WO2020134740A1 - Electrolysed water catalytic material of platinum-doped carbide and preparation method thereof - Google Patents

Electrolysed water catalytic material of platinum-doped carbide and preparation method thereof Download PDF

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WO2020134740A1
WO2020134740A1 PCT/CN2019/119840 CN2019119840W WO2020134740A1 WO 2020134740 A1 WO2020134740 A1 WO 2020134740A1 CN 2019119840 W CN2019119840 W CN 2019119840W WO 2020134740 A1 WO2020134740 A1 WO 2020134740A1
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platinum
catalytic material
water catalytic
carbide
doped
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陆双龙
杜明亮
朱罕
段芳
潘星星
胡洪寅
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江南大学
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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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • 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
    • 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
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • 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
    • 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

Definitions

  • the invention relates to a platinum-doped carbide electrolytic water catalytic material and a preparation method thereof, which belong to the technical field of electrolytic water catalysis.
  • Nano-carbon fiber is a fibrous nano-carbon material made by rolling multiple layers of graphite sheets. Because of its high strength, high electrical conductivity and good thermal conductivity, it is used in fuel cell electrodes, capacitor electrode materials, heavy metal detection and other fields; In addition, nano-carbon fiber is widely used in the field of catalysis due to its simple preparation, large specific surface area, acid and alkali resistance, and good conductivity.
  • Carbide especially metal carbide has good stability and strong corrosion resistance, but its catalytic activity is poor, when introducing some other metal elements in the metal carbide, such as: Ni, Co and other elements, Forming metal-doped carbides, the catalytic performance of the carbides is greatly improved at this time, but there are relatively few researches on the use of metal-doped carbides in the electrolysis of electrolyzed water.
  • the main preparation methods of metal-doped carbides are: template method, hydrothermal method, electrodeposition method and so on. These preparation methods are relatively cumbersome, and some methods require more stringent conditions.
  • the prepared metal-doped carbides have problems of uneven dispersion, large and non-uniform size, and insignificant synergistic catalytic effect.
  • the object of the present invention is to provide a platinum-doped carbide electrolytic water catalytic material and a preparation method thereof.
  • the method is simple in process and relatively low in cost.
  • the platinum-doped carbide catalyst obtained in the preparation of platinum-doped carbide catalyst is dispersed With good performance and small particle size, the prepared catalyst has high catalytic activity.
  • the technical solution provided by the present invention is: a method for preparing a platinum-doped carbide electrolytic water catalytic material, the method comprising:
  • the solvent for the ultrafine fiber precursor is prepared into a spinning solution with a mass concentration of 5 to 15%, and the platinum precursor and the carbide precursor are dissolved in the spinning solution, and the mass ratio of the two is 1 : 2 ⁇ 5, then use the electrospinning method to prepare the spinning solution into ultrafine fiber membrane;
  • the ultrafine fiber precursor is one or more of polyacrylonitrile, polyvinyl alcohol, and polyvinylpyrrolidone.
  • the metal platinum precursor is one or more of chloroplatinic acid, platinum chloride, and platinum acetylacetonate.
  • the precursor of the carbide is one of phosphomolybdic acid, phosphotungstic acid, ammonium metatungstate, and molybdenum carbonyl.
  • the solvent is any one of dimethylformamide, ethanol, or water.
  • the operating parameters of the electrospinning method are: the spinning voltage is 4 to 20 kV, the distance from the spinning needle to the receiving device is 5 to 20 cm, and the solution pushing speed is 0.01 to 0.05 mL /min.
  • the calcination is to place the ultrafine fiber membrane in the corundum boat, and then place it in the middle of the tube furnace for calcination.
  • the temperature increase rate in the calcination process is 1 to 5°C/min.
  • the invention provides a platinum-doped carbide electrolyzed water catalytic material prepared by the above preparation method, the electrolytic water catalyst material is composed of a catalytically active substance and a carrier, the catalytically active substance is a platinum-doped carbide, the carrier It is ultra-fine carbon fiber.
  • the diameter of the ultra-fine carbon fiber is 100-1000 nm.
  • the size of the platinum-doped carbide is 2-10 nm.
  • the invention also provides the application of the platinum-doped carbide electrolysis water catalytic material in the field of electrolysis water.
  • the present invention has significant advantages:
  • the electrospinning method is used to dissolve the ultrafine fiber precursor, metal salt and carbide precursor in a solvent to prepare a spinning solution, and then use the electrostatic spinning method to prepare the spinning solution into ultrafine fibers ,
  • the method is simple and easy to operate.
  • the ultra-fine carbon fiber can effectively protect the doped metals and carbides from the corrosion of the electrolyte, giving the catalyst good stability and durability.
  • the catalyst After the catalyst has passed 5000 cycles of cyclic voltammetry, it is at 10mA ⁇
  • the corresponding over-potential at the current density of cm -2 is only reduced by 15mV, and it can still maintain a high catalytic activity.
  • Fig.1 Polarization curves of electrolyzed water catalytic materials Ar-Pt/MoC(2:1)-CNFs and Pt/MoC(2:1)-CNFs in 0.5M H 2 SO 4 (Ar represents the whole process of catalyst preparation under argon protection Bottom; 2:1 represents the molar ratio of platinum acetylacetonate to phosphomolybdic acid).
  • FIG. 1 Microstructure of Pt/MoC(2:1)-CNFs electrolyzed water catalytic material, where (a): field emission scanning electron micrograph; (b): transmission electron micrograph.
  • Figure 6 Field emission scanning electron micrograph of Pt/MoC(2:1)-NFs-4% electrolyzed water catalytic material.
  • Fig.7 Polarization curves of electrolyzed water catalytic materials Pt/MoC(0.08:1)-CNFs, Pt/MoC(2:1)-CNFs and Pt/MoC(3.8:1)-CNFs in 0.5M H 2 SO 4 .
  • the electrocatalytic hydrogen evolution activity was tested in a 0.5M sulfuric acid solution.
  • the data obtained are shown in FIG. 1.
  • the curve represented by the solid small square in FIG. 1 is the Ar-Pt/MoC prepared in Example 1. 2:1)-The polarization curve of CNFs hybrid material in 0.5MH 2 SO 4 is based on the current density of 10mA ⁇ cm -2 , and the over-potential corresponding to the material is compared to determine the catalytic hydrogen evolution performance of the material. Corresponding value for the abscissa. Through the polarization curve, the catalyst performance can be obtained
  • FIG. 1 shows the Ar-Pt/MoC(2:1)-CNFs prepared in Example 1 and its implementation.
  • Example 2 The polarization curves of the two Pt/MoC(2:1)-CNFs hybrid materials prepared in 0.5MH 2 SO 4 based on the current density of 10mA ⁇ cm -2 and comparing the corresponding overpotentials of the materials To determine the catalytic hydrogen evolution performance of the material, the closer the overpotential (that is, the value corresponding to the abscissa) to 0, the better the catalytic performance. By comparison, it is found that the pre-oxidized material has better catalytic performance. Therefore, the firing conditions are preferred Pre-oxidation.
  • Fig. 2 is the microscopic morphology of Pt/MoC(2:1)-CNFs hybrid material, where (a) is a field emission scanning electron microscope photograph, showing that the Pt/MoC(2:1)-CNFs hybrid prepared by the present invention
  • the fiber diameter of the chemical material is about 250nm, the surface of the fiber is relatively smooth, and there are no large particles.
  • (b) is a transmission electron micrograph. It can be seen that the particles of the Pt/MoC(2:1)-CNFs hybrid material are evenly dispersed on the carbon fiber.
  • the size is 2 ⁇ 3nm, the particle size distribution is very narrow, and the size is very uniform, which is better than platinum doped carbide prepared by other methods (>5nm, poor uniformity).
