CN112831800A - Preparation method of molybdenum-based composite material electrode plate - Google Patents

Preparation method of molybdenum-based composite material electrode plate Download PDF

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CN112831800A
CN112831800A CN202011607892.3A CN202011607892A CN112831800A CN 112831800 A CN112831800 A CN 112831800A CN 202011607892 A CN202011607892 A CN 202011607892A CN 112831800 A CN112831800 A CN 112831800A
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molybdenum
electrode plate
quartz crucible
based composite
sample
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CN112831800B (en
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魏世忠
杨璐
潘昆明
夏梁彬
吴宏辉
赵阳
徐流杰
张玢
单康宁
周玉成
司岸恒
王晓东
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Henan University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • 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
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention relates to a preparation method of a molybdenum-based composite electrode plate, which comprises the steps of pouring molybdenum powder and nickel powder into excessive titanium tetrachloride in a glove box filled with argon, fully stirring and filtering, placing mixed powder adhered with the titanium tetrachloride in a quartz tube of a tube furnace, introducing oxygen for heat treatment, placing the mixed powder after the heat treatment in a graphite mold for discharge plasma sintering, soaking a sintered sample in the titanium tetrachloride again, taking out the sample after filtering, placing the sample in the quartz tube of the tube furnace again, sequentially introducing the oxygen and hydrogen sulfide for heat treatment, and obtaining the molybdenum-based composite electrode plate after the heat treatment. The invention has low cost, convenient operation and controllable process. The obtained electrode plate has high catalytic activity, good conductivity, certain mechanical property and machinability, can be used as a catalyst, a current collector and an electrode to catalyze water decomposition, and has wide industrial production prospect.

Description

Preparation method of molybdenum-based composite material electrode plate
Technical Field
The invention relates to the technical field of preparation of catalytic materials, in particular to a preparation method of a molybdenum-based composite material electrode plate, and belongs to a technical application of preparing catalytic materials by a powder metallurgy method.
Background
With the gradual shortage of petroleum resources and the increasing severity of environmental pollution, hydrogen energy is considered as the most promising alternative clean energy. The development and utilization of hydrogen energy firstly needs to solve the problem of cheap and large-scale production of hydrogen. In recent years, a great deal of research has shown that the use of electrocatalytic water splitting to produce hydrogen is an efficient and sustainable process. In theory, water electrolysis can be carried out at a voltage exceeding 1.23V, but in practice, higher voltage is required for water decomposition due to the presence of overpotential in the hydrogen and oxygen generation reaction, electrolyte resistance, and internal resistance of the electronic circuit. The electrolyzed water consists of two half reactions, namely cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER). Where HER is a two electron transfer reaction and OER is a four electron-proton coupling reaction, higher energy (higher overpotential) is required, and therefore the oxygen evolution overpotential is much higher than the theoretical decomposition voltage of water (1.23V). Therefore, the design and synthesis of the high-efficiency catalyst are the key points for improving the energy efficiency of the hydrogen production by water electrolysis.
Although noble metal catalysts such as platinum show excellent activity, the high cost thereof seriously restricts the industrialization process of hydrogen production by water decomposition. Among the non-noble metal catalysts, compounds of molybdenum such as MoS2，MoSe2Etc. exhibit excellent catalytic performance and exciting application potential. TiO 22Is a common photocatalyst in the field of catalysis, and shows excellent electron transfer activity under ultraviolet light. If TiO 2 is added2And MoS2And by coupling, the synergistic effect can be effectively exerted, so that water can be efficiently decomposed and separated out of hydrogen under the photoelectric dual drive. At present, reported TiO2/MoS2The composite material is in a powder form, is mainly applied to the aspects of photocatalytic degradation of organic pollutants and the like, and adopts the principle of utilizing MoS2Reduction of TiO2To exert TiO to the maximum2The function of (1). Patent document CN105944738A, for example, discloses a TiO based surface modification2/MoS2The preparation method of the composite material influences the interface electronic performance of the composite material through surface modification treatment, thereby influencing TiO2/MoS2The energy band material of the heterojunction is beneficial to improving the photocatalytic performance of the composite material. Another patent CN106902846B discloses a hollow TiO2/MoS2The composite material, the preparation method and the flow thereof effectively improve the utilization rate of visible light, thereby improving the photocatalytic efficiency. In summary, the prior art is on TiO2As the main body of the catalytic phase.
