阅读说明：本技术 一种高分散性金属催化材料的制备方法 (Preparation method of high-dispersity metal catalytic material ) 是由 李炳钟 宫地浩 宁玉虎 肖雨露 于 2021-08-26 设计创作，主要内容包括：本发明的目的是提供一种高分散性金属催化材料的制备方法,进一步提高了催化剂的分散性,从而达到更高的催化率。为了实现上述目的,本发明一种高分散性金属催化材料的制备方法,包括步骤1：获取金属催化材料,步骤2：制备处理液,步骤3：急速冷却,步骤4：将冷却完毕后的溶液进行超声波沐浴步骤5：超声波沐浴过程中发现有粒子聚合时停止沐浴,将晶体粒子成型固化。通过本发明的制备方法,具有强亲水性、高分散性的无序排列的粒子占比在70％以上,确保了液体和催化剂的充分接触,提高了催化的效果。(The invention aims to provide a preparation method of a high-dispersity metal catalytic material, which further improves the dispersity of a catalyst so as to achieve higher catalytic rate. In order to achieve the above object, the present invention provides a method for preparing a highly dispersible metal catalytic material, comprising the steps of 1: obtaining the metal catalytic material, and step 2: preparing a treatment solution, and step 3: and (4) rapidly cooling, step 4: and 5, performing ultrasonic bath on the cooled solution: stopping bathing when the particles are polymerized during the ultrasonic bathing process, and forming and curing the crystal particles. The preparation method of the invention has the advantages that the proportion of the randomly arranged particles with strong hydrophilicity and high dispersibility is more than 70 percent, the full contact between the liquid and the catalyst is ensured, and the catalytic effect is improved.)

1. A preparation method of a high-dispersity metal catalytic material is characterized by comprising the following steps of 1: obtaining a metal catalytic material, wherein the metal catalytic material is at least 2 of platinum, ruthenium, iridium, chromium and manganese;

step 2: preparing a treating fluid, namely adding an alkane compound into a dispersant until the dispersant solution is saturated;

and step 3: adding metal powder into the solution generated in the step (2), uniformly mixing, and rapidly cooling at the temperature of minus 70-minus 80 ℃ for 1-5 minutes;

and 4, step 4: carrying out ultrasonic bath on the cooled solution;

and 5: stopping bathing when the particles are polymerized in the ultrasonic bathing process, and placing the product obtained in the step 4 in an environment of 120 ℃ for high-temperature curing to finally form the crystalline material containing the small particles with the particle size of 500-1000 nm in disordered arrangement.

2. The method of claim 1, wherein the number of the metal catalyst species is not more than 3.

3. The method as claimed in claim 1, wherein the particle size of the metal catalyst material is 200-400 mesh.

4. The method of claim 1, wherein the dispersant is isopropyl alcohol.

5. The method of claim 1, wherein the dispersant is ethanol.

6. The method of any one of claims 1-5, wherein the cooling time is 2 minutes.

7. The method of any one of claims 1 to 5, wherein the ultrasonic bath is applied at a frequency of 80Hz or higher.

8. A highly dispersible metal catalyst material prepared by the method of any one of claims 1 to 7, comprising ordered particles and disordered particles, wherein the quantity of disordered particles is 70% to 90% of the total quantity of particles.

9. The highly dispersible metal catalyst material of claim 8, wherein: added to a hydrogen production plant to increase the amount of hydrogen produced.

Technical Field

The invention relates to a catalytic material prepared by hydrogen energy, in particular to a preparation method of a high-dispersity metal catalytic material.

Background

Elements that constitute the electrocatalyst. These elements are roughly classified into three groups according to their physical and chemical properties: noble metal platinum (Pt), a common noble metal electrocatalyst at present; secondly, transition metal elements for constructing the non-noble metal electrocatalyst mainly comprise iron (Fe), cobalt (Co), nickel (N i), copper (Cu), molybdenum (Mo) and tungsten (W); and the non-metal elements for constructing the non-noble metal electrocatalyst mainly comprise boron (B), carbon (C), nitrogen (N), phosphorus (P), sulfur (S) and selenium (Se). However, in practical process, in order to achieve better catalytic effect, the metal which can be used actually is only noble metal. In order to realize mass production, it is desirable to reduce the amount of precious metals as much as possible. Two main ways are to reduce the consumption of noble metal, 1) the quantity of exposed active sites of the catalyst is increased; (2) increase intrinsic activity, i.e. unit active site activity. In the prior art, in order to increase the number of exposed active sites, methods such as nanocrystallization of noble metals, doping of non-noble metals into noble metal materials, or loading of noble metals on non-noble metal carrier materials are generally adopted. For example, in the patent of patent application No. cn202010112028.x in the prior art, an anode catalyst for hydrogen production by water electrolysis using transition metal doped titanium oxide as a carrier and a preparation method thereof, an anode catalyst for hydrogen production by water electrolysis using transition metal doped titanium oxide as a carrier and a preparation method and application thereof are disclosed, wherein porous transition metal doped titanium oxide with stability, conductivity and high specific surface area is selected as a carrier of noble metal oxide nanoparticles, and the catalyst prepared by combining a nano noble metal material can greatly improve the dispersibility and the surface active site density of active noble metal, thereby improving the utilization rate and the specific activity of noble metal, further leading the specific activity of oxygen evolution quality to reach 7-8 times of commercial iridium oxide and simultaneously reducing the loading amount of noble metal in a membrane electrode of a water electrolyzer.