  • Figure 3 is the XRD spectrum of Pt/MoC(2:1)-CNFs hybrid material.
  • the spectrum proves the existence of MoC in Pt/MoC(2:1)-CNFs hybrid material, but no metal appears in the spectrum.
  • the peak of platinum indicates that the platinum particles are extremely small, doped in MoC and carbon fiber, and thus cannot be seen.
  • Pt/MoC(2:1)-CNFs (Pt content of 1.7wt%) were directly used as electrodes, and their electrocatalytic hydrogen evolution activity was tested in 0.5M sulfuric acid solution.
  • the data obtained are shown in Figure 4, at a current density of 10mA ⁇ cm -2 Under the same conditions, the overpotential value of the commercial Pt/C electrode (Pt content is 20wt%) under the current density of 10mA ⁇ cm -2 , the overpotential value is 30mV, it can be seen that Catalytic materials can achieve almost uniform catalytic hydrogen evolution activity of commercial Pt/C electrodes with a small amount of Pt content.
  • the electrocatalytic hydrogen evolution stability was tested in 0.5M sulfuric acid solution. The data obtained is shown in Figure 5. It can be seen that after 5000 cycles of CV testing, it is 10mA ⁇ cm -2 At current density, the overpotential value is only reduced by 15mV. It can be seen that the electrocatalytic material prepared by the present invention has excellent stability and is a material that is expected to replace commercial Pt/C electrodes.
  • Examples 1-2 and Comparative Examples 1-2 it can be seen that the electrocatalytic material prepared by the present invention has strong hydrogen evolution activity, (b) is commercialized Pt/C (20wt%), Pt/MoC (2:1)- The Tafel slopes of the four materials CNFs, MoC-CNFs and Pt-CNFs in 0.5MH 2 SO 4 , this graph compares the catalytic performance of electrolyzed water in terms of kinetics, that is, the lower the slope value, the more conducive to the improvement of catalytic performance . It can be seen that the Pt/MoC(2:1)-CNFs electrolyzed water catalytic material prepared by the method of Example 2 has excellent catalytic performance.
  • the spinning voltage is preferably 12 kV.
  • the ultrafine fiber film obtained under the same spinning conditions to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200°C, and at 200°C Hold for 1h; then raise the temperature to 900°C at a heating rate of 5°C/min for 3h, while passing argon inert gas, and finally cool to room temperature under the protection of argon to obtain electrolysis of metal doped in carbide particles Water catalytic material. Use it directly as an electrode, and test its electrocatalytic hydrogen evolution activity in 0.5M sulfuric acid solution. It was found that the performance of the resulting catalyst The catalyst in Example 2 In comparison, the overpotential has increased. Therefore, the optimum firing temperature of the catalyst is preferably 1000°C.
  • the mass ratio of platinum acetylacetonate to phosphomolybdic acid is preferably 1:2.38.
  • the fiber precursor is preferably polyacrylonitrile.
  • the mass concentration of the spinning precursor is too low or too high to affect whether high-quality fibers can be spun.
  • the optimal amount of platinum acetylacetonate is preferably 0.078g.

Abstract

Disclosed is an electrolysed water catalytic material of platinum-doped carbide and a preparation method thereof. First, an electrostatic spinning method is used to prepare an ultrafine fiber membrane from a metal precursor, a carbide precursor, and an ultrafine fiber precursor. Next, a pre-oxidization or non pre-oxidization method and a high temperature carbonization method are employed to prepare the electrolysed water catalytic material of platinum-doped carbide. The electrolysed water catalytic material of platinum-doped carbide prepared therefrom has both the high conductivity of carbon fiber and the synergistic effect between carbide and metal, improving the catalytic activity and stability of hydrogen evolution, and is simple and safe by using electrostatic spinning in the preparation.

Description

一种铂掺杂碳化物的电解水催化材料及其制备方法Platinum-doped carbide electrolytic water catalytic material and preparation method thereof 技术领域Technical field
本发明涉及一种铂掺杂碳化物的电解水催化材料及其制备方法，属于电解水催化技术领域。The invention relates to a platinum-doped carbide electrolytic water catalytic material and a preparation method thereof, which belong to the technical field of electrolytic water catalysis.
背景技术Background technique
在新能源发展中，氢气由于其具有零排放，来源丰富的特点而备受研究者喜爱。在众多产氢方法中，电解水制氢被认为是一种高效、便捷和最有前途的制备方法。在电解水制氢过程中，主要有两个基本的半反应：阴极析氢反应和阳极析氧反应。由于反应具有较大的动力学阻碍，所以这两个反应都需借助催化剂来完成。迄今为止，铂金属催化剂在电解水析氢方面的催化性能最优异，然而因其价格昂贵且在地球的储存量低，大大限制了它的应用。电解水制氢领域的研究者一直在找寻低成本、高性能、高稳定性的催化材料。In the development of new energy, hydrogen is popular among researchers because of its zero emission and abundant sources. Among many hydrogen production methods, electrolysis of water to produce hydrogen is considered to be an efficient, convenient and most promising preparation method. In the process of producing hydrogen from electrolyzed water, there are two basic half reactions: cathodic hydrogen evolution reaction and anode oxygen evolution reaction. Since the reaction has a large kinetic hindrance, both reactions need to be completed with the aid of a catalyst. To date, platinum metal catalysts have the best catalytic performance in hydrogen evolution from electrolyzed water. However, because of their high price and low storage capacity on the earth, their application is greatly limited. Researchers in the field of hydrogen production from electrolyzed water have been looking for catalytic materials with low cost, high performance and high stability.
纳米碳纤维是由多层石墨片卷曲而成的纤维状纳米碳材料，因其具有高强度、高导电性以及较好的导热性而被应用于燃料电池电极、电容电极材料、重金属检测等领域；此外，纳米碳纤维还由于其制备简单、比表面积大、耐酸耐碱以及导电性好的优点，使得其被广泛应用于催化领域。Nano-carbon fiber is a fibrous nano-carbon material made by rolling multiple layers of graphite sheets. Because of its high strength, high electrical conductivity and good thermal conductivity, it is used in fuel cell electrodes, capacitor electrode materials, heavy metal detection and other fields; In addition, nano-carbon fiber is widely used in the field of catalysis due to its simple preparation, large specific surface area, acid and alkali resistance, and good conductivity.
碳化物，尤其是金属碳化物具有较好的稳定性与较强的耐腐蚀性，但其催化活性较差，当在金属碳化物中引入其他的一些金属元素，如：Ni、Co等元素，形成金属掺杂的碳化物，这时碳化物的催化性能大大提高，但是目前关于金属掺杂碳化物用于电解水催化的相关研究还相对较少。Carbide, especially metal carbide has good stability and strong corrosion resistance, but its catalytic activity is poor, when introducing some other metal elements in the metal carbide, such as: Ni, Co and other elements, Forming metal-doped carbides, the catalytic performance of the carbides is greatly improved at this time, but there are relatively few researches on the use of metal-doped carbides in the electrolysis of electrolyzed water.
目前金属掺杂碳化物的制备方法主要有：模板法、水热法、电沉积法等。这些制备方法相对来说较为繁琐，有些方法所需条件较为苛刻，所制备的金属掺杂碳化物存在分散不均匀，尺寸较大且不均一，协同催化效果不明显等问题。At present, the main preparation methods of metal-doped carbides are: template method, hydrothermal method, electrodeposition method and so on. These preparation methods are relatively cumbersome, and some methods require more stringent conditions. The prepared metal-doped carbides have problems of uneven dispersion, large and non-uniform size, and insignificant synergistic catalytic effect.
