阅读说明：本技术 与采用模板辅助法制备微纳米马达相适用的电镀槽及电镀 (Electroplating bath and electroplating suitable for preparing micro-nano motor by template auxiliary method ) 是由 王莹 逯浩 李钟昊 李贞� 于 2021-09-30 设计创作，主要内容包括：本发明涉及一种与采用模板辅助法制备微纳米马达相适用的电镀槽及电镀方法,所述电镀槽包括底座、反应器和弹性密封圈,所述反应器设置在底座上,所述反应器的中部贯穿开设有用于盛放电镀液的腔室,所述腔室的顶部开放,所述弹性密封圈沿周向设置在腔室的底部。电镀方法具体为：取表面镀有金的聚碳酸酯模板放置在通孔中,在反应器中加入电镀液,之后固定参比电极、对电极和工作电极并分别与电化学工作站相连接,工作电极和聚碳酸酯模板相接触,启动电化学工作站进行电镀沉积,重复多次直至电镀完成,得到微纳米马达。与现有技术相比,本发明可以连续进行多次电镀,为多次沉积材料提供了选择。(The invention relates to a plating bath and a plating method suitable for preparing a micro-nano motor by adopting a template-assisted method. The electroplating method comprises the following specific steps: placing the polycarbonate template with the gold-plated surface in the through hole, adding electroplating solution into the reactor, fixing the reference electrode, the counter electrode and the working electrode and respectively connecting the reference electrode, the counter electrode and the working electrode with the electrochemical workstation, enabling the working electrode to be in contact with the polycarbonate template, starting the electrochemical workstation to perform electroplating deposition, and repeating the steps for multiple times until the electroplating is completed to obtain the micro-nano motor. Compared with the prior art, the invention can continuously carry out multiple times of electroplating and provides a choice for depositing materials for multiple times.)

1. The utility model provides a plating bath that is suitable for with adopt template auxiliary method preparation micro-nano motor looks, its characterized in that, the plating bath includes base, reactor and elastic seal circle, the reactor sets up on the base, the middle part of reactor runs through and offers the cavity that is used for holding the plating solution, the top of cavity is open, elastic seal circle sets up the bottom at the cavity along circumference.

2. The electroplating bath suitable for preparing the micro-nano motor by the template-assisted method according to claim 1, wherein a plurality of connecting holes are formed in corners of the reactor in a penetrating manner, positioning holes matched with the connecting holes are formed in the base in a penetrating manner, the electroplating bath further comprises screws and butterfly nuts, the screws are inserted into the positioning holes and the connecting holes, and the butterfly nuts are arranged at ends of the screws.

3. The electroplating bath suitable for preparing the micro-nano motor by the template-assisted method according to claim 1, wherein the chamber is step-shaped and sequentially divided into an upper chamber and a lower chamber from top to bottom, the inner diameter of the upper chamber is smaller than that of the lower chamber, and the elastic sealing ring is positioned in the lower chamber.

4. The electroplating bath suitable for preparing the micro-nano motor by the template-assisted method according to claim 3, wherein the depth of the lower cavity is smaller than the thickness of the elastic sealing ring.

5. The electroplating bath suitable for preparing the micro-nano motor by the template-assisted method according to claim 1, wherein a support is further arranged in the chamber.

6. The electroplating bath suitable for preparing the micro-nano motor by the template-assisted method according to claim 1, wherein the base and the reactor are made of polytetrafluoroethylene;

the elastic sealing ring is made of rubber.

7. An electroplating method for preparing a micro-nano motor based on the electroplating tank as claimed in any one of claims 1 to 6, wherein the electroplating method specifically comprises the following steps: placing a polycarbonate template with a gold-plated surface in the bottom of a chamber, adding electroplating solution into the chamber of a reactor, fixing a reference electrode, a counter electrode and a working electrode, inserting the reference electrode, the counter electrode and the working electrode into the electroplating solution, respectively connecting the reference electrode, the counter electrode and the working electrode with an electrochemical workstation, contacting the working electrode with the polycarbonate template, starting the electrochemical workstation for electroplating deposition, pouring out the electroplating solution after one-time electroplating is completed, adding new electroplating solution for second electroplating, and repeating for multiple times until the electroplating is completed to obtain the micro-nano motor.