Disclosure of Invention
The invention aims to provide a preparation method of a molybdenum-based composite material electrode plate, which is implemented by MoS2Being a main body of catalytic phase, TiO2Assisted by increasing the light energy utilization, widens MoS2The catalytic application range of (1). Meanwhile, the invention originally manufactures the composite material into the self-supporting electrode plate, has certain mechanical property, is convenient to process into parts with various shapes, and is suitable for the design requirement of the catalytic hydrogen evolution device.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a molybdenum-based composite electrode plate comprises the following steps:
step one, weighing molybdenum powder and nickel powder according to the required size of a final product, and selecting a proper graphite mold for later use;
step two, taking excessive titanium tetrachloride liquid into a beaker in a glove box filled with argon, slowly pouring the mixed powder in the step one into the beaker, and fully stirring;
thirdly, filtering the mixed system in the beaker in the second step in a glove box filled with argon, reserving mixed powder stained with titanium tetrachloride, placing the mixed powder in a quartz crucible, integrally storing the quartz crucible in a closed container, and taking out the closed container filled with the quartz crucible from the glove box;
taking the quartz crucible out of the closed container in the third step, quickly putting the quartz crucible into a quartz tube of a tube furnace, introducing oxygen, taking the quartz crucible out after the oxidation reaction is finished, and collecting mixed powder in the quartz crucible;
step five, putting the mixed powder obtained in the step four into the graphite mould in the step one, and then putting the graphite mould into a discharge plasma sintering furnace to sinter the mixed powder;
step six, taking the sintered sample obtained in the step five into a glove box filled with argon again, fully soaking the sample in titanium tetrachloride liquid, fully stirring the mixture, filtering the mixture, reserving the sample stained with titanium tetrachloride, placing the sample in a quartz crucible, storing the quartz crucible in a closed container, and taking the closed container out of the glove box;
step seven, taking the quartz crucible in the step six out of the closed container and putting the quartz crucible into a quartz tube of a tube furnace, and carrying out heat treatment in an oxygen atmosphere and a hydrogen sulfide atmosphere in sequence; and taking out the sample after the heat treatment is finished to obtain the final product, namely the molybdenum-based composite material electrode plate.
Preferably, in the first step, the mass ratio of the molybdenum powder to the nickel powder is (3-10): 1.
preferably, in the fourth step, the flow rate of the oxygen is 30 to 100 sccm.
Preferably, in the fifth step, the sintering temperature of the discharge plasma sintering furnace is 1200-1800 ℃, and the heating rate is 50-100 ℃/min.
Preferably, in the seventh step, the heat treatment temperature is 500-650 ℃, oxygen is firstly introduced, the oxygen flow is 30-100 sccm, and the time is 0.5-1 h; then hydrogen sulfide is introduced, wherein the flow of the hydrogen sulfide is 10-30 sccm, and the time is 1-2 h.
Preferably, the obtained molybdenum-based composite electrode plate is used for hydrogen production through catalytic water decomposition.
Furthermore, the second step, the third step and the sixth step of the invention are all operated in a glove box filled with argon.
Furthermore, the main body of the catalytic phase of the electrode plate made of the molybdenum-based composite material is TiO2And MoS2However, other substances with catalytic properties (such as tungsten sulfide, nickel sulfide, cobalt sulfide, etc.) can be loaded on the metal substrate by the above method of the present invention to obtain the electrode material with catalytic properties.
The invention evenly attaches the liquid titanium tetrachloride on the molybdenum-nickel powder particles, and then oxidizes the liquid titanium tetrachloride in situ in oxygen to obtain the molybdenum-nickel metal powder with titanium dioxide evenly attached on the surfaces of the particles. During sintering, molybdenum, nickel and titanium dioxide interact with each other to restrict the growth of crystal grains, and finally the porous and loose metal matrix is formed. And soaking the flaky metal matrix in titanium tetrachloride liquid again, covering a layer of titanium dioxide on the surface of the metal matrix through oxidation and vulcanization, and forming a heterostructure with sulfide to synergistically improve the catalytic activity of the product.
In the preparation process, the obtained molybdenum matrix is in a porous and loose microstructure through temperature control, flow control, concentration control and the like, so that more sites for attaching catalysts are provided, the contact area of the materials and electrolyte can be greatly increased, and the catalytic reaction is carried out more fully. In addition, hydrogen and oxygen which are water decomposition products easily escape from the pores of the material, so that the catalytic efficiency of the material is further optimized.
