阅读说明：本技术 一种水相等离子体气相沉积法制备过渡金属碳氮化物材料陶瓷膜层高效oer催化剂的方法 (Method for preparing transition metal carbonitride material ceramic film layer efficient OER catalyst by aqueous phase plasma vapor deposition method ) 是由 姚忠平 戴鹏程 夏琦兴 李东琦 姜兆华 于 2018-07-31 设计创作，主要内容包括：本发明公开了一种水相等离子体气相沉积法制备过渡金属碳氮化物材料陶瓷膜层高效OER催化剂的方法,属于催化剂制备领域,技术方案为：TC4钛基体前处理：镜面处理；将步骤一中得到的光亮的TC4基体置于电解液中,辉光放电,在TC4表面得到碳氮改性陶瓷膜层高效OER催化剂。本发明电解液体系简单,经济实用,且制备工艺简单。制得的OER催化剂可在1M KOH溶液中过电位降至200mV,法拉第效率高达90％,电子传输效率明显提升。(The invention discloses a method for preparing a transition metal carbonitride material ceramic film layer high-efficiency OER catalyst by a water-phase plasma vapor deposition method, which belongs to the field of catalyst preparation, and adopts the technical scheme that: pretreatment of a TC4 titanium substrate: mirror surface treatment; and (3) placing the bright TC4 substrate obtained in the step one in electrolyte, performing glow discharge, and obtaining the high-efficiency OER catalyst with the carbon-nitrogen modified ceramic film layer on the surface of TC 4. The electrolyte disclosed by the invention is simple in system, economical and practical, and simple in preparation process. The prepared OER catalyst can reduce the overpotential to 200mV in a 1M KOH solution, the Faraday efficiency reaches up to 90 percent, and the electron transmission efficiency is obviously improved.)

1. A method for preparing a transition metal carbonitride material ceramic film layer high-efficiency OER catalyst by a water-phase plasma vapor deposition method is characterized by comprising the following steps: the method comprises the following steps:

firstly, pretreatment of a TC4 titanium substrate: performing mirror surface treatment on the surface of a TC4 titanium substrate;

placing the bright TC4 matrix obtained in the step one into electrolyte in a stainless steel electrolytic tank to serve as a cathode, and connecting the stainless steel electrolytic tank with a positive electrode of a power supply to serve as an anode; the electrolyte consists of triethanolamine, formamide, urea, ammonium chloride and water;

thirdly, a micro-arc oxidation power supply is adopted for supplying power, glow discharge is carried out, and the high-efficiency OER catalyst with the carbon-nitrogen modified ceramic film layer is obtained on the surface of TC 4.

2. The method of claim 1, further comprising: the electrolyte in the second step consists of the following components in parts by mass or volume: 500-1000 mL of triethanolamine, 400-800 mL of formamide, 60-120 g of urea, 53-106 g of ammonium chloride and 100-200 mL of water.

3. The method of claim 2, further comprising: the first step is specifically as follows: firstly, polishing the surface of a TC4 titanium substrate into a mirror surface, and drying the mirror surface after washing.

4. The method of claim 3, further comprising: the first step is specifically as follows: grinding the surface of the TC4 titanium matrix by using sand paper until the surface of the TC4 matrix is a mirror surface; washing the surface of the TC4 titanium matrix with deionized water for 3 to 5 times, washing the surface of the TC4 titanium matrix with absolute ethyl alcohol for 3 to 5 times, and finally blowing and drying the surface of the TC4 titanium matrix with a blower in a room to obtain the bright surface of the TC4 titanium matrix.

5. The method of claim 4, further comprising: the sand paper is 500# sand paper, 1500# sand paper and 2500# sand paper, and the using sequence is sequentially used.

6. The method of claim 1, further comprising: and step three, the power voltage is 100-120V.

7. The method of claim 6, further comprising: and step three, the power frequency is 100 Hz.

8. The method of claim 7, further comprising: and step three, glow discharge is carried out under the condition that the duty ratio is 30% -40%, and the discharge time is 10min-15 min.

Technical Field

The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for preparing a transition metal carbonitride material ceramic film layer efficient OER catalyst by a water-phase plasma vapor deposition method.

Background

With the progress of the times, the problem of energy crisis is increasingly highlighted, so that the sustainable development of global economy is covered by serious crisis shadows. The development of renewable energy is now becoming a consensus. Wherein, the hydrogen energy has the characteristics of cleanness, reproducibility and abundant storage, and becomes a dazzling bright bead in new energy. The conventional method for preparing hydrogen is a petroleum cracking method, which, although it is technically simple and cost-effective and widely used, is unable to change the reality of global energy shortage, is not like drinking \40489andquenching thirst. Therefore, the development of a novel efficient method for preparing hydrogen energy becomes the key to whether the hydrogen energy can replace the traditional energy in the future.

