阅读说明：本技术 一种二硫化钨/二氧化锰微马达及其制备与应用 (Tungsten disulfide/manganese dioxide micromotor and preparation and application thereof ) 是由 王莹 逯浩 李钟昊 谢忠洲 于 2021-09-30 设计创作，主要内容包括：本发明涉及一种二硫化钨/二氧化锰微马达及其制备与应用,所述制备方法包括以下步骤：(1)取模板进行预处理,之后在模板的一侧镀上一层导电层；(2)配制二硫化钨电沉积液和二氧化锰电沉积液；(3)将步骤(1)得到的模板置于电镀槽中,加入步骤(2)得到的二硫化钨电沉积液和二氧化锰沉积液,依次进行二硫化钨和二氧化锰的电沉积,之后进行后处理去除模板,得到所述二硫化钨/二氧化锰微马达。与现有技术相比,本发明制得的二硫化钨/二氧化锰微马达具有出色的催化性能,且制备方法简单,原料自然丰度高成本低,产物具有良好的化学稳定性,整个制备过程具有环境友好性。(The invention relates to a tungsten disulfide/manganese dioxide micromotor and preparation and application thereof, wherein the preparation method comprises the following steps: (1) pretreating a template, and plating a conductive layer on one side of the template; (2) preparing tungsten disulfide electrodeposition liquid and manganese dioxide electrodeposition liquid; (3) and (3) placing the template obtained in the step (1) in an electroplating bath, adding the tungsten disulfide electrodeposition solution and the manganese dioxide deposition solution obtained in the step (2), sequentially performing electrodeposition of tungsten disulfide and manganese dioxide, and performing aftertreatment to remove the template, thereby obtaining the tungsten disulfide/manganese dioxide micromotor. Compared with the prior art, the tungsten disulfide/manganese dioxide micromotor prepared by the invention has excellent catalytic performance, the preparation method is simple, the natural abundance of the raw materials is high, the cost is low, the product has good chemical stability, and the whole preparation process is environment-friendly.)

1. A preparation method of a tungsten disulfide/manganese dioxide micromotor is characterized by comprising the following steps:

(1) pretreating a template, and plating a conductive layer on one side of the template;

(2) preparing tungsten disulfide electrodeposition liquid and manganese dioxide electrodeposition liquid;

(3) and (3) placing the template obtained in the step (1) in an electroplating bath, adding the tungsten disulfide electrodeposition solution and the manganese dioxide deposition solution obtained in the step (2), sequentially performing electrodeposition of tungsten disulfide and manganese dioxide, and performing aftertreatment to remove the template, thereby obtaining the tungsten disulfide/manganese dioxide micromotor.

2. The method as claimed in claim 1, wherein in step (1), the template is made of polycarbonate.

3. The method according to claim 1, wherein in the step (1), the thickness of the conductive layer is 80nm, and the conductive layer is made of gold.

4. The method for preparing a tungsten disulfide/manganese dioxide micromotor according to claim 1, wherein in the step (2), the tungsten disulfide electrodeposition solution contains tungstic acid, sodium tungstate and sodium sulfite, and the molar ratio of the tungstic acid, the sodium tungstate and the sodium sulfite is 0.0054:0.0061: 0.0457.

5. The method of claim 1, wherein in step (2), said manganese dioxide bath comprises manganese acetate and sodium sulfite, and the molar ratio of manganese acetate to sodium sulfite is 0.0051: 0.0152.

6. The method for preparing a tungsten disulfide/manganese dioxide micromotor as claimed in claim 1, wherein in the step (3), during the deposition of tungsten disulfide, cyclic voltammetry is adopted for deposition, the voltage is 0.3-1.2V, the deposition rate is 40-60 mV/s, and 8-12 cycles are finished.

7. The method as claimed in claim 1, wherein in the step (3), the manganese dioxide is deposited by a constant voltage method, the voltage is 0.8-1.2V, the deposition time is 450-550 s, and the amount of deposited charge is 8-12C.

8. The method of claim 1, wherein in step (3), the deposited template is dried in a drying oven at 60 ℃ for 24 hours, then the conductive layer previously evaporated by heat is removed by nylon polishing cloth, and is washed clean by water, the template is dissolved by dichloromethane, and finally the template is washed by dichloromethane, alcohol and water respectively by a centrifuge at 6000 rpm for three minutes, and each solution is washed three times.

