阅读说明：本技术 一种三维MXene基载体的析氢催化剂的制备方法 (Preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst ) 是由 徐晨曦 王冉冉 常周 方中威 于 2020-08-05 设计创作，主要内容包括：本发明公开了一种三维MXene基载体的析氢催化剂的制备方法,利用三维MXene基材料作为碱性条件下电解水析氢反应催化剂载体,并负载催化活性颗粒,从而制备三维结构催化剂。相比于传统的贵金属催化剂如(Pt/C)催化剂,本发明制备的新型催化剂,表现出更好的电催化活性和稳定性。(The invention discloses a preparation method of a three-dimensional MXene-based catalyst for hydrogen evolution reaction, which utilizes a three-dimensional MXene-based material as a catalyst carrier for the electrolysis water hydrogen evolution reaction under an alkaline condition and loads catalytic active particles so as to prepare the three-dimensional catalyst. Compared with the traditional noble metal catalyst such as (Pt/C) catalyst, the novel catalyst prepared by the invention has better electrocatalytic activity and stability.)

1. A preparation method of a three-dimensional MXene-based supported hydrogen evolution catalyst is characterized by comprising the following steps:

step 1: adding MXene into a solvent, and uniformly dispersing by ultrasonic to obtain MXene dispersion liquid;

step 2: adding a carbon material into a solvent, and uniformly dispersing by using ultrasonic waves to obtain a carbon material dispersion liquid;

and step 3: mixing the MXene dispersion liquid obtained in the step 1 and the carbon material dispersion liquid obtained in the step 2, uniformly dispersing by ultrasonic waves, transferring the mixture into a hydrothermal reaction kettle, introducing nitrogen for 0.5-5 hours, then carrying out hydrothermal reaction, cooling and washing for a plurality of times after the reaction is finished, and carrying out freeze drying for 12 hours to obtain an MXene-carbon material three-dimensional composite carrier;

and 4, step 4: dispersing the MXene-carbon material three-dimensional composite carrier obtained in the step (3) into a solvent, and performing ultrasonic dispersion for 0.1-20 hours;

and 5: calculating the amount of a precursor of the required catalyst active particles according to the proportion that the mass of the catalyst active particles is 1-60% of the total mass of the catalyst, and adding the precursor of the required catalyst active particles into the dispersion liquid obtained in the step (4) after the precursor of the catalyst active particles is uniformly dispersed in a solvent by ultrasonic;

step 6: and (3) dropwise adding a reducing agent solution into the mixed dispersion liquid obtained in the step (5), washing with deionized water after dropwise adding is finished, and then placing in a vacuum drying oven for vacuum drying for more than 0.5 hour to obtain the three-dimensional MXene-based carrier hydrogen evolution catalyst.

2. The preparation method of claim 1, wherein the raw materials comprise the following components in parts by mass:

3. the production method according to claim 1 or 2, characterized in that:

the MXene is Ti₃C₂、Ti₂C、Nb₃C₂、Nb₂C、TiNbC、Cr₂TiC、Ti₃CN、Ti₄N₃、Ta₄C₃、V₂C、Mo₂C or MoTiC₂。

4. The production method according to claim 1 or 2, characterized in that:

the carbon material is graphene oxide, graphene, carbon nanotubes or activated carbon.

5. The production method according to claim 1 or 2, characterized in that:

the precursor of the active particles of the catalyst is H₂PtCl₆·6H₂O、PdCl₂、Na₂PdCl₄、K₂PdCl₆、NiCl₂、CoCl₂、CuCl₂、ZnCl₂Any one of the above.

6. The production method according to claim 1 or 2, characterized in that:

the reducing agent is NaBH₄Hydrazine hydrate, LiBH₄And formaldehyde.

7. The production method according to claim 1 or 2, characterized in that:

the solvent is any one of deionized water and ethylene glycol.

8. The production method according to claim 1 or 2, characterized in that:

the mass ratio of the MXene to the carbon material in the mixed solution is 0.1-10: 0.1 to 10.

9. The method of claim 1, wherein:

in the step 3, the reaction temperature of the hydrothermal reaction is 80-160 ℃, and the reaction time is 1-10 hours.

10. The production method according to claim 1 or 2, characterized in that:

the mass ratio of the reducing agent to the catalyst active particle precursor is 1-20: 1.

Technical Field

The invention belongs to the technical field of electrocatalysis, and particularly relates to a preparation method of a three-dimensional MXene-based carrier hydrogen evolution catalyst.

Background

The hydrogen production by water electrolysis is a clean and efficient hydrogen production technology, the preparation conditions are mild, the requirement on equipment is low, the purity of the prepared hydrogen can reach 99.99 percent, and the method has high economic and social benefits. Compared with other hydrogen production methods, the hydrogen production by electrolyzing water utilizes clean water as a raw material for reaction, and the preparation method is green and environment-friendly, so that the method is known as a method for continuously producing hydrogen. Therefore, the water electrolysis hydrogen production technology will become the core technology of the future hydrogen production industry.