The method for preparing hydrogen by electrolyzing water is a main source for preparing high-purity laboratory hydrogen for a long time, and the principle is that water is reduced to hydrogen on the surface of a cathode in a mode of an external power supply. The method has the advantages of simple operation, wide source of raw material water, high purity of the product hydrogen and the like, and occupies a certain amount of market in the field of hydrogen preparation. However, because the oxidation of water on the surface of the anode in the electrolytic loop into oxygen involves the transfer of four electrons, the electrochemical polarization is obvious, the overpotential is usually as high as more than 1V, the Faraday efficiency is low, and the electric energy loss is serious. Because the problems of high point position, poor stability, high cost and the like generally exist in the traditional OER electrocatalyst, the development of a novel efficient OER catalyst is the key point for overcoming the defects and solving the energy problem.

Disclosure of Invention

The invention aims to solve the defects of high overpotential, poor stability and high cost of the traditional OER electrocatalyst, and provides a method for preparing a transition metal carbonitride material ceramic membrane layer high-efficiency OER catalyst by an aqueous phase plasma vapor deposition method.

A method for preparing a transition metal carbonitride material ceramic film layer high-efficiency OER catalyst by a water-phase plasma vapor deposition method is completed according to the following steps:

firstly, pretreatment of a TC4 titanium substrate: performing mirror surface treatment on the surface of a TC4 titanium substrate;

placing the bright TC4 matrix obtained in the step one in an electrolyte in a stainless steel electrolytic tank to serve as a cathode, wherein the stainless steel electrolytic tank is connected with a positive electrode of a power supply to serve as an anode; the electrolyte consists of triethanolamine, formamide, urea, ammonium chloride and water;

thirdly, a micro-arc oxidation power supply is adopted for supplying power, glow discharge is carried out, and the high-efficiency OER catalyst with the carbon-nitrogen modified ceramic film layer is obtained on the surface of TC 4.

Preferably, the electrolyte in the second step is composed of the following components in parts by mass or volume: 500mL-1000mL of triethanolamine, 400mL-800mL of formamide, 60g-120g of urea, 53g-106g of ammonium chloride and 100mL-200mL of water

Preferably, the step one is specifically: firstly, polishing the surface of a TC4 titanium substrate into a mirror surface, and drying the mirror surface after washing.

Preferably, the step one is specifically: grinding the surface of the TC4 titanium matrix by using sand paper until the surface of the TC4 matrix is a mirror surface; washing the surface of TC4 matrix with deionized water for 3-5 times, washing the surface of TC4 titanium matrix with anhydrous ethanol for 3-5 times, and blow-drying with blower in room to obtain bright surface of TC4 titanium matrix

Preferably, the sandpaper of the first step is 500# sandpaper, 1500# sandpaper and 2500# sandpaper, and the using sequence is in turn.

Preferably, the power voltage in step three is 100-120V.

Preferably, the power supply frequency in the third step is 100 Hz.

Preferably, the glow discharge in the third step is performed under the condition that the duty ratio is 30% -40%, and the discharge time is 10min-15 min.

Advantageous effects

The carbon-nitrogen modified iron-nickel composite material ceramic film layer efficient OER catalyst is used for reducing the high overpotential phenomenon caused by electrochemical polarization on the surface of an anode in the water electrolysis process, and is beneficial to reducing the electric energy loss and improving the Faraday efficiency.

The invention has the advantages that:

the electrolyte disclosed by the invention is simple in system, economical and practical, and simple in preparation process.

The invention synthesizes the carbon-nitrogen modified iron-nickel ceramic film layer high-efficiency OER catalyst on the surface of TC4 by using a PCVD method for the first time.

The carbon and nitrogen modified iron-nickel ceramic film layer prepared by the method is a rough black film layer, the surface particles are covered by a porous structure, and the average pore diameter is 1-2 microns.

The invention can be used for producing the high-efficiency OER catalyst with the carbon-nitrogen modified transition metal ceramic film layer in a large scale.

The carbon-nitrogen modified iron-nickel ceramic membrane layer composite material OER catalyst prepared by the invention can reduce the overpotential to 200mV in a 1M KOH solution, the Faraday efficiency is up to 90%, and the electron transmission efficiency is obviously improved.

Description of the drawings:

FIG. 1: LSV curve of high efficiency OER catalyst prepared in example 1;

FIG. 2: tafel curve for the high efficiency OER catalyst prepared in example 1;

FIG. 3: CP curve of the high efficiency OER catalyst prepared in example 1;

FIG. 4: ECSA test curve for high efficiency OER catalyst prepared in example 1;

FIG. 5: the ac impedance spectrum of the high efficiency OER catalyst prepared in example 1;

FIG. 6: XPS of the high efficiency OER catalyst prepared in example 1 a) Fe spectra, b) N spectra, C) C spectra;

FIG. 7: the high efficiency OER catalyst prepared in example 1 SEM a) 5000-fold magnification, b) 10000-fold magnification.

Detailed Description