需要寻找一种简单的、反应温度温和的制备金属掺杂碳化物的电解水催化材料的方法。There is a need to find a simple, mild reaction temperature method for preparing metal-doped carbide electrolytic water catalytic materials.
发明内容Summary of the invention
本发明的目的在于提供一种铂掺杂碳化物的电解水催化材料及其制备方法，该方法工艺简单、成本较为低廉，制备的铂掺杂碳化物的催化剂中得铂掺杂碳化物得分散性好、颗粒尺寸小，制备得到催化剂得催化活性较高。The object of the present invention is to provide a platinum-doped carbide electrolytic water catalytic material and a preparation method thereof. The method is simple in process and relatively low in cost. The platinum-doped carbide catalyst obtained in the preparation of platinum-doped carbide catalyst is dispersed With good performance and small particle size, the prepared catalyst has high catalytic activity.
具体的，本发明提供的技术方案为：一种铂掺杂碳化物的电解水催化材料的制备方法，所述方法包括：Specifically, the technical solution provided by the present invention is: a method for preparing a platinum-doped carbide electrolytic water catalytic material, the method comprising:
(1)将超细纤维前驱体用溶剂配成质量浓度为5～15％的纺丝液，将金属铂的前驱体和碳化物的前驱体溶解于纺丝液中，两者质量比为1:2～5，然后采用静电纺丝法将纺丝液制备成超细纤维膜；(1) The solvent for the ultrafine fiber precursor is prepared into a spinning solution with a mass concentration of 5 to 15%, and the platinum precursor and the carbide precursor are dissolved in the spinning solution, and the mass ratio of the two is 1 : 2～5, then use the electrospinning method to prepare the spinning solution into ultrafine fiber membrane;
(2)将超细纤维膜进行煅烧，首先在200～280℃下，在空气中预氧化保温1～3h，或在惰性气体中无预氧化保温1～3h，保温结束后，在惰性气氛下，之后升温至800～1200℃，保温3～6h，最后在惰性气体保护下冷却至室温，即得制备得到铂掺杂碳化物的电解水催化材料，其中，金属铂的负载量为1～5wt％。(2) For the calcination of ultrafine fiber membranes, firstly pre-oxidize at 200-280°C in the air for 1 to 3 hours, or in an inert gas without pre-oxidation for 1 to 3 hours. After the end of the insulation, under an inert atmosphere Then, the temperature is raised to 800～1200℃, the temperature is kept for 3～6h, and finally it is cooled to room temperature under the protection of inert gas to obtain the platinum-doped carbide electrolytic water catalytic material, in which the loading of metallic platinum is 1～5wt %.
在本发明的一种实施方式中，所述超细纤维前驱体为聚丙烯腈、聚乙烯醇、聚乙烯吡咯烷酮中的一种或几种。In one embodiment of the present invention, the ultrafine fiber precursor is one or more of polyacrylonitrile, polyvinyl alcohol, and polyvinylpyrrolidone.
在本发明的一种实施方式中，所述金属铂的前驱体为氯铂酸、氯化铂、乙酰丙酮铂中的一种或几种。In one embodiment of the present invention, the metal platinum precursor is one or more of chloroplatinic acid, platinum chloride, and platinum acetylacetonate.
在本发明的一种实施方式中，所述碳化物的前驱体为磷钼酸、磷钨酸、偏钨酸铵、羰基钼中的一种。In one embodiment of the present invention, the precursor of the carbide is one of phosphomolybdic acid, phosphotungstic acid, ammonium metatungstate, and molybdenum carbonyl.
在本发明的一种实施方式中，所述溶剂为二甲基甲酰胺、乙醇或水中的任一种。In one embodiment of the present invention, the solvent is any one of dimethylformamide, ethanol, or water.
在本发明的一种实施方式中，所述静电纺丝法的操作参数为：纺丝电压为4～20kV，纺丝针头到接收装置的距离为5～20cm，溶液推速为0.01～0.05mL/min。In one embodiment of the present invention, the operating parameters of the electrospinning method are: the spinning voltage is 4 to 20 kV, the distance from the spinning needle to the receiving device is 5 to 20 cm, and the solution pushing speed is 0.01 to 0.05 mL /min.
在本发明的一种实施方式中，所述煅烧为将超细纤维膜放置于刚玉舟中，再放置在管式炉中部进行煅烧。In one embodiment of the present invention, the calcination is to place the ultrafine fiber membrane in the corundum boat, and then place it in the middle of the tube furnace for calcination.
在本发明的一种实施方式中，所述煅烧过程中的升温速率为1～5℃/min。In one embodiment of the present invention, the temperature increase rate in the calcination process is 1 to 5°C/min.
本发明提供了上述制备方法制备得到的铂掺杂碳化物的电解水催化材料，所述电解水催化剂材料由催化活性物和载体组成，所述催化活性物为铂掺杂碳化物，所述载体为超细碳纤维。The invention provides a platinum-doped carbide electrolyzed water catalytic material prepared by the above preparation method, the electrolytic water catalyst material is composed of a catalytically active substance and a carrier, the catalytically active substance is a platinum-doped carbide, the carrier It is ultra-fine carbon fiber.
在本发明的一种实施方式中，所述超细碳纤维的直径为100～1000nm。In one embodiment of the present invention, the diameter of the ultra-fine carbon fiber is 100-1000 nm.
在本发明的一种实施方式中，所述铂掺杂碳化物的尺寸为2～10nm。In one embodiment of the present invention, the size of the platinum-doped carbide is 2-10 nm.
本发明还提供了上述铂掺杂碳化物的电解水催化材料在电解水领域的应用。The invention also provides the application of the platinum-doped carbide electrolysis water catalytic material in the field of electrolysis water.
本发明与现有技术相比，具有显著优点：Compared with the prior art, the present invention has significant advantages:
(1)本发明采用静电纺丝法将超细纤维前驱体、金属盐和碳化物前驱体溶于溶剂中，配成纺丝液，随后利用静电纺丝法将纺丝液制备成超细纤维，该方法简单，易操作。(1) In the present invention, the electrospinning method is used to dissolve the ultrafine fiber precursor, metal salt and carbide precursor in a solvent to prepare a spinning solution, and then use the electrostatic spinning method to prepare the spinning solution into ultrafine fibers , The method is simple and easy to operate.
(2)本发明所制备的铂掺杂碳化物的电解水催化材料，其中金属Pt的质量比小于5wt％，Pt掺杂碳化物粒子分散均匀，尺寸均一，为2～10nm；本发明利用掺杂金属与碳化物粒子之 间的协同作用，能够显著提高催化剂的催化活性，在相同的测试条件下，Pt(1.7wt％)掺杂碳化钼的电解水催化材料的催化性能(10mA·cm -1处的过电位为η 10＝38mV)接近商业铂碳(20wt％)的催化性能(10mA·cm -1处的过电位为η 10＝30mV)。 (2) The platinum-doped carbide electrolytic water catalytic material prepared by the present invention, wherein the mass ratio of the metal Pt is less than 5 wt%, the Pt-doped carbide particles are uniformly dispersed, and the size is uniform, 2 to 10 nm; heteroaryl synergy between the metal and the carbide particles, can significantly increase the catalytic activity of the catalyst, under the same test conditions, Pt (1.7wt%) the catalytic performance of molybdenum carbide doped catalytic materials electrolyzed water (10mA · cm - The overpotential at 1 is η 10 =38 mV) close to the catalytic performance of commercial platinum carbon (20 wt%) (the overpotential at 10 mA·cm -1 is η 10 =30 mV).