8. The electroplating method for preparing the micro-nano motor according to claim 7, wherein the reference electrode is AgCl, the counter electrode is platinum, and the working electrode is copper or aluminum.

9. The electroplating method for preparing the micro-nano motor according to claim 7, wherein the electroplating solution comprises chloroplatinic acid with a concentration of 0.01mol/l and sulfuric acid with a concentration of 0.5 mol/l;

or the electroplating solution comprises sodium sulfate with the concentration of 0.5mol/l, sulfuric acid with the concentration of 0.1mol/l and graphene with the concentration of 5 mol/l;

or the electroplating solution comprises copper sulfate with the concentration of 160g/L and boric acid with the concentration of 20 g/L;

or the plating bath contains NiCl at a concentration of 20g/L₂·6H₂O, Ni (H) at 515g/L₂NSO₃)₂·4H₂O and H with a concentration of 20g/L₃BO₃；

Or the electroplating solution contains sodium sulfate with the concentration of 0.5mol/l, sulfuric acid with the concentration of 0.1mol/l and aniline with the concentration of 0.1 mol/l;

or the electroplating solution contains manganese acetate with the concentration of 0.1mol/l and sodium sulfate with the concentration of 0.1 mol/l;

or the electroplating solution comprises 0.02mol/l of silver nitrate and 0.02mol/l of boric acid;

or the plating liquid contains gold chlorate of 0.01mol/l concentration and boric acid of 0.01mol/l concentration.

10. The electroplating method for preparing the micro-nano motor according to claim 7, wherein when metal or graphene is deposited on the surface of the polycarbonate template, electroplating deposition is performed by a constant current method, and the deposition conditions are as follows: the current is 2mA, and the deposition time is 200 and 400 s;

when depositing metal oxide on the surface of the polycarbonate template, electroplating deposition is carried out by adopting a potentiostatic method, wherein the deposition conditions are as follows: the voltage is 1V, the deposition time is 1000s, the sensitivity is 1e-001, and the charge amount is 20C as a control amount;

when nonmetallic sulfide is deposited on the surface of the polycarbonate template, electroplating deposition is carried out by adopting a moving point position method, and the deposition conditions are as follows: the maximum voltage is 0.3V, the minimum voltage is-1.5V, the cycle rate is 0.05V/s, the cycle period is 10, the sensitivity is 1e-001, and the deposition time is 65 s.

Technical Field

The invention belongs to the field of preparation of nano materials, and particularly relates to an electroplating bath and an electroplating method which are suitable for preparing a micro-nano motor by adopting a template auxiliary method.

Background

The micro-nano motor refers to micro-nano particles capable of converting chemical energy, optical energy, sound energy or other forms of energy into mechanical motion and completing complex tasks, and is generally called as a micro-nano motor because the micro-nano motor is similar to a motor in the traditional sense in function. The micro-nano motor is different from other colloidal particles which only do brownian motion on the micro-nano scale, and can realize the purpose of mechanical motion through the conversion between energy, so the micro-nano motor has very interesting application prospects in the aspects of drug transportation, biosensing, cell separation, environmental management and the like due to the unique motion characteristics and the size advantages of the micro-nano motor.

At present, the preparation methods of the micro-nano motor comprise a curling method, a solution etching method, a dry releasing method and a template assisting method. In the preparation of the tubular micromotor, the template auxiliary method is popular with people in a simple, efficient and mass production mode, but the template auxiliary method needs to combine an electrochemical workstation with electrolyte to complete the work, and the electroplating bath becomes a bridge for connecting the electrochemical workstation and the electrolyte. The previous electroplating tank is mostly in a totally-enclosed environment, and the electroplating tank needs to be disassembled, cleaned and reassembled after each electroplating.

Patent CN102808201A discloses an assembled all-plastic integral electrolytic tank, which comprises a tank body including a base, an electrolytic tank inner container and a plurality of partition walls, wherein the plurality of partition walls are arranged on the base to form an inner container frame, the electrolytic tank inner container is arranged in the inner container frame, and the upper part of the electrolytic tank inner container is open. The patent is suitable for industrial large-scale electrochemical deposition, can carry out a series of deposition processes, is limited in the application range of the invention only in the preparation of the tubular micromotor by a template-assisted method, has the advantages of simple operation, continuous electrodeposition, simple and convenient cleaning after each electrodeposition, and capability of fixing the polycarbonate template in the electroplating bath, thereby ensuring that the deposition process is more stable.