Noble metal materials such as platinum, palladium and the like are the most suitable hydrogen evolution catalysts with the best catalytic performance at present, but the noble metal materials have low earth crust storage capacity and high price and cannot be applied to industrial hydrogen production on a large scale. Currently, researchers are working on finding catalysts for the hydrogen evolution reaction by electrolysis, which have a novel structure, higher catalytic activity and more stable electrochemical performance. Therefore, the research on the catalyst for the water electrolysis hydrogen evolution reaction which has a stable structure and can carry out high-efficiency catalytic reaction is an important development trend of hydrogen production by water electrolysis.

Disclosure of Invention

The invention aims to provide a preparation method of a three-dimensional MXene-based carrier hydrogen evolution catalyst, which synthesizes the hydrogen evolution catalyst by using novel three-dimensional MXene-based composite carrier loaded catalyst active particles. The carrier has a three-dimensional structure, has a large specific surface area and more catalyst active particle attachment sites, and has more advantages than the traditional carbon black as a catalyst carrier. The catalyst prepared by the carrier has higher catalytic activity and better electrochemical stability.

The preparation method of the three-dimensional MXene-based carrier hydrogen evolution catalyst comprises the steps of compounding MXene and a carbon material to serve as a catalyst carrier for an electrolytic water hydrogen evolution reaction under an alkaline condition, and then loading catalyst active particles to obtain a novel carrier hydrogen evolution catalyst so as to improve the catalytic activity and the stability of the catalyst. The method specifically comprises the following steps:

step 1: adding 0.1-20 parts of MXene into 1-20 parts of solvent, and uniformly dispersing by ultrasonic to obtain MXene dispersion liquid;

step 2: adding 0.1-20 parts of carbon material into 1-20 parts of solvent, and uniformly dispersing by ultrasonic to obtain a carbon material dispersion liquid;

and step 3: mixing the MXene dispersion liquid obtained in the step 1 and the carbon material dispersion liquid obtained in the step 2, uniformly dispersing by ultrasonic waves, transferring the mixture into a hydrothermal reaction kettle, introducing nitrogen for 0.5-5 hours, then carrying out hydrothermal reaction, cooling and washing for a plurality of times after the reaction is finished, and carrying out freeze drying for 12 hours to obtain an MXene-carbon material three-dimensional composite carrier;

and 4, step 4: dispersing 0.1-40 parts of the MXene-carbon material three-dimensional composite carrier obtained in the step (3) into 1-40 parts of a solvent, and performing ultrasonic dispersion for 0.1-20 hours;

and 5: calculating the amount of a precursor of the required catalyst active particles according to the proportion that the mass of the catalyst active particles is 1-60% of the total mass of the catalyst, and adding the precursor of the required catalyst active particles into the dispersion liquid obtained in the step (4) after the precursor of the catalyst active particles is uniformly dispersed in a solvent by ultrasonic;

step 6: and (3) dropwise adding a reducing agent solution into the mixed dispersion liquid obtained in the step (5), washing with deionized water after dropwise adding is finished, and then placing in a vacuum drying oven for vacuum drying for more than 0.5 hour to obtain the three-dimensional MXene-based carrier hydrogen evolution catalyst.

In the preparation process of the invention, the raw materials comprise the following components in parts by mass:

the MXene is Ti₃C₂、Ti₂C、Nb₃C₂、Nb₂C、TiNbC、Cr₂TiC、Ti₃CN、Ti₄N₃、Ta₄C₃、V₂C、Mo₂C or MoTiC₂。

The carbon material is Graphene Oxide (GO), graphene, Carbon Nanotubes (CNT) or activated carbon.

The precursor of the active particles of the catalyst is H₂PtCl₆·6H₂O、PdCl₂、Na₂PdCl₄、K₂PdCl₆、NiCl₂、CoCl₂、CuCl₂、ZnCl₂Any one of the above.

The reducing agent is NaBH₄Hydrazine hydrate, LiBH₄And formaldehyde.

The solvent is any one of deionized water and ethylene glycol. The mass parts of the solvent refer to the total amount of the solvent used in the preparation process.

Further, the mass ratio of the MXene to the carbon material in the mixed solution is 0.1-10: 0.1 to 10.

Further, in the step 3, the reaction temperature of the hydrothermal reaction is 80-160 ℃, and the reaction time is 1-10 hours.

Further, the mass ratio of the reducing agent to the catalyst active particle precursor is 1-20: 1.

The invention has the beneficial effects that:

the invention prepares a new material with a three-dimensional structure by compounding MXene and a carbon material under high-temperature hydrothermal conditions, and the new material is used as a carrier of a catalyst for an electrolytic water hydrogen evolution reaction. The carrier has interconnected pores and is a porous three-dimensional structure. Compared with the traditional Pt/C catalyst, the hydrogen evolution catalyst prepared by utilizing the novel carrier has better electrocatalytic performance and electrochemical stability.

Drawings

FIG. 1 is Ti₃C₂T_x-a micro-topography of the GO three-dimensional composite support.

FIG. 2 is a graph in which Pt particles are supported on Ti₃C₂T_x-catalytic hydrogen evolution polarization curve of catalyst obtained on GO three-dimensional composite carrier in 1M KOH solution environment.

FIG. 3 is a graph in which Pt particles are supported on Ti₃C₂T_xAnd (3) testing the 25000s constant current stability of the catalyst obtained on the GO three-dimensional composite carrier in a 1M KOH solution environment.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.