(3)超细碳纤维可以有效保护掺杂金属以及碳化物免受电解液的侵蚀，赋予催化剂良好的稳定性与耐久性，在电解质溶液中，催化剂经过5000圈循环伏安测试后，其在10mA·cm -2电流密度下所对应的过电位只降低了15mV，仍能够保持较高的催化活性。 (3) The ultra-fine carbon fiber can effectively protect the doped metals and carbides from the corrosion of the electrolyte, giving the catalyst good stability and durability. In the electrolyte solution, after the catalyst has passed 5000 cycles of cyclic voltammetry, it is at 10mA · The corresponding over-potential at the current density of cm -2 is only reduced by 15mV, and it can still maintain a high catalytic activity.
附图说明BRIEF DESCRIPTION
图1电解水催化材料Ar-Pt/MoC(2:1)-CNFs和Pt/MoC(2:1)-CNFs在0.5M H 2SO 4中的极化曲线(Ar代表催化剂制备全程在氩气保护下；2:1代表乙酰丙酮铂和磷钼酸的摩尔比)。 Fig.1 Polarization curves of electrolyzed water catalytic materials Ar-Pt/MoC(2:1)-CNFs and Pt/MoC(2:1)-CNFs in 0.5M H 2 SO 4 (Ar represents the whole process of catalyst preparation under argon protection Bottom; 2:1 represents the molar ratio of platinum acetylacetonate to phosphomolybdic acid).
图2Pt/MoC(2:1)-CNFs电解水催化材料的微观形貌，其中，(a)：场发扫描电镜照片；(b)：透射电镜照片。Figure 2 Microstructure of Pt/MoC(2:1)-CNFs electrolyzed water catalytic material, where (a): field emission scanning electron micrograph; (b): transmission electron micrograph.
图3Pt/MoC(2:1)-CNFs电解水催化材料的XRD谱图。Figure 3 XRD spectrum of Pt/MoC(2:1)-CNFs electrolysis water catalytic material.
图4实施例2～4制备得到的电解水催化材料的电催化活性，其中，(a)：电解水催化材料在0.5M H 2SO 4中的极化曲线；(b)：电解水催化材料在0.5M H 2SO 4中的Tafel斜率。 Fig. 4 Electrocatalytic activity of the electrolyzed water catalytic material prepared in Examples 2 to 4, wherein (a): polarization curve of the electrolyzed water catalytic material in 0.5M H 2 SO 4 ; (b): electrolyzed water catalytic material in Tafel slope in 0.5MH 2 SO 4 .
图5Pt/MoC(2:1)-CNFs电解水催化材料的经过5000圈循环伏安测试后的极化曲线。Figure 5 Polarization curve of Pt/MoC(2:1)-CNFs electrolyzed water catalytic material after 5000 cycles of cyclic voltammetry test.
图6Pt/MoC(2:1)-NFs-4％电解水催化材料的场发扫描电镜照片。Figure 6 Field emission scanning electron micrograph of Pt/MoC(2:1)-NFs-4% electrolyzed water catalytic material.
图7电解水催化材料Pt/MoC(0.08:1)-CNFs、Pt/MoC(2:1)-CNFs和Pt/MoC(3.8:1)-CNFs在0.5M H 2SO 4中的极化曲线。 Fig.7 Polarization curves of electrolyzed water catalytic materials Pt/MoC(0.08:1)-CNFs, Pt/MoC(2:1)-CNFs and Pt/MoC(3.8:1)-CNFs in 0.5M H 2 SO 4 .
具体实施方式detailed description
实施例1Example 1
取0.078g乙酰丙酮铂、0.1857g磷钼酸和1g聚丙烯腈加入到6.8g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为12.8％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，即得到超细纤维膜；0.078g platinum acetylacetonate, 0.1857g phosphomolybdic acid and 1g polyacrylonitrile were added to 6.8g dimethylformamide solution (the mass concentration of polyacrylonitrile was 12.8%), and then the solution was electrospinning method Spinning is carried out, the spinning voltage is controlled to 12 kV, the distance from the receiving device to the spinning needle is 12 cm (that is, the receiving distance is 12 cm), and the flow rate of the solution is 0.01 mL/min to obtain the ultrafine fiber membrane;
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；打开氩气通气30min，随后运行程序，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至1000℃，维持3h，反应一直维持在氩气惰性气体中，最后在氩气保护下冷却至室温，得到金属掺杂在碳化物粒子中的电解水催化材料，命名为Ar-Pt/MoC(2:1)-CNFs。Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; turn on the argon gas for 30min, and then run the program, from room temperature to 200 ℃, it takes 4h, and 200 Incubate at ℃ for 1h; then raise the temperature to 1000℃ at a heating rate of 5℃/min for 3h. The reaction has been maintained in argon inert gas, and finally cooled to room temperature under the protection of argon to obtain metal doped in carbide particles The electrolyzed water catalytic material is named Ar-Pt/MoC(2:1)-CNFs.
将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性，所得数据如图1所示，图1中实心小正方形所表示的曲线为实施例1制备得到的Ar-Pt/MoC(2:1)-CNFs杂化材料在 0.5M H 2SO 4中的极化曲线，以10mA·cm -2电流密度为基准，对比材料所对应的过电位来判定材料的催化析氢性能，过电位即为横坐标对应数值。通过极化曲线图，可得催化剂性能为
Figure PCTCN2019119840-appb-000001
Using it directly as an electrode, the electrocatalytic hydrogen evolution activity was tested in a 0.5M sulfuric acid solution. The data obtained are shown in FIG. 1. The curve represented by the solid small square in FIG. 1 is the Ar-Pt/MoC prepared in Example 1. 2:1)-The polarization curve of CNFs hybrid material in 0.5MH 2 SO 4 is based on the current density of 10mA·cm -2 , and the over-potential corresponding to the material is compared to determine the catalytic hydrogen evolution performance of the material. Corresponding value for the abscissa. Through the polarization curve, the catalyst performance can be obtained
Figure PCTCN2019119840-appb-000001
实施例2Example 2
取0.078g乙酰丙酮铂、0.1857g磷钼酸和1g聚丙烯腈加入到6.8g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为12.8％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，即得到超细纤维膜。0.078g platinum acetylacetonate, 0.1857g phosphomolybdic acid and 1g polyacrylonitrile were added to 6.8g dimethylformamide solution (the mass concentration of polyacrylonitrile was 12.8%), and then the solution was electrospinning method Spinning is carried out, the spinning voltage is controlled to 12 kV, the distance from the receiving device to the spinning needle is 12 cm (that is, the receiving distance is 12 cm), and the solution flow rate is 0.01 mL/min to obtain an ultrafine fiber membrane.
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至1000℃，维持3h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在碳化物粒子中的电解水催化材料，命名为Pt/MoC(2:1)-CNFs。Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200℃, and keep it at 200℃ for 1h; Then, the temperature is raised to 1000°C at a heating rate of 5°C/min for 3 hours, at the same time, an inert gas of argon is passed, and finally cooled to room temperature under the protection of argon to obtain an electrolytic water catalytic material in which metal is doped in carbide particles. Named Pt/MoC(2:1)-CNFs.
将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性，所得数据如图1所示，图1为实施例1制备得到的Ar-Pt/MoC(2:1)-CNFs和实施例2制备得到的Pt/MoC(2:1)-CNFs两种杂化材料在0.5M H 2SO 4中的极化曲线，以10mA·cm -2电流密度为基准，对比材料所对应的过电位来判定材料的催化析氢性能，过电位(即为横坐标对应数值)越接近0，说明催化性能越好，通过对比发现，预氧化后的材料，催化性能更好，由此，烧制条件优选预氧化。 Using it directly as an electrode, the electrocatalytic hydrogen evolution activity was tested in 0.5M sulfuric acid solution. The data obtained are shown in Figure 1. Figure 1 shows the Ar-Pt/MoC(2:1)-CNFs prepared in Example 1 and its implementation. Example 2 The polarization curves of the two Pt/MoC(2:1)-CNFs hybrid materials prepared in 0.5MH 2 SO 4 based on the current density of 10mA·cm -2 and comparing the corresponding overpotentials of the materials To determine the catalytic hydrogen evolution performance of the material, the closer the overpotential (that is, the value corresponding to the abscissa) to 0, the better the catalytic performance. By comparison, it is found that the pre-oxidized material has better catalytic performance. Therefore, the firing conditions are preferred Pre-oxidation.