Compared with the existing smelting method, the preparation process has the advantages of lower cost, more convenient operation, controllable process and stronger applicability. The prepared molybdenum-based composite electrode plate has high catalytic activity, good conductivity and certain mechanical property and machinability, can be machined to a certain extent to be made into various shapes, can be used as a catalyst and a current collector, can be particularly directly used as an electrode for catalyzing water decomposition, and has wide industrial production prospect on a large scale.
Drawings
Fig. 1 is a photograph of a sample of the molybdenum-based composite electrode plate prepared in example 1;
FIG. 2 is an SEM electron micrograph (5-thousand magnification) of the electrode plate made of the molybdenum-based composite material prepared in example 2;
FIG. 3 is an SEM electron micrograph (magnification: 1 ten thousand times) of the molybdenum-based composite electrode plate prepared in example 2;
FIG. 4 is a line graph showing the photoelectric response of the electrode plate made of the molybdenum-based composite material prepared in examples 1, 2 and 3;
fig. 5 is a graph showing electrocatalytic water decomposition performance of the molybdenum-based composite electrode plate prepared in example 3.
Detailed Description
The technical solution of the present invention will be further explained and explained in detail with reference to the drawings and the specific embodiments.
A preparation method of a molybdenum-based composite electrode plate mainly comprises the following steps:
step one, weighing a certain amount of molybdenum powder and nickel powder according to the required size of a final electrode product, and selecting a proper graphite mold for later use.
For example, the volume and shape parameters are determined according to the size of the final product, so that a graphite mold with a proper size is selected, and the mass of the required powder is estimated through the product of the volume and the density. The mass ratio of the molybdenum powder to the nickel powder is (3-10): 1. the molybdenum powder is the main body of the electrode material, and the nickel powder plays a role in assisting sintering and preparing a porous matrix material.
And step two, putting excessive titanium tetrachloride liquid into a beaker in a glove box filled with argon, slowly pouring the mixed powder obtained in the step one into the beaker, and fully stirring.
Based on the chemical property of titanium tetrachloride, the titanium tetrachloride is strictly prevented from contacting with air, otherwise, the phenomenon of white smoke is easily generated, and the product quality is influenced, so that the operation is carried out in an argon glove box. The purpose of the thorough stirring is to make the metal powder particles evenly stained with the titanium tetrachloride liquid.
Thirdly, filtering the mixed system in the beaker in the second step in a glove box filled with argon, reserving mixed powder stained with titanium tetrachloride, placing the mixed powder in a quartz crucible, integrally storing the quartz crucible in a closed container, and taking the closed container filled with the quartz crucible out of the glove box;
and step four, taking the quartz crucible out of the closed container in the step three, quickly putting the quartz crucible into a quartz tube of a tube furnace, introducing oxygen, taking the quartz crucible out after the oxidation reaction is finished, and collecting mixed powder in the quartz crucible.
The purpose here is to generate titanium dioxide in situ on the surface of the metal particles by reacting oxygen with titanium tetrachloride adhering to the surface of the metal particles. The relevant reaction equation is as follows:
TiCl4+O2＝TiO2+2Cl2
because chlorine is generated in the reaction, attention is paid to tail gas treatment to avoid poisoning and pollution. Tail gas treatment is well known in the art and will not be described further herein.
And step five, filling the mixed powder obtained in the step four into the graphite mould in the step one, then putting the graphite mould into a Spark Plasma Sintering furnace (SPS), and Sintering the mixed powder.
The SPS pre-sintering temperature is 1200-1800 ℃ and the heating rate is 50-100 ℃/min. The temperature and the heating rate need to be strictly controlled, because molybdenum is a high-temperature refractory metal, the powder forming needs higher temperature, and the nickel melting point is relatively lower, therefore, the nickel powder can be quickly converted into liquid to be adhered to the surface of the molybdenum particles at the temperature, and meanwhile, the growth of crystal grains is restricted by the interaction of nickel, molybdenum and titanium dioxide, and finally, the porous and loose metal matrix is formed. If the temperature is too low, the forming degree is poor, and the powder is easy to pulverize; however, if the temperature is too high, the density of the molded sample is high, and the molded sample has no porous structure, which is not favorable for the adhesion and the function of the catalyst. Similarly, the rate of temperature increase also affects the size of the product pores.
Step six, taking the sintered sample obtained in the step five into a glove box filled with argon again, fully soaking the sample in titanium tetrachloride liquid, fully stirring and filtering the mixture, reserving the sample stained with titanium tetrachloride, placing the sample in a quartz crucible, storing the quartz crucible in a closed container, and taking the closed container filled with the quartz crucible out of the glove box;
this step is to adhere titanium tetrachloride liquid again to the outer surface and the loose inner hole surface of the molded sintered sample obtained in the above step. The similar colloid theory makes titanium tetrachloride molecule adsorbed onto the formed titanium dioxide particle stably to reach the aim of firm combination with the base body.
