C (JCPDS no20-1315), and hybrid WC/W 2 C diffraction peak, no other miscellaneous peak generation, prove the product has very high purity.
(2) FIGS. 3 to 5 are hollow carbon dodecahedron packaged biphase WC/W, respectively 2 C nanoparticles, hollow-carbon dodecahedral-encapsulated WC nanoparticles, and hollow-carbon dodecahedral-encapsulated W 2 The transmission electron microscope images of the C nanoparticles show that a hollow dodecahedron structure with good crystallinity can be obtained by three different carbonization methods, as shown in the transmission electron microscope images of fig. 3 to 5. By high scoreThe results of transmission electron microscopy show that FIG. 3(b) has two sets of lattice fringes corresponding to WC crystal planes (100) with lattice spacing of
W 2 C has a lattice spacing of (200) planes of
And (102) a lattice spacing of crystal planes of
Prove that the hollow carbon dodecahedral encapsulated nano-particles are biphase WC/W 2 C, consistent with XRD diffraction results. In addition, the surfaces with clear high resolution transmission patterns of fig. 4(b) and 5(b) show lattice spacings of
And
corresponding to the (001) plane of WC and W 2 The (200) crystal face of C proves that the hollow carbon dodecahedron is encapsulated by WC nano-particles and W respectively 2 And C, nano-particles.
(3) FIG. 6 is a hollow carbon dodecahedron packaged biphase WC/W 2 C nanoparticle, hollow carbon dodecahedron-encapsulated WC nanoparticle, and hollow carbon dodecahedron-encapsulated W 2 The comparative graph of the hydrogen evolution performance of the C nano-particles and the commercial platinum carbon as the electro-catalyst by electrolysis water is shown in FIG. 6, and the hollow carbon dodecahedron packaged biphase WC/W 2 C nano-particles are in a range of 10mAcm -2 The lowest overpotential of 96mV at current density is shown, which is only 56mV different from commercial Pt/C. Hollow carbon dodecahedron packaged single-phase WC nano-particles and hollow carbon dodecahedron packaged single-phase W 2 C nanoparticles at 10mA cm -2 The lowest overpotential exhibited 158mV and 241mV at current density. The comparison result of the acidic hydrogen evolution performance shows that W is introduced into WC 2 C can effectively improve the electron structure outside the WC core and optimize the hydrogen evolution reaction process H + Adsorption energy, lowering potential barrier of catalytic reaction and increasingThe reaction rate of the speed control step is controlled, so that the catalytic capability is improved.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. Hollow carbon dodecahedron packaged double-phase WC/W 2 The preparation method of the C nano-particle electrocatalyst is characterized by comprising the following steps of:
s1, mixing a phosphotungstic acid aqueous solution and a potassium chloride aqueous solution to obtain a hydrothermal reaction mixed solution, placing the hydrothermal reaction mixed solution into a high-pressure hydrothermal kettle for hydrothermal reaction, centrifuging after the reaction is finished, and repeatedly cleaning precipitates for several times by using deionized water and an ethanol solution in sequence to obtain white potassium phosphotungstate dodecahedron powder;
s2, adding potassium phosphotungstate dodecahedron powder into deionized water, adding dopamine hydrochloride after ultrasonic dispersion is uniform, stirring uniformly at room temperature, adjusting the pH to 13 by using ammonia water, continuing stirring for reaction for 0.5-6 h, centrifuging to obtain black brown powder, repeatedly cleaning for several times by using deionized water and ethanol solution in sequence, and drying in vacuum to obtain hollow W-polydopamine dodecahedron powder;
s3, carrying out high-temperature carbonization treatment on the hollow W-polydopamine dodecahedron powder in inert atmosphere to obtain the hollow carbon dodecahedron packaged dual-phase WC/W 2 And C, nano-particles.
2. The hollow carbon dodecahedron encapsulated biphasic WC/W of claim 1 2 The preparation method of the C nanoparticle electrocatalyst is characterized in that the concentration of the phosphotungstic acid aqueous solution and the concentration of the potassium chloride aqueous solution in S1 are both 0.5-1.5%, the volume of the phosphotungstic acid aqueous solution is 10-20 ml, and the volume of the potassium chloride aqueous solution is 5-10 ml.
3. The hollow carbon dodecahedral encapsulated biphasic WC/W of claim 1 2 C nanoparticle electrocatalysisThe preparation method of the agent is characterized in that the hydrothermal temperature in S1 is 100-130 ℃, and the time is 1-24 h.
4. The hollow carbon dodecahedral encapsulated biphasic WC/W of claim 1 2 The preparation method of the C nano-particle electrocatalyst is characterized in that the mass ratio of potassium phosphotungstate dodecahedral powder to dopamine hydrochloride in S2 is 1: 1.
5. The hollow carbon dodecahedral encapsulated biphasic WC/W of claim 1 2 The preparation method of the C nanoparticle electrocatalyst is characterized in that the volume of ammonia water added in S2 is 0.1-2 ml.
6. The hollow carbon dodecahedral encapsulated biphasic WC/W of claim 1 2 The preparation method of the C nano-particle electrocatalyst is characterized in that the inert atmosphere in S3 is nitrogen, helium, neon, argon, krypton, xenon or radon atmosphere.
7. The hollow carbon dodecahedral encapsulated biphasic WC/W of claim 1 2 The preparation method of the C nanoparticle electrocatalyst is characterized in that the high-temperature carbonization temperature in S3 is 700-1000 ℃, and the time is 1-12 h.
8. A method for preparing a hollow carbon dodecahedron encapsulated WC nanoparticle electrocatalyst, characterized in that S3 in claim 1 is replaced with: and (3) carrying out high-temperature carbonization treatment on the hollow W-polydopamine dodecahedron powder under the auxiliary condition of a carbon source to obtain the hollow carbon dodecahedron encapsulated WC nano-particles.
9. The preparation method of the hollow carbon dodecahedron encapsulated WC nanoparticle electrocatalyst according to claim 8, wherein a carbon source is dicyanodiamine or melamine, and the mass ratio of the carbon source to the hollow W-polydopamine dodecahedron powder is (1-6): 1.
10. hollow carbon dodecahedronPackage W 2 A method for preparing a C nanoparticle electrocatalyst, characterized in that S3 in claim 1 is replaced with: carrying out high-temperature carbonization treatment on the hollow W-polydopamine dodecahedron powder under the vacuum condition to obtain the hollow carbon dodecahedron packaged W 2 And C, nano-particles.
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