图2为Pt/MoC(2:1)-CNFs杂化材料的微观形貌，其中，(a)为场发射扫描电镜照片，可见本发明制备得到的Pt/MoC(2:1)-CNFs杂化材料的纤维直径大概在250nm，纤维表面较为光滑，无大粒子，(b)为透射电镜照片，可见，Pt/MoC(2:1)-CNFs杂化材料的粒子均匀分散在碳纤维上，粒子尺寸在2～3nm，粒径分布很窄，尺寸非常均一，优于其他方法制备得到的铂掺杂碳化物(>5nm，均一性较差)。Fig. 2 is the microscopic morphology of Pt/MoC(2:1)-CNFs hybrid material, where (a) is a field emission scanning electron microscope photograph, showing that the Pt/MoC(2:1)-CNFs hybrid prepared by the present invention The fiber diameter of the chemical material is about 250nm, the surface of the fiber is relatively smooth, and there are no large particles. (b) is a transmission electron micrograph. It can be seen that the particles of the Pt/MoC(2:1)-CNFs hybrid material are evenly dispersed on the carbon fiber. The size is 2~3nm, the particle size distribution is very narrow, and the size is very uniform, which is better than platinum doped carbide prepared by other methods (>5nm, poor uniformity).
图3为Pt/MoC(2:1)-CNFs杂化材料的XRD谱图，谱图证明了在Pt/MoC(2:1)-CNFs杂化材料中MoC的存在，而图谱中没有出现金属铂的峰，这说明了铂粒子特别小，掺杂在MoC和碳纤维中，因而显现不出来。Figure 3 is the XRD spectrum of Pt/MoC(2:1)-CNFs hybrid material. The spectrum proves the existence of MoC in Pt/MoC(2:1)-CNFs hybrid material, but no metal appears in the spectrum. The peak of platinum indicates that the platinum particles are extremely small, doped in MoC and carbon fiber, and thus cannot be seen.
将Pt/MoC(2:1)-CNFs(Pt含量为1.7wt％)直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性，所得数据如图4，在10mA·cm -2电流密度下，其过电位值为38mV，相同条件下，商业Pt/C电极(Pt含量为20wt％)在10mA·cm -2电流密度下，其过电位值为30mV，可见，本发明制备得到得电催化材料能够在少量Pt含量的情况下，达到商业Pt/C电极几乎一致的催化析氢活性。 Pt/MoC(2:1)-CNFs (Pt content of 1.7wt%) were directly used as electrodes, and their electrocatalytic hydrogen evolution activity was tested in 0.5M sulfuric acid solution. The data obtained are shown in Figure 4, at a current density of 10mA·cm -2 Under the same conditions, the overpotential value of the commercial Pt/C electrode (Pt content is 20wt%) under the current density of 10mA·cm -2 , the overpotential value is 30mV, it can be seen that Catalytic materials can achieve almost uniform catalytic hydrogen evolution activity of commercial Pt/C electrodes with a small amount of Pt content.
将Pt/MoC(2:1)-CNFs直接作为电极，在0.5M硫酸溶液中测试其电催化析氢稳定性，所得数据如图5，可见，经过5000圈CV测试后，在10mA·cm -2电流密度下，其过电位值仅降低15mV，可见，本发明制备得到得电催化材料具有优良的稳定性，是一种有望替代商业Pt/C电极的材料。 Using Pt/MoC(2:1)-CNFs as the electrode directly, the electrocatalytic hydrogen evolution stability was tested in 0.5M sulfuric acid solution. The data obtained is shown in Figure 5. It can be seen that after 5000 cycles of CV testing, it is 10mA·cm -2 At current density, the overpotential value is only reduced by 15mV. It can be seen that the electrocatalytic material prepared by the present invention has excellent stability and is a material that is expected to replace commercial Pt/C electrodes.
对比例1Comparative Example 1
取0.1857g磷钼酸和1g聚丙烯腈加入到6.8g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为12.8％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，即得到超细纤维膜。Add 0.1857g of phosphomolybdic acid and 1g of polyacrylonitrile to 6.8g of dimethylformamide solution (in which the mass concentration of polyacrylonitrile is 12.8%), and then use the electrospinning method to spin the solution to control the spinning The silk voltage is 12 kV, the distance from the receiving device to the spinning needle is 12 cm (that is, the receiving distance is 12 cm), and the solution flow rate is 0.01 mL/min, that is, an ultra-fine fiber membrane is obtained.
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至1000℃，维持3h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在超细碳纤维中的电解水催化材料，命名为MoC-CNFs。Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200℃, and keep it at 200℃ for 1h; Then, the temperature is raised to 1000°C at a heating rate of 5°C/min for 3 hours, at the same time, an argon inert gas is passed, and finally cooled to room temperature under the protection of argon to obtain an electrolytic water catalytic material doped with metal in ultrafine carbon fibers. Named MoC-CNFs.
将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性，所得数据如图4，可见，未掺杂金属铂的碳化物电催化材料的析氢活性大大降低。Using it directly as an electrode, the electrocatalytic hydrogen evolution activity was tested in 0.5M sulfuric acid solution. The data obtained is shown in Figure 4. It can be seen that the hydrogen evolution activity of the carbide electrocatalytic material not doped with platinum metal is greatly reduced.
对比例2Comparative Example 2
取0.078g乙酰丙酮铂和1g聚丙烯腈加入到6.8g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为12.8％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，即得到超细纤维膜。Take 0.078g of platinum acetylacetonate and 1g of polyacrylonitrile and add it to 6.8g of dimethylformamide solution (the mass concentration of polyacrylonitrile is 12.8%), then use electrospinning to spin the solution to control the spinning The silk voltage is 12 kV, the distance from the receiving device to the spinning needle is 12 cm (that is, the receiving distance is 12 cm), and the solution flow rate is 0.01 mL/min, that is, an ultra-fine fiber membrane is obtained.
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至1000℃，维持3h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在超细碳纤维中的电解水催化材料，命名为Pt-CNFs。Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200℃, and keep it at 200℃ for 1h; Then, the temperature is raised to 1000°C at a heating rate of 5°C/min for 3 hours, at the same time, an argon inert gas is passed, and finally cooled to room temperature under the protection of argon to obtain an electrolytic water catalytic material doped with metal in ultrafine carbon fibers. Named Pt-CNFs.
将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性，所得数据如图4，可见单独使用金属Pt负载在碳纤维上，制备得到的电催化材料的析氢活性较差，综合比较实施例1～2和对比例1～2，可见，本发明制备得到电催化材料具有较强的析氢活性，(b)为商业化Pt/C(20wt％)、Pt/MoC(2:1)-CNFs、MoC-CNFs和Pt-CNFs四种材料在0.5M H 2SO 4中的Tafel斜率，这个图从动力学方面比较了电解水的催化性能，即斜率值越低，越有利于催化性能的提高。可见，实施例2方法制备得到的Pt/MoC(2:1)-CNFs电解水催化材料的催化性能优异。 Using it directly as an electrode, the electrocatalytic hydrogen evolution activity was tested in a 0.5M sulfuric acid solution. The data obtained is shown in Figure 4. It can be seen that the use of metal Pt alone on carbon fibers results in poor hydrogen evolution activity of the prepared electrocatalytic material. Examples 1-2 and Comparative Examples 1-2, it can be seen that the electrocatalytic material prepared by the present invention has strong hydrogen evolution activity, (b) is commercialized Pt/C (20wt%), Pt/MoC (2:1)- The Tafel slopes of the four materials CNFs, MoC-CNFs and Pt-CNFs in 0.5MH 2 SO 4 , this graph compares the catalytic performance of electrolyzed water in terms of kinetics, that is, the lower the slope value, the more conducive to the improvement of catalytic performance . It can be seen that the Pt/MoC(2:1)-CNFs electrolyzed water catalytic material prepared by the method of Example 2 has excellent catalytic performance.