However, in actual use, we have found that the dispersibility of such catalyst materials can be further improved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a preparation method of a high-dispersity metal catalytic material, which further improves the dispersity of a catalyst compared with the prior similar products so as to achieve higher catalytic rate. The cost is not increased on this basis.

In order to achieve the above object, the present invention provides a method for preparing a highly dispersible metal catalytic material, comprising the steps of 1: obtaining a metal catalytic material, wherein the metal catalytic material is at least 2 of platinum, ruthenium, iridium, chromium and manganese;

step 2: preparing a treating fluid, namely adding an alkane compound into a dispersant until the dispersant solution is saturated; and step 3: adding metal powder into the solution generated in the step (2), uniformly mixing, and rapidly cooling at-75 ℃ for 1-5 minutes; only by such a pretreatment is it ensured that a sufficient amount of crystal particles are precipitated in the later step.

And 4, step 4: carrying out ultrasonic bath on the cooled solution; crystalline particles having a diameter of 1-500 nm can be produced in this process.

And 5: stopping bathing when the particles are polymerized in the ultrasonic bathing process, and placing the product obtained in the step 4 in an environment of 120 ℃ for high-temperature curing to finally form the crystalline material containing the small particles with the particle size of 500-1000 nm in disordered arrangement. The precipitated crystal particles can be molded and solidified at a temperature of 120 ℃.

Preferably, the number of the metal catalytic material species is not more than 3. Too many kinds of metal catalyst materials increase the processing time and the amount of deposited bulk crystal particles is reduced.

Preferably, the particle size of the metal catalytic material is 200-400 meshes. The particle size of the raw material must not be too large, which is difficult to handle. While particles that are too small are more costly.

Preferably, isopropanol is used as the dispersant. Isopropanol is the most effective dispersant to use, but due to its limitations, it can only be used for industrial hydrogen production.

Preferably, ethanol is used as the dispersant. The dispersing effect of the ethanol is slightly inferior to that of the isopropanol, but the ethanol is basically nontoxic and can be used in the field of civil hydrogen production.

Preferably, the cooling time is 2 minutes. With the existing equipment, the cooling effect of the synthetic solution can be completely finished within 2 minutes, and the increase of the cooling time can reduce the activity of the particles and is not beneficial to the precipitation of crystal particles.

Preferably, the ultrasonic bath adopts a frequency of more than 80 Hz. At this frequency, the crystal particle precipitation rate is highest.

The invention also comprises a high-dispersity metal catalytic material which comprises ordered particles and disordered particles, wherein the quantity of the disordered particles accounts for 70-90% of the total quantity of the particles.

Further, the high-dispersity metal catalytic material is added into a hydrogen production device to improve the hydrogen production. In particular, its application areas include industrial hydrogen production, such as: an electrode catalyst for a hydrogen-powered automobile. Pages include domestic hydrogen production, such as drinking water hydrotreaters, face masks in the home.

In the scheme, the mixing of various metals is adopted, and through the steps, a large amount of crystal particles formed by mixing various metal elements are finally prepared. And part of the metal which does not participate in the reaction is finally mixed in the crystal particles as a single metal element. The crystal particles formed by single metal elements are orderly arranged particles, and the structure of the particles is stable, so that water molecules are difficult to enter, and the catalytic effect is influenced. The particles formed by mixing a plurality of metal elements are randomly arranged particles, and the particles have strong hydrophilicity and high dispersibility. The catalyst can be used for increasing the contact area with liquid as much as possible, and the preparation method of the invention has the advantages that the proportion of randomly arranged particles with strong hydrophilicity and high dispersibility is more than 70 percent, thereby ensuring the sufficient contact between the liquid and the catalyst and improving the catalytic effect.

Compared with the prior art, the catalytic capacity of the high-dispersity metal catalytic material finally prepared by adopting the technical scheme of the invention is about 20% higher than that of the catalyst prepared by combining the nano-sized noble metal material with the highest catalytic capacity in the prior art, and the preparation cost is lower than that of the catalyst prepared by combining the nano-sized noble metal material with the same type.

Detailed Description

The present disclosure is described in further detail below. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure.