Disclosure of Invention

The invention aims to provide a plating bath suitable for preparing a micro-nano motor by adopting a template auxiliary method.

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

the utility model provides a plating bath that is suitable for with adopt template auxiliary method preparation micro-nano motor mutually, the plating bath includes base, reactor and elastic sealing circle, the reactor sets up on the base, the middle part of reactor is run through and is offered the cavity that is used for holding the plating solution, the top of cavity is open, elastic sealing circle sets up the bottom at the cavity along circumference. This plating bath adopts semi-enclosed structure, and the base is solid promptly, and the reactor is the fretwork, in the during operation, need add the plating solution to the reactor, and the outflow of plating solution can be prevented to the elastic sealing circle.

The electroplating bath further comprises a screw and a butterfly nut, the screw is inserted into the positioning hole and the connecting hole from bottom to top, and the butterfly nut is arranged at the top of the screw.

The cavity is step-shaped, and top-down divides into chamber and lower cavity in proper order, the internal diameter of going up the chamber is less than the internal diameter of chamber down, the elasticity sealing washer is arranged in the chamber down.

The depth of the lower cavity is smaller than the thickness of the elastic sealing ring, so that the elastic sealing ring can be in interference contact with the reactor and the base, and the tightness is guaranteed.

When the inner diameter of the upper chamber is 20mm, the inner diameter of the lower chamber is 26 mm;

when the thickness of the elastic sealing ring is 2mm, the depth of the lower cavity is 1.5 mm.

The inside diameter of the chamber is related to the size of the polycarbonate template used in the template-assisted process, and the reactor holds a maximum volume of 16ml of plating solution, typically 10ml of solution is dosed during electrodeposition.

The base is made of polytetrafluoroethylene.

The base is cuboid and 40 × 15mm in size.

The reactor is made of polytetrafluoroethylene.

The reactor was rectangular parallelepiped in shape with dimensions 40 x 30 mm.

The sizes of the contact surfaces of the base and the reactor are the same, and the heights of the base and the reactor are set according to the conditions.

The chamber is also provided with a bracket, the bracket is used for fixing a reference electrode, a counter electrode or a working electrode when electroplating is carried out, and the bracket can be a common micro bracket.

Another object of the present invention is to provide an electroplating method for preparing a micro-nano motor based on an electroplating bath, wherein the electroplating method specifically comprises: placing a polycarbonate template with a gold-plated surface at the bottom of a chamber, adding electroplating solution into the chamber of a reactor, fixing a reference electrode, a counter electrode and a working electrode (the positions of the reference electrode, the counter electrode and the working electrode can be placed according to conditions), inserting the reference electrode, the counter electrode and the working electrode into the electroplating solution, respectively connecting the reference electrode, the counter electrode and the working electrode with an electrochemical workstation, contacting the working electrode with the polycarbonate template, starting the electrochemical workstation for electroplating deposition, pouring out the electroplating solution after one-time electroplating is completed, adding new electroplating solution for second electroplating, and repeating for multiple times until the electroplating is completed to obtain the micro-nano motor. The gold plating on the polycarbonate template is intended to act as a conductive layer in the electrochemical deposition. In the process of preparing the micro-nano motor, the adopted template is similar to a porous culture dish, namely, a pore channel exists in the template, thermal evaporation gold plating is plated on the surface of the template, electrodeposition is to form a substance by ionizing ions and combining the ions on the pore wall of the pore channel of the template again, each pore channel is similar to a sandwich biscuit, the micro-nano motor grows completely after drying, the template is dissolved by dichloromethane after a conducting layer is removed, and only dispersed tubular micro-nano motors are left.

The reference electrode is AgCl and is connected with a white line of the electrochemical workstation, the counter electrode is platinum (adopting a platinum wire) and is connected with a red line of the electrochemical workstation, and the working electrode is copper or aluminum (adopting a copper foil or an aluminum foil with the width of 25 mm) and is connected with a green line of the electrochemical workstation.