And step seven, taking the quartz crucible in the step six out of the closed container, putting the quartz crucible into a quartz tube of a tube furnace, and performing heat treatment in an oxygen atmosphere and a hydrogen sulfide atmosphere in sequence. And taking out the sample after the heat treatment is finished to obtain the final product, namely the molybdenum-based composite material electrode plate.
Similar to step four, but here again the sample was placed in a tube furnace and oxygen was passed through and heated for the purpose of: (1) promoting the titanium tetrachloride attached to the surface of the metal particles to be completely converted into titanium dioxide; (2) promoting the surface of the metal matrix (nickel and molybdenum) to form a layer of compact metal oxide film, and being beneficial to the subsequent vulcanization process. Therefore, the temperature range of 500 ℃ to 650 ℃ should be set to satisfy the above purpose at the same time. The flow of oxygen is 30-100 sccm, the heating time is 0.5-1 h, the purpose is to fully and rapidly oxidize nickel, molybdenum and titanium tetrachloride in the sample, the flow of hydrogen sulfide is 10-30 sccm, and the purpose of the heating time is 1-2 h, the purpose is to ensure that particles on the surface of the product are generated into a uniform and ordered shape.
The second step, the third step and the sixth step of the preparation method are all operated in a glove box filled with argon.
Example 1:
(1) weighing 3g of molybdenum powder and 1g of nickel powder, and selecting a graphite die with the diameter of phi 20 for later use.
(2) In a glove box filled with argon, an excess amount of titanium tetrachloride liquid was taken in a beaker, and the mixed powder in step (1) was slowly poured into the beaker and sufficiently stirred.
(3) Filtering the mixed system in the beaker in the step (2) in a glove box filled with argon, reserving mixed metal powder stained with titanium tetrachloride, placing the mixed metal powder in a quartz crucible, storing the whole quartz crucible in a closed container, and taking the closed container filled with the quartz crucible out of the glove box;
(4) and (4) taking the quartz crucible in the step (3) out of the closed container, quickly putting the quartz crucible into a quartz tube of a tube furnace, introducing oxygen with the flow rate of 30sccm, taking out the quartz crucible after the oxidation reaction is finished, and collecting the mixed powder in the quartz crucible.
(5) And (3) putting the mixed powder obtained in the step (4) into the graphite mould in the step (1), and then putting the graphite mould into an SPS discharge plasma sintering furnace to sinter the mixed powder, wherein the sintering temperature is set to be 1200 ℃, and the heating rate is set to be 50 ℃/min.
(6) Taking the sintered sample obtained in the step (5) into a glove box filled with argon again, fully soaking the sample in titanium tetrachloride liquid, fully stirring and filtering the sample, reserving the sample stained with titanium tetrachloride, putting the sample into a quartz crucible, storing the quartz crucible in a closed container, and taking the closed container out of the glove box;
(7) and (4) taking the quartz crucible in the step (6) out of the closed container, putting the quartz crucible into a quartz tube of a tube furnace, setting the heating temperature to be 500 ℃, firstly introducing oxygen at the flow rate of 30sccm, introducing hydrogen sulfide after 0.5h, setting the flow rate to be 10sccm and the time to be 1h, and carrying out heat treatment on the sample in the quartz tube. And taking out the sample after the heat treatment is finished to obtain the final product, namely the molybdenum-based composite material electrode plate.
The finished electrode plate prepared in this example was macroscopically and microscopically characterized, and the results are shown in fig. 1. As can be seen from fig. 1: the product obtained in this example is in the form of black small discs having a diameter of 20mm and a thickness of 2 mm.
Example 2:
(1) weighing 5g of molybdenum powder and 1g of nickel powder, and selecting a graphite die with the diameter of phi 30 for later use.
(2) In a glove box filled with argon, an excess amount of titanium tetrachloride liquid was taken in a beaker, and the mixed powder in step (1) was slowly poured into the beaker and sufficiently stirred.