实施例3Example 3
取0.078g乙酰丙酮铂、0.1857g磷钼酸和1g聚丙烯腈加入到6.8g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为12.8％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为16kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，即得到超细纤维膜。0.078g platinum acetylacetonate, 0.1857g phosphomolybdic acid and 1g polyacrylonitrile were added to 6.8g dimethylformamide solution (the mass concentration of polyacrylonitrile was 12.8%), and then the solution was electrospinning method Spinning is carried out, the spinning voltage is controlled to 16 kV, the distance from the receiving device to the spinning needle is 12 cm (that is, the receiving distance is 12 cm), and the solution flow rate is 0.01 mL/min to obtain an ultrafine fiber membrane.
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至1000℃，维持3h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在碳化物粒子中的电解水催化材料。Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200℃, and keep it at 200℃ for 1h; Then, the temperature was raised to 1000°C at a heating rate of 5°C/min for 3 hours. At the same time, an inert gas of argon was passed, and finally cooled to room temperature under the protection of argon to obtain an electrolytic water catalytic material doped with metal particles in carbide particles.
将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性。结果发现，所得催化剂性能(η 10＝90mV)与实施例2中催化剂
Figure PCTCN2019119840-appb-000002
相比，过电位增大。所以，纺丝电压优选为12kV。 Use it directly as an electrode, and test its electrocatalytic hydrogen evolution activity in 0.5M sulfuric acid solution. As a result, it was found that the performance of the obtained catalyst (η 10 = 90 mV) was the same as that of the catalyst in Example 2.
Figure PCTCN2019119840-appb-000002
In comparison, the overpotential increases. Therefore, the spinning voltage is preferably 12 kV.
实施例4Example 4
取0.078g乙酰丙酮铂、0.1857g磷钼酸和1g聚丙烯腈加入到6.8g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为12.8％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，即得到超细纤维膜。0.078g platinum acetylacetonate, 0.1857g phosphomolybdic acid and 1g polyacrylonitrile were added to 6.8g dimethylformamide solution (the mass concentration of polyacrylonitrile was 12.8%), and then the solution was electrospinning method Spinning is carried out, the spinning voltage is controlled to 12 kV, the distance from the receiving device to the spinning needle is 12 cm (that is, the receiving distance is 12 cm), and the solution flow rate is 0.01 mL/min to obtain an ultrafine fiber membrane.
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至1100℃，维持3h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在碳化物粒子中的电解水催化材料。将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性。结果发现，所得催化剂
Figure PCTCN2019119840-appb-000003
与实施例2中催化剂
Figure PCTCN2019119840-appb-000004
相比，过电位有所增大。 Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200℃, and keep it at 200℃ for 1h; Then, the temperature was raised to 1100°C at a heating rate of 5°C/min for 3 hours. At the same time, an inert gas of argon was passed, and finally cooled to room temperature under the protection of argon to obtain an electrolytic water catalytic material doped with metal particles in carbide particles. Use it directly as an electrode, and test its electrocatalytic hydrogen evolution activity in 0.5M sulfuric acid solution. It was found that the resulting catalyst
Figure PCTCN2019119840-appb-000003
The catalyst in Example 2
Figure PCTCN2019119840-appb-000004
In comparison, the overpotential has increased.
将同样纺丝条件下所得的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至900℃，维持3h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在碳化物粒子中的电解水催化材料。将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性。结果发现，所得催化剂性能
Figure PCTCN2019119840-appb-000005
与实施例2中催化剂
Figure PCTCN2019119840-appb-000006
相比，过电位有所增大。因而优选出催化剂最佳烧制温度为1000℃。 Add the ultrafine fiber film obtained under the same spinning conditions to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200℃, and at 200℃ Hold for 1h; then raise the temperature to 900°C at a heating rate of 5°C/min for 3h, while passing argon inert gas, and finally cool to room temperature under the protection of argon to obtain electrolysis of metal doped in carbide particles Water catalytic material. Use it directly as an electrode, and test its electrocatalytic hydrogen evolution activity in 0.5M sulfuric acid solution. It was found that the performance of the resulting catalyst
Figure PCTCN2019119840-appb-000005
The catalyst in Example 2
Figure PCTCN2019119840-appb-000006
In comparison, the overpotential has increased. Therefore, the optimum firing temperature of the catalyst is preferably 1000°C.
实施例5Example 5
取0.078g乙酰丙酮铂、0.0931g磷钼酸和1g聚丙烯腈加入到6.8g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为12.8％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为 12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，即得到超细纤维膜。Take 0.078g of platinum acetylacetonate, 0.0931g of phosphomolybdic acid and 1g of polyacrylonitrile into 6.8g of dimethylformamide solution (the mass concentration of polyacrylonitrile is 12.8%), and then use electrospinning method to the solution Spinning is carried out, the spinning voltage is controlled to 12 kV, the distance from the receiving device to the spinning needle is 12 cm (that is, the receiving distance is 12 cm), and the solution flow rate is 0.01 mL/min to obtain an ultrafine fiber membrane.
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至1000℃，维持3h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在碳化物粒子中的电解水催化材料。将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性。结果发现，所得催化剂性能
Figure PCTCN2019119840-appb-000007
与实施例2中催化剂
Figure PCTCN2019119840-appb-000008
相比，过电位有所增大。仅改变磷钼酸的加入量(0.2275g)，其它条件保持不变，所得催化剂的性能
Figure PCTCN2019119840-appb-000009
与实施例2中催化剂
Figure PCTCN2019119840-appb-000010
相比，过电位有所增大。因而，优选出乙酰丙酮铂与磷钼酸的质量比为1：2.38。 Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200℃, and keep it at 200℃ for 1h; Then, the temperature was raised to 1000°C at a heating rate of 5°C/min for 3 hours. At the same time, an inert gas of argon was passed, and finally cooled to room temperature under the protection of argon to obtain an electrolytic water catalytic material doped with metal particles in carbide particles. Use it directly as an electrode, and test its electrocatalytic hydrogen evolution activity in 0.5M sulfuric acid solution. It was found that the performance of the resulting catalyst
Figure PCTCN2019119840-appb-000007
The catalyst in Example 2
Figure PCTCN2019119840-appb-000008
In comparison, the overpotential has increased. Only change the amount of phosphomolybdic acid added (0.2275g), other conditions remain unchanged, the performance of the resulting catalyst
Figure PCTCN2019119840-appb-000009
The catalyst in Example 2
Figure PCTCN2019119840-appb-000010
In comparison, the overpotential has increased. Therefore, the mass ratio of platinum acetylacetonate to phosphomolybdic acid is preferably 1:2.38.