9. A tungsten disulfide/manganese dioxide micromotor obtainable by the process of any one of claims 1 to 8.

10. Use of a tungsten disulphide/manganese dioxide micromotor according to claim 9.

Technical Field

The invention relates to the technical field of micro-nano motors, in particular to a tungsten disulfide/manganese dioxide micro motor and preparation and application thereof.

Background

The nano robot is also called a nano motor, is a micron-sized material capable of autonomously moving in an environment, and shows movement characteristics very similar to those of microorganisms in many aspects. They can transform other forms of energy from a particular environment into mechanical energy to perform motion, for example, they can be dispersed and concentrated by controls like microorganisms. In addition, they can capture target cells and transport and release drugs to designated sites. In the aspect of environmental management, the nano robot can degrade pollutants in water. In most of these materials, the electrochemistry becomes an integral part. The deposition of non-metal oxides in electrochemical deposition mode is currently still a very well-developed process (especially WS)₂Much research on electrochemical deposition as a sulfide is not available, and WS is deposited in the same way as graphene₂Not necessarily the best way) to do so, the patent will describe how to do so in terms of solution formulation and specific deposition.

Patent CN110611455A is a hollow tubular MnO2 based micro motor with cubic Ag nano-particle inner surface and its preparation method, the preparation method comprises the following steps: step 1, taking a polycarbonate film subjected to Au sputtering as a working electrode, a platinum wire as an auxiliary electrode, an Ag/AgCl electrode as a reference electrode, pouring electrolyte of a PEDOT layer into an electrolytic cell, and performing electrochemical deposition of an outer PEDOT support layer of polyethylene dioxythiophene in a CHI 660E type electrochemical workstation; step 2, taking the polycarbonate film subjected to Au sputtering as a working electrode, a stainless steel sheet as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and performing Ag-doped MnO on the basis of the PEDOT support outer layer prepared in the step 1₂Electrochemical deposition of the inner layer; step 3, MnO containing PEDOT outer layer and Ag doping obtained in the step 2₂Polishing and dissolving the inner layer of polycarbonate film to obtain the hollow tubular micron motor (PEDOT/MnO)₂@ Ag). This patent provides a relatively mature MnO₂And Ag, and the patent provides a novel photocatalysisMaterial WS₂The electro-deposition mode is a cyclic voltammetry mode, and the prepared sample has a photocatalytic effect and can be applied more.

Disclosure of Invention

It is a first object of the present invention to provide a method of making a tungsten disulfide/manganese dioxide micromotor that provides an optimal solution for electrochemically deposited materials.

It is a second object of the present invention to provide a tungsten disulfide/manganese dioxide micromotor.

The purpose of the invention is realized by the following technical scheme:

a preparation method of a tungsten disulfide/manganese dioxide micromotor comprises the following steps:

(1) pretreating a template, and plating a conductive layer on one side of the template, wherein holes are formed in the template, and the conductive layer is plated on the surface of the template;

(2) preparing tungsten disulfide electrodeposition liquid and manganese dioxide electrodeposition liquid;

(3) and (3) placing the template obtained in the step (1) in an electroplating bath, adding the tungsten disulfide electrodeposition solution and the manganese dioxide deposition solution obtained in the step (2), sequentially performing electrodeposition of tungsten disulfide and manganese dioxide, and performing aftertreatment to remove the template to obtain the tungsten disulfide/manganese dioxide micromotor, wherein tungsten disulfide and manganese dioxide are electrodeposited in holes.

In the step (1), the template is made of polycarbonate, and the material can be dissolved without influencing a subsequent dissolution experiment and is low in cost.

In the step (1), the pretreatment process specifically comprises the following steps: and removing organic impurities on the surface of the template by using a vacuum plasma cleaner.

In the step (1), the thickness of the conducting layer is 80nm, and the conducting layer is made of gold.

In the step (2), the tungsten disulfide electrodeposition solution contains tungstic acid, sodium tungstate and sodium sulfite, wherein the molar ratio of the tungstic acid to the sodium tungstate to the sodium sulfite is 0.0054:0.0061: 0.0457.

In the step (2), manganese dioxide electrodeposition solution contains manganese acetate and sodium sulfite, and the molar ratio of manganese acetate to sodium sulfite is 0.0051: 0.0152.