(3) Filtering the mixed system in the beaker in the step (2) in a glove box filled with argon, reserving mixed metal powder stained with titanium tetrachloride, placing the mixed metal powder in a quartz crucible, storing the whole quartz crucible in a closed container, and taking the closed container filled with the quartz crucible out of the glove box;
(4) and (4) taking the quartz crucible in the step (3) out of the closed container, quickly putting the quartz crucible into a quartz tube of a tube furnace, introducing oxygen with the flow rate of 100sccm, taking out the quartz crucible after the oxidation reaction is finished, and collecting the mixed powder in the quartz crucible.
(5) And (3) putting the mixed powder obtained in the step (4) into the graphite mould in the step (1), and then putting the graphite mould into an SPS discharge plasma sintering furnace to sinter the mixed powder, wherein the sintering temperature is set to be 1500 ℃, and the heating rate is 100 ℃/min.
(6) Taking the sintered sample obtained in the step (5) into a glove box filled with argon again, fully soaking the sample in titanium tetrachloride liquid, fully stirring and filtering the sample, reserving the sample stained with titanium tetrachloride, putting the sample into a quartz crucible, storing the quartz crucible in a closed container, and taking the closed container out of the glove box;
(7) and (3) putting the quartz crucible in the step (6) into a quartz tube of a tube furnace, setting the heating temperature to be 650 ℃, firstly introducing oxygen with the flow rate set to be 100sccm, then introducing hydrogen sulfide with the flow rate set to be 30sccm for 1h, and carrying out heat treatment on the sample in the quartz tube. And taking out the sample after the heat treatment is finished to obtain the final product, namely the molybdenum-based composite material electrode plate.
The finished electrode plate prepared in this example was characterized by SEM electron micrographs, and the results are shown in fig. 2 and fig. 3. As can be seen from fig. 2: after the product prepared by the embodiment is amplified by 5 thousand times, the small particles with uniform, thick and agglomerated shapes are formed on the surface of the matrix, gaps exist among the microspheres in an agglomerated state, a loose surface is formed, and the combination of the particles and the matrix is relatively compact, so that the good combination of the catalytic phase material and the matrix is proved. As can be seen from fig. 3: after magnifying the product obtained in this example by 1 ten thousand times, it can be seen that the particles forming the agglomerates are mainly composed of small spherical, irregular and flaky particles, which can correspond to different metal sulfides, respectively.
Example 3:
(1) weighing 10g of molybdenum powder and 1g of nickel powder, and selecting a graphite die with the diameter of phi 50 for later use.
(2) In a glove box filled with argon, an excess amount of titanium tetrachloride liquid was taken in a beaker, and the mixed powder in step (1) was slowly poured into the beaker and sufficiently stirred.
(3) Filtering the mixed system in the beaker in the step (2) in a glove box filled with argon, reserving mixed metal powder stained with titanium tetrachloride, placing the mixed metal powder in a quartz crucible, storing the whole quartz crucible in a closed container, and taking the closed container filled with the quartz crucible out of the glove box;
(4) and (4) taking the quartz crucible in the step (3) out of the closed container, quickly putting the quartz crucible into a quartz tube of a tube furnace, introducing oxygen with the flow rate of 50sccm, taking the quartz crucible out after the oxidation reaction is finished, and collecting the mixed powder in the quartz crucible.
(5) And (3) putting the mixed powder obtained in the step (4) into the graphite mould in the step (1), and then putting the graphite mould into an SPS discharge plasma sintering furnace to sinter the mixed powder, wherein the sintering temperature is 1800 ℃ and the heating rate is 80 ℃/min.
(6) Taking the sintered sample obtained in the step (5) into a glove box filled with argon again, fully soaking the sample in titanium tetrachloride liquid, fully stirring and filtering the sample, reserving the sample stained with titanium tetrachloride, putting the sample into a quartz crucible, storing the quartz crucible in a closed container, and taking the closed container out of the glove box;
(7) and (3) putting the quartz crucible in the step (6) into a quartz tube of a tube furnace, setting the heating temperature to be 600 ℃, firstly introducing oxygen with the flow rate set to be 80sccm, introducing hydrogen sulfide after 0.8h, setting the flow rate to be 20sccm, and carrying out heat treatment on the sample in the quartz tube for 1.5 h. And taking out the sample after the heat treatment is finished to obtain the final product, namely the molybdenum-based composite material electrode plate.