实施例6Example 6
取0.078g氯铂酸、0.1857g磷钨酸和1g聚乙烯醇加入到9mL水溶液中，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为20kV，接收装置到纺丝针头的距离为20cm(即接收距离为20cm)，溶液流速为0.04mL/min，即得到超细纤维膜。Take 0.078g of chloroplatinic acid, 0.1857g of phosphotungstic acid and 1g of polyvinyl alcohol into 9mL of aqueous solution, and then use electrospinning method to spin the solution, control the spinning voltage to 20kV, the receiving device to the spinning needle The distance is 20 cm (that is, the receiving distance is 20 cm), and the flow rate of the solution is 0.04 mL/min, that is, an ultrafine fiber membrane is obtained.
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至260℃，需要1h，并在260℃下保温3h；然后以5℃/min升温速率升温至1000℃，维持5h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在碳化物粒子中的电解水催化材料。Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 1h to rise from room temperature to 260℃, and keep it at 260℃ for 3h; Then, the temperature was raised to 1000°C at a heating rate of 5°C/min for 5 hours, at the same time, an inert gas of argon was passed, and finally cooled to room temperature under the protection of argon to obtain an electrolytic water catalytic material doped with metal particles in carbide particles.
将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性，所得催化剂性能
Figure PCTCN2019119840-appb-000011
与实施例2中催化剂
Figure PCTCN2019119840-appb-000012
相比，过电位有所增大。所以，纤维前驱体优选为聚丙烯腈。 Use it directly as an electrode and test its electrocatalytic hydrogen evolution activity in 0.5M sulfuric acid solution
Figure PCTCN2019119840-appb-000011
The catalyst in Example 2
Figure PCTCN2019119840-appb-000012
In comparison, the overpotential has increased. Therefore, the fiber precursor is preferably polyacrylonitrile.
对比例3Comparative Example 3
取0.078g乙酰丙酮铂、0.1857g磷钼酸和1g聚丙烯腈加入到24g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为4％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，所得材料命名为Pt/MoC(2:1)-NFs-4％(NF表示没有经过碳化过程的原始纤维)。在纺丝过程中，滴液现象严重，得到的催化材料纤维形貌差，如图6所示。Add 0.078g platinum acetylacetonate, 0.1857g phosphomolybdic acid and 1g polyacrylonitrile to 24g dimethylformamide solution (where the mass concentration of polyacrylonitrile is 4%), and then use electrospinning method to carry out the solution Spinning, control the spinning voltage to 12kV, the distance from the receiving device to the spinning needle is 12cm (that is, the receiving distance is 12cm), the solution flow rate is 0.01mL/min, the resulting material is named Pt/MoC(2:1)-NFs -4% (NF means raw fiber that has not undergone the carbonization process). In the spinning process, the dripping phenomenon is serious, and the fiber morphology of the obtained catalytic material is poor, as shown in FIG. 6.
取0.078g乙酰丙酮铂、0.1857g磷钼酸和1g聚丙烯腈加入到5.25g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为16％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min， 在纺丝过程中，由于纺丝液浓度大，纺丝针头易堵，难得到纤维。0.078g platinum acetylacetonate, 0.1857g phosphomolybdic acid and 1g polyacrylonitrile were added to 5.25g dimethylformamide solution (the mass concentration of polyacrylonitrile was 16%), and then the solution was electrospinning method Spinning is carried out, the spinning voltage is controlled to 12kV, the distance from the receiving device to the spinning needle is 12cm (that is, the receiving distance is 12cm), the solution flow rate is 0.01mL/min. During the spinning process, due to the high concentration of the spinning solution, Spinning needles are easy to block and difficult to obtain fibers.
可见，纺丝前驱体的质量浓度太低或者太高都影响能否纺出高品质的纤维。It can be seen that the mass concentration of the spinning precursor is too low or too high to affect whether high-quality fibers can be spun.
对比例4Comparative Example 4
取0.0312g乙酰丙酮铂、0.1857g磷钼酸和1g聚丙烯腈加入到6.8g二甲基甲酰胺溶液中(其中聚丙烯腈的质量浓度为12.8％)，然后采用静电纺丝法对该溶液进行纺丝，控制纺丝电压为12kV，接收装置到纺丝针头的距离为12cm(即接收距离为12cm)，溶液流速为0.01mL/min，即得到超细纤维膜。Take 0.0312g of platinum acetylacetonate, 0.1857g of phosphomolybdic acid and 1g of polyacrylonitrile to 6.8g of dimethylformamide solution (the mass concentration of polyacrylonitrile is 12.8%), and then use electrospinning method to the solution Spinning is carried out, the spinning voltage is controlled to 12 kV, the distance from the receiving device to the spinning needle is 12 cm (that is, the receiving distance is 12 cm), and the solution flow rate is 0.01 mL/min to obtain an ultrafine fiber membrane.
将一定量的超细纤维膜加入到刚玉舟中，并将刚玉舟置于管式炉中间部位；在空气条件下，从室温升至200℃，需要4h，并在200℃下保温1h；然后以5℃/min升温速率升温至1000℃，维持3h，与此同时通氩气惰性气体，最后在氩气保护下冷却至室温，得到金属掺杂在碳化物粒子中的电解水催化材料，命名为Pt/MoC(0.08:1)-CNFs。Add a certain amount of ultra-fine fiber membrane to the corundum boat, and place the corundum boat in the middle of the tube furnace; under air conditions, it needs 4h to rise from room temperature to 200℃, and keep it at 200℃ for 1h; Then, the temperature is raised to 1000°C at a heating rate of 5°C/min for 3 hours, at the same time, an inert gas of argon is passed, and finally cooled to room temperature under the protection of argon to obtain an electrolytic water catalytic material in which metal is doped in carbide particles. Named Pt/MoC(0.08:1)-CNFs.
将其直接作为电极，在0.5M硫酸溶液中测试其电催化析氢活性，所得数据如图7所示。结果发现，所得催化剂性能
Figure PCTCN2019119840-appb-000013
与实施例2中催化剂
Figure PCTCN2019119840-appb-000014
相比，过电位有所增大。仅改变乙酰丙酮铂的加入量(0.1482g)，其它条件保持不变，所得催化材料命名为Pt/MoC(3.8:1)-CNFs，催化剂的性能(Pt含量为3.32wt％，
Figure PCTCN2019119840-appb-000015
)，与实施例2中催化剂(Pt含量为1.5wt％，
Figure PCTCN2019119840-appb-000016
)相比，过电位有所增大。以38mV过电位为衡量标准，进行质量比活性计算，计算结果表明，实施例2中的催化剂质量比活性(3.49A mg -1)远大于Pt/MoC(3.8:1)-CNFs(0.32A mg -1)。因而，优选出最优的乙酰丙酮铂用量为0.078g。 Using it directly as an electrode, its electrocatalytic hydrogen evolution activity was tested in 0.5M sulfuric acid solution. The data obtained are shown in Figure 7. It was found that the performance of the resulting catalyst
Figure PCTCN2019119840-appb-000013
The catalyst in Example 2
Figure PCTCN2019119840-appb-000014
In comparison, the overpotential has increased. Only the amount of platinum acetylacetonate added (0.1482g) was changed, other conditions remained unchanged, the resulting catalytic material was named Pt/MoC(3.8:1)-CNFs, the performance of the catalyst (Pt content was 3.32wt%,
Figure PCTCN2019119840-appb-000015
), and the catalyst in Example 2 (Pt content is 1.5wt%,
Figure PCTCN2019119840-appb-000016
) Compared to the overpotential increase. Using the 38mV overpotential as the measurement standard, the mass specific activity calculation was performed. The calculation results showed that the mass specific activity of the catalyst in Example 2 (3.49A mg -1 ) was much greater than Pt/MoC(3.8:1)-CNFs (0.32A mg -1 ). Therefore, the optimal amount of platinum acetylacetonate is preferably 0.078g.