The electroplating solution comprises chloroplatinic acid with the concentration of 0.01mol/l and sulfuric acid with the concentration of 0.5 mol/l;

or the electroplating solution comprises sodium sulfate with the concentration of 0.5mol/l, sulfuric acid with the concentration of 0.1mol/l and graphene with the concentration of 5 mol/l;

or the electroplating solution comprises copper sulfate with the concentration of 160g/L and boric acid with the concentration of 20 g/L;

or the plating bath contains NiCl at a concentration of 20g/L₂·6H₂O, Ni (H) at 515g/L₂NSO₃)₂·4H₂O and H with a concentration of 20g/L₃BO₃；

Or the electroplating solution contains sodium sulfate with the concentration of 0.5mol/l, sulfuric acid with the concentration of 0.1mol/l and aniline with the concentration of 0.1 mol/l;

or the electroplating solution contains manganese acetate with the concentration of 0.1mol/l and sodium sulfate with the concentration of 0.1 mol/l;

or the electroplating solution comprises 0.02mol/l of silver nitrate and 0.02mol/l of boric acid;

or the plating liquid contains gold chlorate of 0.01mol/l concentration and boric acid of 0.01mol/l concentration.

When metal or graphene is deposited on the surface of the polycarbonate template, a constant current method, namely chron, is adopted for electroplating deposition, and the deposition conditions are as follows: the current is 2mA, the deposition time is 200-400s, the sensitivity is 1e-001, and the metal is one or more of Pt, Au, Ag or Cu.

When depositing metal oxide on the surface of the polycarbonate template, performing electroplating deposition by adopting a potentiostatic method, namely i-t, wherein the deposition conditions are as follows: the voltage is 1V, the deposition time is 1000s, the sensitivity is 1e-001, the charge amount is 20C, and MnO can be used as the metal oxide₂。

When nonmetallic sulfide is deposited on the surface of the polycarbonate template, electroplating deposition is carried out by adopting a moving point position method, and the deposition conditions are as follows: maximum voltage of 0.3V, minimum voltage of-1.5V, cycle rate of 0.05V/s, cycle period of 10, sensitivity of 1e-001, deposition time of 65s, and non-metal sulfide selected from WS₂Or MoS₂One or more of; the duration of the deposition is determined by the cycle rate, when the deposition is carried out at a cycle rate of 0.01V/sThe time is about 330 s.

Compared with the prior art, the invention has the following advantages:

(1) the plating bath can be used for continuously carrying out multiple times of plating to obtain the multi-layer structure micro-nano motor, has simple structure, low manufacturing cost, firmness and corrosion resistance, and provides a choice for multiple times of material deposition.

(2) The invention takes the polycarbonate template as a carrier, controls the voltage and time of deposition through an electrochemical workstation, deposits multilayer nanotube materials in a three-electrode connection electroplating bath, and has convenient operation.

(3) The invention can clean in time after each electrodeposition and then continue the deposition of the next material, and has simple and convenient operation.

Drawings

FIG. 1 is a cross-sectional view of a plating cell at a location adjacent to a side edge thereof;

FIG. 2 is a cross-sectional view of the plating cell at a location near the center thereof;

FIG. 3 is a cross-sectional view of the plating bath from a top view;

FIG. 4 is a perspective view of the base;

FIG. 5 is a perspective view of the reactor;

fig. 6 is a schematic diagram of the prepared micro-nano motor;

7-9 are the deposition results of silver, gold and graphene obtained in example 2 in sequence;

FIG. 10 shows the deposition of manganese dioxide obtained in example 3;

FIG. 11 is Au @ MnO obtained in example 4₂Deposition results of micro-nano motors.

In the figure: 1-a base; 101-a positioning hole; 2-a reactor; 201-upper chamber; 202-a lower chamber; 203-connecting hole; 3-an elastic sealing ring; 4-a screw; 5-butterfly nuts; 6-a gasket; 7-a functional layer; 8-a guiding layer; 9-catalyst layer.