Example 1

This example provides a preparation method for preparing a high-dispersibility metal catalytic material, which is used for preparing an electrode catalyst for a hydrogen energy vehicle:

step 1: obtaining a metal catalytic material, wherein the metal catalytic material is platinum, iridium and manganese with the particle size of 400 meshes;

step 2: preparing a treating fluid, namely putting heptane into a dispersing agent isopropanol until the dispersing agent solution is saturated;

and step 3: adding metal powder into the solution generated in the step (2), uniformly mixing, and rapidly cooling at-75 ℃ for 5 minutes; the metal catalyst material selected in this embodiment is larger in particle size, and therefore requires a longer cooling time to ensure that sufficient crystal particles are precipitated in the later step only by such pretreatment.

And 4, step 4: carrying out ultrasonic bath with the frequency of 80MHz on the cooled solution; this process produced crystalline particles having a diameter of 500 nm.

And 5: stopping bathing when the particles are polymerized in the ultrasonic bathing process, and placing the product obtained in the step 4 in an environment of 120 ℃ for high-temperature curing to finally form the crystalline material containing the small particles which are randomly arranged and have the particle size of about 1000 nanometers. The precipitated crystal particles can be molded and solidified at a temperature of 120 ℃.

Finally, the high-dispersity metal catalytic material is formed, and the disordered particles in the high-dispersity metal catalytic material are 70-75% by observing through an electron microscope. Compared with other embodiments, the cost of the catalyst in the embodiment 1 is lower than that of the catalyst prepared by combining the similar nano noble metal materials. But compared with the catalyst prepared by the existing similar noble metal material combined with nanocrystallization, the catalytic capability is improved by at least 12 percent.

Example 2

The embodiment provides a preparation method for preparing a high-dispersity metal catalytic material, which is used for preparing a catalyst of a household hydrogen production device, and comprises the following steps of 1: obtaining a metal catalytic material, wherein the metal catalytic material is platinum or ruthenium.

Step 2: preparing a treating fluid, namely putting methane into dispersant ethanol, and pressurizing until the dispersant solution is saturated;

and step 3: adding metal powder into the solution generated in the step (2), uniformly mixing, and rapidly cooling at-70 ℃ for 1 minute; only by such a pretreatment is it ensured that a sufficient amount of crystal particles are precipitated in the later step. And because the solubility between the methane and the ethanol as the dispersant is not high, the cooling time cannot be too long.

And 4, step 4: carrying out ultrasonic bath with the frequency of 80MHz on the cooled solution; in this process, crystalline particles having a diameter of 200 nm can be produced.

And 5: stopping bathing when the particles are polymerized in the ultrasonic bathing process, and placing the product obtained in the step 4 in an environment of 120 ℃ for high-temperature curing to finally form the crystalline material containing the small particles with the particle size of 500-700 nm in disordered arrangement. The precipitated crystal particles can be molded and solidified at a temperature of 120 ℃.

Finally forming the high-dispersity metal catalytic material, wherein the proportion of the particles in the disordered arrangement is 85-90%. Such catalysts are used for domestic hydrogen production, for example in domestic drinking water hydrotreaters. The technical method adopted by the embodiment enables the final catalyst to have at least 20% of catalytic capability, and the cost is lower than that of the catalyst prepared by combining the similar nano noble metal materials. The relative hydrogen production rate of the household drinking water hydrogenation machine using the invention can be increased from the highest 6 ml hydrogen per minute in the prior art to 8-10 ml hydrogen per minute. The upper limit of hydrogen saturation in a 550 ml bottle of standard mineral water can be increased from 1.6ppm in the prior art to 4 ppm.

Example 3

The embodiment provides a preparation method for preparing a high-dispersity metal catalytic material, which is used for preparing a catalyst of a hydrogen production device for production, and comprises the following steps of 1: obtaining a metal catalytic material, wherein the metal catalytic material is platinum, chromium and manganese.

Step 2: preparing a treating fluid, namely putting n-hexane into dispersant ethanol until the dispersant solution is saturated;

and step 3: adding metal powder into the solution generated in the step (2), uniformly mixing, and rapidly cooling at-75 ℃ for 2 minutes; only by such a pretreatment is it ensured that a sufficient amount of crystal particles are precipitated in the later step.

And 4, step 4: carrying out ultrasonic bath with the frequency of 80MHz on the cooled solution; in this process, crystalline particles having a diameter of 300 nm can be produced.

And 5: stopping bathing when the particles are polymerized in the ultrasonic bathing process, and placing the product obtained in the step 4 in an environment of 120 ℃ for high-temperature curing to finally form the crystalline material containing the small particles with the particle size of 500-1000 nm in disordered arrangement. The precipitated crystal particles can be molded and solidified at a temperature of 120 ℃.

Finally forming the high-dispersity metal catalytic material, wherein the disordered particles account for 75-85%. Such catalysts are used in hydrogen production plants for producing hydrogen, such as hydrogen masks. Or other medical and American hydrogen production equipment. The catalytic capability is improved by about 17 percent, and the production cost is between that of the embodiment 1 and that of the embodiment 2.

Although the present invention has been described with reference to the preferred embodiments, it is not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that changes may be made without departing from the scope of the invention, and it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.

It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.