The photoelectric response of the finished electrode plates prepared in examples 1-3 was characterized, and the results are shown in FIG. 4. As can be seen from fig. 4: the finished electrode plates prepared in examples 1-3 were placed in a photoelectrocatalysis reaction apparatus, an electrochemical workstation was used to assist in testing the photoresponse data of the materials prepared in examples 1, 2, 3 under 300w xenon lamp irradiation, a three-electrode system was used to test the photoresponse data of the materials prepared in examples 1, 2, 3, the light source was turned on every 50s, and each time the irradiation time was 50s, it could be seen that each electrode plate material had a different degree of sensitivity to the light, wherein the product (red curve) of example 3 had a greater current response signal, which proved that the product had a better light sensitivity. The product electrode plate of example 3 was then used directly as a hydrogen evolution catalytic working electrode, and its hydrogen evolution polarization curve was tested with an electrochemical workstation. The electrolyte used in the experiment is a 1mol/L KOH solution, a graphite rod is used as a counter electrode, and a calomel electrode is used as a reference electrode. And setting a voltage scanning interval to be-1.4-0V to obtain a polarization curve. The results are shown in FIG. 5. As can be seen from fig. 5: the starting potential of the finished molybdenum electrode plate hydrogen evolution catalytic reaction is 120mV (eta 10). The material has excellent electrocatalytic hydrogen evolution performance.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any simple modification, equivalent change and modification made by those skilled in the art according to the technical spirit of the present invention are still within the technical scope of the present invention without departing from the technical scope of the present invention.

Claims (8)

1. The preparation method of the molybdenum-based composite electrode plate is characterized by comprising the following steps of:
step one, weighing molybdenum powder and nickel powder according to the required size of a final product, and selecting a proper graphite mold for later use;
step two, taking excessive titanium tetrachloride liquid into a beaker in a glove box filled with argon, slowly pouring the mixed powder in the step one into the beaker, and fully stirring;
thirdly, filtering the mixed system in the beaker in the second step in a glove box filled with argon, reserving mixed powder stained with titanium tetrachloride, placing the mixed powder in a quartz crucible, integrally storing the quartz crucible in a closed container, and taking out the closed container filled with the quartz crucible from the glove box;
taking the quartz crucible out of the closed container in the third step, quickly putting the quartz crucible into a quartz tube of a tube furnace, introducing oxygen, taking the quartz crucible out after the reaction is finished, and collecting mixed powder in the quartz crucible;
step five, putting the mixed powder obtained in the step four into the graphite mould in the step one, and then putting the graphite mould into a discharge plasma sintering furnace to sinter the mixed powder;
step six, taking the sintered sample obtained in the step five into a glove box filled with argon again, fully soaking the sample in titanium tetrachloride liquid, fully stirring the mixture, filtering the mixture, reserving the sample stained with titanium tetrachloride, placing the sample in a quartz crucible, storing the quartz crucible in a closed container, and taking the closed container out of the glove box;
step seven, taking the quartz crucible in the step six out of the closed container and putting the quartz crucible into a quartz tube of a tube furnace, and carrying out heat treatment in an oxygen atmosphere and a hydrogen sulfide atmosphere in sequence; and taking out the sample after the heat treatment is finished to obtain the final product, namely the molybdenum-based composite material electrode plate.
2. The method for manufacturing the molybdenum-based composite electrode plate according to claim 1, wherein: in the first step, the mass ratio of the molybdenum powder to the nickel powder is (3-10): 1.
3. the method for manufacturing the molybdenum-based composite electrode plate according to claim 1, wherein: in the fourth step, the flow rate of oxygen is 30-100 sccm.
4. The method for manufacturing the molybdenum-based composite electrode plate according to claim 1, wherein: in the fifth step, the sintering temperature of the discharge plasma sintering furnace is 1200-1800 ℃, and the heating rate is 50-100 ℃/min.
5. The method for manufacturing the molybdenum-based composite electrode plate according to claim 1, wherein: in the seventh step, the heat treatment temperature is 500-650 ℃, oxygen is firstly introduced, the oxygen flow is 30-100 sccm, and the time is 0.5-1 h; then hydrogen sulfide is introduced, wherein the flow of the hydrogen sulfide is 10-30 sccm, and the time is 1-2 h.
6. The method for manufacturing the molybdenum-based composite electrode plate according to claim 1, wherein: the obtained molybdenum-based composite material electrode plate is used for hydrogen production through water decomposition.
7. The method for manufacturing a molybdenum-based composite electrode plate according to claims 1 to 5, wherein: other substances with catalytic properties are loaded on the metal substrate by the method to prepare the electrode material with catalytic properties.
8. The method for manufacturing the molybdenum-based composite electrode plate according to claim 7, wherein: other materials with catalytic properties are tungsten sulphide, nickel sulphide, cobalt sulphide.
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