Detailed Description

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

Example 1

As shown in fig. 1, 2, 3, 4, and 5, an electroplating bath suitable for preparing a micro-nano motor by a template-assisted method includes a base 1, a reactor 2, an elastic sealing ring 3, a screw 4, and a wing nut 5, wherein the reactor 2 is disposed on the base 1, a plurality of connecting holes 203 are disposed at corners of the reactor 2, a positioning hole 101 adapted to the connecting hole 203 is disposed on the base 1, the screw 4 (with a long diameter) is inserted into the connecting hole 203 and the positioning hole 101, the wing nut 5 is disposed at an end of the screw 4 (in this embodiment, the wing nut is disposed at a bottom, a gasket 6 is disposed between the wing nut 5 and the base, and a gasket 6 is also disposed between a head of the screw and the reactor), a chamber for containing an electroplating solution is disposed at a middle of the reactor 2, a top of the chamber is open, the chamber is step-shaped, and is sequentially divided into an upper chamber 201 and a lower chamber 202 from top to bottom, the inner diameter of the upper chamber 201 is smaller than that of the lower chamber 202, the elastic sealing ring 3 is circumferentially positioned in the lower chamber 202, the depth of the lower chamber 202 is smaller than the thickness of the elastic sealing ring 3, and a bracket (omitted in the figure) can be arranged in the chamber. The base 1 and the reactor 2 are made of polytetrafluoroethylene, the base is in a cuboid shape and 40 × 15mm in size, the reactor is in a cuboid shape and 40 × 30mm in size, the elastic sealing ring 3 is made of rubber, the inner diameter of the upper chamber 201 is 20mm, the inner diameter of the lower chamber 202 is 26mm, the thickness of the elastic sealing ring 3 is 2mm, and the depth of the lower chamber is 1.5 mm.

The embodiment also provides an electroplating method for preparing the micro-nano motor based on the electroplating bath, and the electroplating method specifically comprises the following steps: placing a polycarbonate template with a gold-plated surface at the bottom of a chamber, adding electroplating solution into the chamber of a reactor, fixing a reference electrode, a counter electrode and a working electrode on a support, inserting the reference electrode, the counter electrode and the working electrode into the electroplating solution, respectively connecting the reference electrode, the counter electrode and the working electrode with an electrochemical workstation, connecting the reference electrode with a white line of the electrochemical workstation by adopting AgCl, connecting the counter electrode with a red line of the electrochemical workstation by adopting platinum (adopting a platinum wire), connecting the working electrode with a green line of the electrochemical workstation by adopting copper or aluminum (adopting copper foil or aluminum foil with the width of 25 mm), contacting the working electrode with the polycarbonate template, starting the electrochemical workstation for electroplating deposition, pouring out the electroplating solution after primary electroplating, adding new electroplating solution for secondary electroplating, repeating for multiple times until electroplating is completed, the obtained micro-nano motor has a structure shown in fig. 6, and sequentially comprises a functional layer, a guide layer and a catalyst layer from outside to inside, wherein the actual composition of each layer is related to the selection of electroplating solution.

The composition of the plating solution is shown in Table 1.

TABLE 1 composition List of the plating solutions

The expression "mass g/volume ml" in the tables means either weighed by mass or weighed by volume.

Example 2

When metal is deposited on the surface of the polycarbonate template, electroplating deposition is carried out by adopting a constant current method, and the deposition conditions are as follows: the current is 2mA, the deposition time is 200-400s, the sensitivity is 1e-001, the metal is one or more of Pt, Au, Ag or Cu, and FIGS. 7, 8 and 9 are specific deposition results, wherein FIG. 7 is obtained by silver nitrate deposition, FIG. 8 is obtained by gold chlorate deposition, and FIG. 9 is obtained by graphene deposition.

Example 3

When non-metal oxide or metal oxide is deposited on the surface of the polycarbonate template, electroplating deposition is carried out by adopting a potentiostatic method, and the deposition conditions are as follows: the voltage is 1V, the deposition time is 1000s, the sensitivity is 1e-001, the charge amount is 20C, and MnO can be used as the metal oxide₂Fig. 10 is a specific deposition outcome, wherein fig. 10 is obtained using acetic acid-based hard deposition.

Example 4

When nonmetallic sulfide is deposited on the surface of the polycarbonate template, electroplating deposition is carried out by adopting a moving point position method, and the deposition conditions are as follows: maximum voltage of 0.3V, minimum voltage of-1.5V, cycle rate of 0.05V/s, cycle period of 10, sensitivity of 1e-001, deposition time of 65s, and nonmetallic sulfide selected from WS₂Or MoS₂One or more of; the time is determined by the circulation rate, the deposition time is about 330s at the circulation rate of 0.01V/s, and fig. 11 is a specific deposition result, wherein fig. 11 is Au @ MnO obtained by sequentially depositing gold chlorate and acetic acid₂。

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.