其中，质量比活性的计算过程为：在0.5M H 2SO 4中测得极化曲线，选取一定过电位，依据极化曲线得到各种材料所对应的电流密度J(单位为mA cm -2)，然后计算出电流J K＝J*S/1000(S为所用电极的表面积，J K单位为A)，再除以负载在电极上Pt的含量m(m＝滴加催化剂质量*Pt wt％，单位为mg，其中，Pt wt％为各催化剂中的Pt含量，用ICP标定)。依据以上数据，计算得质量活性＝J K/m(A/mg)。 Among them, the calculation process of the mass specific activity is: the polarization curve is measured in 0.5M H 2 SO 4 , a certain overpotential is selected, and the current density J corresponding to various materials is obtained according to the polarization curve (unit is mA cm -2 ) , And then calculate the current J K = J*S/1000 (S is the surface area of the electrode used, J K unit is A), and then divided by the content of Pt supported on the electrode m (m = the mass of the added catalyst * Pt wt% , The unit is mg, where Pt wt% is the Pt content in each catalyst, which is calibrated by ICP). Based on the above data, the calculated mass activity = J K /m (A/mg).
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。Although the present invention has been disclosed as the preferred embodiments above, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be defined by the claims.

Claims (14)

  1. 一种铂掺杂碳化物的电解水催化材料的制备方法，其特征在于，所述方法包括：A method for preparing a platinum-doped carbide electrolytic water catalytic material, characterized in that the method includes:
    (1)将超细纤维前驱体用溶剂配成质量浓度为5～15％的纺丝液，将金属铂的前驱体和碳化物的前驱体溶解于纺丝液中，两者质量比为1:2～5，然后采用静电纺丝法将纺丝液制备成超细纤维膜；(1) The solvent for the ultrafine fiber precursor is prepared into a spinning solution with a mass concentration of 5 to 15%, and the platinum precursor and the carbide precursor are dissolved in the spinning solution, and the mass ratio of the two is 1 : 2～5, then use the electrospinning method to prepare the spinning solution into ultrafine fiber membrane;
    (2)将超细纤维膜进行煅烧：首先在200～280℃下，在空气中预氧化保温1～3h或在惰性气体中无预氧化保温1～3h，保温结束后，在惰性气氛下升温至800～1200℃，保温3～6h，最后在惰性气体保护下冷却至室温，即得制备得到铂掺杂碳化物的电解水催化材料，其中，金属铂的负载量为1wt％～5wt％。(2) Calcining the ultra-fine fiber membrane: first at 200-280°C, pre-oxidation and heat preservation in the air for 1 to 3 hours or in an inert gas without pre-oxidation and heat preservation for 1 to 3 hours. To 800 ~ 1200 ℃, holding for 3 ~ 6h, and finally cooled to room temperature under the protection of inert gas, that is to prepare a platinum-doped carbide electrolytic water catalytic material, in which the loading of metal platinum is 1wt% ~ 5wt%.
  2. 根据权利要求1所述的一种铂掺杂碳化物的电解水催化材料的制备方法，其特征在于，所述超细纤维前驱体为聚丙烯腈、聚乙烯醇、聚乙烯吡咯烷酮中的一种或几种。The method for preparing a platinum-doped carbide electrolytic water catalytic material according to claim 1, wherein the precursor of the ultrafine fiber is one of polyacrylonitrile, polyvinyl alcohol, and polyvinylpyrrolidone Or several.
  3. 根据权利要求1所述的一种铂掺杂碳化物的电解水催化材料的制备方法，其特征在于，所述金属铂的前驱体为氯铂酸、氯化铂、乙酰丙酮铂中的一种或几种。The method for preparing a platinum-doped carbide electrolytic water catalytic material according to claim 1, wherein the precursor of the metal platinum is one of chloroplatinic acid, platinum chloride, and platinum acetylacetonate Or several.
  4. 根据权利要求1所述的一种铂掺杂碳化物的电解水催化材料的制备方法，其特征在于，所述碳化物的前驱体为磷钼酸、磷钨酸、偏钨酸铵、羰基钼中的任一种或几种。The method for preparing a platinum-doped carbide electrolytic water catalytic material according to claim 1, wherein the precursor of the carbide is phosphomolybdic acid, phosphotungstic acid, ammonium metatungstate, molybdenum carbonyl Any one or more of them.
  5. 根据权利要求1～4任一所述的一种铂掺杂碳化物的电解水催化材料的制备方法，其特征在于，所述静电纺丝法的操作参数为：纺丝电压为4～20kV，纺丝针头到接收装置的距离为5～20cm，溶液推速为0.01～0.05mL/min。The method for preparing a platinum-doped carbide electrolytic water catalytic material according to any one of claims 1 to 4, wherein the operating parameters of the electrospinning method are: the spinning voltage is 4 to 20 kV, The distance between the spinning needle and the receiving device is 5-20 cm, and the solution pushing speed is 0.01-0.05 mL/min.
  6. 根据权利要求1～4任一所述的一种铂掺杂碳化物的电解水催化材料的制备方法，其特征在于，所述预氧化或者无预氧化过程的升温的速率为1～5℃/min。The method for preparing a platinum-doped carbide electrolytic water catalytic material according to any one of claims 1 to 4, wherein the rate of temperature increase in the pre-oxidation or non-pre-oxidation process is 1 to 5°C/ min.
  7. 根据权利要求5所述的一种铂掺杂碳化物的电解水催化材料的制备方法，其特征在于，所述预氧化或者无预氧化过程的升温的速率为1～5℃/min。The method for preparing a platinum-doped carbide electrolytic water catalytic material according to claim 5, characterized in that the temperature increase rate of the pre-oxidation or non-pre-oxidation process is 1 to 5°C/min.
  8. 权利要求1～4任一所述的一种铂掺杂碳化物的电解水催化材料的制备方法制备得到的铂掺杂碳化物的电解水催化材料。The method for preparing a platinum-doped carbide electrolytic water catalytic material according to any one of claims 1 to 4 is prepared by a platinum-doped carbide electrolytic water catalytic material.
  9. 权利要求5所述的一种铂掺杂碳化物的电解水催化材料的制备方法制备得到的铂掺杂碳化物的电解水催化材料。The platinum-doped carbide electrolytic water catalytic material prepared by the method of claim 5 is a platinum-doped carbide electrolytic water catalytic material.
  10. 根据权利要求8或9所述的铂掺杂碳化物的电解水催化材料，其特征在于，所述电解水催化材料包括超细碳纤维和铂掺杂碳化物，其中所述超细碳纤维的直径为100～1000nm，所述铂掺杂碳化物的尺寸为2～10nm。The platinum-doped carbide electrolytic water catalytic material according to claim 8 or 9, wherein the electrolytic water catalytic material comprises ultra-fine carbon fiber and platinum-doped carbide, wherein the diameter of the ultra-fine carbon fiber is 100 to 1000 nm, and the size of the platinum-doped carbide is 2 to 10 nm.
  11. 包含权利要求8或9所述的铂掺杂碳化物的电解水催化材料的电解水装置或者电极。An electrolyzed water device or electrode comprising the platinum-doped carbide electrolyzed water catalytic material according to claim 8 or 9.
  12. 包含权利要求10所述的铂掺杂碳化物的电解水催化材料的电解水装置或者电极。An electrolyzed water device or electrode comprising the platinum-doped carbide electrolyzed water catalytic material of claim 10.
  13. 权利要求8或9所述的铂掺杂碳化物的电解水催化材料在电解水领域的应用。Use of the platinum-doped carbide electrolysis water catalytic material according to claim 8 or 9 in the field of electrolysis water.
  14. 权利要求10所述的铂掺杂碳化物的电解水催化材料在电解水领域的应用。The application of the platinum-doped carbide electrolysis water catalytic material according to claim 10 in the field of electrolysis water.
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