And (2) respectively placing the prepared tungsten disulfide electrodeposition liquid and manganese dioxide electrodeposition liquid in a stirrer to stir for 15min so as to fully mix the compounds.

In the step (3), during electrodeposition, the electroplating bath and the electrochemical workstation are assembled, so that the reference electrode is connected with the AgCl electrode, the counter electrode is connected with the Pt electrode, and the working electrode is connected with the conducting layer on the template.

In the step (3), when tungsten disulfide is deposited, cyclic voltammetry deposition is adopted, the voltage is 0.3-1.2V, the deposition rate is 40-60 mV/s, 8-12 cycles are finished, the number of cycles influences the thickness of a deposited sample, and the greater the number of times, the thicker the thickness.

Preferably, during the deposition of tungsten disulfide, cyclic voltammetry is used for deposition, the voltage is 0.3-1.2V, the deposition rate is 50mV/s, and 10 cycles are ended.

In the step (3), when depositing manganese dioxide, a constant voltage method is adopted for deposition, the voltage is 0.8-1.2V, the deposition time is 450-550 s, and the deposition charge amount is 8-12C.

Preferably, in depositing manganese dioxide, a constant voltage method is used for deposition, the voltage is 1V, the deposition time is 500s, and the deposition charge amount is 10C.

In the step (3), the post-treatment process specifically comprises the following steps: and sequentially drying the deposited template, removing the conductive layer, cleaning, dissolving the template and cleaning for the second time. The method specifically comprises the following steps: drying the deposited template in a drying oven at 60 ℃ for 24h, removing the conductive layer on the previous thermal evaporation by using nylon polishing cloth, cleaning the conductive layer by using water, dissolving the template by using dichloromethane, and finally respectively using dichloromethane, alcohol and water to continuously wash the template for three minutes by using a centrifugal machine at the rotating speed of 6000 revolutions per minute, wherein the washing time is three times under each solution condition.

A tungsten disulfide/manganese dioxide micromotor is of a hollow tubular structure, a tungsten disulfide layer is an outer supporting layer, a manganese dioxide layer is an inner layer, the length of the tungsten disulfide/manganese dioxide micromotor is 13-15 mu m, and the outer diameter of the tungsten disulfide/manganese dioxide micromotor is 5 mu m.

An application of tungsten disulfide/manganese dioxide micromotor.

The tungsten disulfide is layered and can be used as an electrochemical active material of a micro super capacitor, and the manganese dioxide is a cheap catalytic material and can also be used for manufacturing a catalytic layer micro motor. According to the invention, tungsten disulfide is deposited on a polycarbonate template through an electrochemical workstation, then manganese dioxide is continuously deposited on a tungsten disulfide layer to serve as a catalytic layer of a micro motor and be used for driving a tubular micro motor, and then the template is removed, so that the hollow tungsten disulfide/manganese dioxide micro-nano motor is obtained. The tungsten disulfide/manganese dioxide micromotor prepared by the invention has excellent catalytic performance, the preparation method is simple, the natural abundance of the raw materials is high, the cost is low, the product has good chemical stability, and the whole preparation process is environment-friendly.

Drawings

FIG. 1 shows WS₂/MnO₂SEM images of the micromotors;

FIG. 2 shows WS₂/MnO₂Elemental semi-quantitative analysis of the micromotors;

FIG. 3 shows WS₂/MnO₂A flow chart for preparing the micromotor.

Detailed Description

The invention is described in detail below with reference to the figures and specific embodiments.

A preparation method of a tungsten disulfide/manganese dioxide micromotor comprises the following steps:

(1) taking polycarbonate as a template for pretreatment, and then plating a conductive layer on one side of the template, wherein the thickness of the conductive layer is 80nm, and the conductive layer is made of gold;

(2) preparing tungsten disulfide electrodeposition solution and manganese dioxide electrodeposition solution, wherein the tungsten disulfide electrodeposition solution contains tungstic acid, sodium tungstate and sodium sulfite, the molar ratio of the tungstic acid to the sodium tungstate to the sodium sulfite is 0.0054:0.0061:0.0457, the manganese dioxide electrodeposition solution contains manganese acetate and sodium sulfite, and the molar ratio of the manganese acetate to the sodium sulfite is 0.0051: 0.0152;

(3) placing the template obtained in the step (1) in an electroplating bath, adding the tungsten disulfide electrodeposition solution and the manganese dioxide deposition solution obtained in the step (2), sequentially performing electrodeposition of tungsten disulfide and manganese dioxide, drying the deposited template in a drying oven at 60 ℃ for 24 hours, removing the conductive layer on the previous thermal evaporation by using nylon polishing cloth, cleaning the template by using water, dissolving the template by using dichloromethane, finally continuously cleaning the template by using a centrifugal machine for three minutes by using dichloromethane, alcohol and water at the rotating speed of 6000 revolutions per minute, cleaning each solution for three times respectively to obtain the tungsten disulfide/manganese dioxide micromotor, depositing by using a cyclic voltammetry method when depositing tungsten disulfide, wherein the voltage is 0.3-1.2V, the deposition rate is 40-60 mV/s, 8-12 cycles are finished, and when depositing manganese dioxide, and (3) depositing by adopting a constant voltage method, wherein the voltage is 0.8-1.2V, the deposition time is 450-550 s, and the deposited electric charge amount is 8-12C.

A tungsten disulfide/manganese dioxide micromotor obtained by the preparation method.

Use of a tungsten disulphide/manganese dioxide micromotor as described above.

Example 1

A tungsten disulfide/manganese dioxide micromotor is of a hollow tubular structure, a tungsten disulfide layer is an outer supporting layer, a manganese dioxide layer is an inner layer, the length of the inner layer is 13-15 mu m, the outer diameter of the inner layer is 5 mu m, and the micromotor is prepared by adopting the process shown in figure 3:

(1) taking polycarbonate as a template, removing organic impurities on the surface of the template by using a vacuum plasma cleaner for pretreatment, and then plating a conductive layer with the thickness of 80nm on one side of the template by using a thermal evaporation instrument (the current is 110A, the evaporation rate is 1-2 per second, and the real thickness is equal to the number of readings of a film thickness meter/10 x 0.7), wherein the conductive layer is made of gold;

(2) preparing tungsten disulfide electrodeposition solution and manganese dioxide electrodeposition solution: 1.3492g of tungstic acid, 1.7812g of sodium tungstate and 5.76g of sodium sulfite are dissolved in 40mL of deionized water, then the mixture is placed in a stirrer to be stirred for 15min to fully mix all the compounds to obtain tungsten disulfide electrodeposition liquid, 0.876g of manganese acetate and 2.16g of sodium sulfate are fully dissolved in 30mL of deionized water, and then the mixture is placed in the stirrer to be stirred for 15min to fully mix all the compounds to obtain manganese dioxide electrodeposition liquid;

(3) placing the template obtained in the step (1) in an electroplating bath, adding the tungsten disulfide electrodeposition solution and the manganese dioxide deposition solution obtained in the step (2), assembling the electroplating bath and an electrochemical workstation, connecting a reference electrode with an AgCl electrode, connecting a counter electrode with a Pt electrode, connecting a working electrode with a conductive layer on the template, sequentially carrying out electrodeposition of tungsten disulfide and manganese dioxide, depositing tungsten disulfide by adopting a cyclic voltammetry method at a voltage of 0.3-1.2V and a deposition rate of 50mV/s, finishing 10 cycles, depositing manganese dioxide by adopting a constant voltage method at a voltage of 1V and a deposition time of 500s and a deposition charge amount of 10C, then placing the deposited template in a drying oven at 60 ℃ for drying for 24h, removing the conductive layer on the previous thermal evaporation by using nylon polishing cloth, and cleaning by using water, dissolving the template with dichloromethane, and finally washing with dichloromethane, alcohol, and water at 6000 rpm for three minutes each using a centrifuge, respectively, three times for each solution, to obtain a tungsten disulfide/manganese dioxide micromotor, as shown in FIG. 1, wherein WS is₂/MnO₂The micromotor growth was good individually and the EDX elements were consistent. When the motor was subjected to elemental semiquantitative analysis, as shown in fig. 2 and table 1, the micromotors produced in both fig. 2 and table 1 did contain corresponding amounts of oxygen, sulfur, manganese, and tungsten.

TABLE 1 eZAF Intelligent quantitation results

An application of tungsten disulfide/manganese dioxide micromotor in photocatalysis.

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.