CN113664198A

CN113664198A - Rapid chemical coating method for compact gold nanoparticles and production equipment thereof

Info

Publication number: CN113664198A
Application number: CN202110977443.6A
Authority: CN
Inventors: 徐景锋; 黄进刚
Original assignee: Hangzhou Weijing Technology Co ltd
Current assignee: Hangzhou Weijing Technology Co ltd
Priority date: 2021-08-24
Filing date: 2021-08-24
Publication date: 2021-11-19
Anticipated expiration: 2041-08-24
Also published as: CN113664198B

Abstract

The invention provides a rapid chemical coating method of compact gold nanoparticles and production equipment thereof, wherein the method comprises the following steps: carrying out surface carboxylation treatment by taking silicon dioxide particles as a coating carrier; adding a reducing agent and an aminosilane coupling agent into a chloroauric acid solution to prepare an amino gold nanoparticle sol B; grafting the amino gold nanoparticle sol B onto the surface of the carboxyl silica particle A through the coupling effect of NHS/EDC to form a particle C containing a compact seed growth layer; and adding a reducing agent and a riboflavin mediator into the particles C, slowly injecting chloroauric acid solution, reacting for 0.5-1h, drying in vacuum, and calcining at a high temperature in an oxygen-insulated manner. The invention can obtain silicon dioxide particles with the surface gold film layer particle size of 5-40nm, and has good mercury enrichment and desorption effects; the recovery rate of mercury measured by a gold film enrichment-cold atom method can reach more than 96 percent, the cycle times can reach more than 3500 times, the product performance is stable, and the gold film particles on the surface are uniform.

Description

Rapid chemical coating method for compact gold nanoparticles and production equipment thereof

Technical Field

The invention relates to the technical field of coating production, in particular to a rapid chemical coating method of compact gold nanoparticles and production equipment thereof.

Background

The gold nanoparticles are widely applied to the fields of biomedicine, environmental monitoring and the like.

In environmental monitoring, mercury in ambient air is typically measured using gold film enrichment/cold atomic absorption spectrophotometry.

By utilizing the gold amalgam reaction, elemental mercury and gold can react at normal temperature, mercury can be evaporated and separated out at high temperature, the existing gold-plated particles have high manufacturing cost, complex flow, difficult control, uneven surface particles and large gold film particles, and the detection effect is influenced.

Therefore, it is necessary to provide a rapid chemical plating method of dense gold nanoparticles and a production apparatus thereof to solve the above technical problems.

Disclosure of Invention

The invention provides a rapid chemical coating method of compact gold nanoparticles and production equipment thereof, which solve the problem of uneven surface particles produced by the existing gold-plated particles.

In order to solve the technical problems, the rapid chemical plating method of the compact gold nanoparticles provided by the invention comprises the following steps:

A. step 1: preparing carboxyl silicon dioxide by taking silicon dioxide particles as a coating carrier; soaking in alkali liquor under ultrasonic condition for 0.5-1 h; vacuum drying after cleaning; then, adding carboxyethyl silanetriol sodium salt and hexadecyl trimethyl ammonium bromide into an ethanol system, carrying out ultrasonic water bath for 1-2h, cleaning, and carrying out vacuum drying to obtain surface-carboxylated silicon dioxide particles A;

B. step 2: adding 1 optional reducing agent and aminosilane coupling agent in chloroauric acid solution, and Cetyl Trimethyl Ammonium Bromide (CTAB) as stabilizer, and reacting for 1-2h in ultrasonic water bath at pH4-5 to obtain 5-20nm particle size of amino gold nanoparticle sol B;

C. and step 3: mixing the carboxylated silicon dioxide particles A obtained in the step 1 with the amino gold nanoparticle sol B obtained in the step 2, adding a coupling agent N-hydroxysuccinimide (NHS) and water-soluble carbodiimide (EDC) to couple carboxyl in the A and amino in the B to generate a stable amido bond, in the process, firstly adding EDC to activate carboxyl in the A for 30min, then adding NHS, and mixing for 10-20h at 40-60 ℃ to generate a stable amido bond, wherein the process mainly aims to graft a compact gold nanoparticle seed growth layer on the surface of the silicon dioxide particles so as to form a thicker gold film plating layer in the following step;

D. and 4, step 4: putting the material obtained in the step 3 into a container, adding a reducing agent solution and a riboflavin mediator at the same time, wherein the solid volume accounts for 20-80%; starting a stirrer, controlling the pH value to be 3-5.5, controlling the temperature to be 50-80 ℃, slowly adding chloroauric acid with the concentration of 1% -3% by using an injection pump, controlling the mass ratio of the chloroauric acid to the reducing agent to be 1: 2-3: 1, reacting for 0.5-1.0h, cleaning with deionized water, and performing vacuum drying;

E. and 5: calcining the material obtained in the step 4 in a tube furnace at the temperature of 700-.

Preferably, the mixed solution and the reducing agent in the step 2 are added in the step 4, the concentration is 0.5% -1%, and any one of the reducing agents can be sodium citrate, tannic acid, ascorbic acid, white phosphorus and sodium borohydride.

A rapid chemical plating production apparatus of compact gold nanoparticles comprising a rapid chemical plating method for compact gold nanoparticles in claims 1-2, comprising: a substrate;

the processing subassembly, the processing subassembly is fixed in on the base plate, the processing subassembly is including rotating a section of thick bamboo, the fixed surface of rotating a section of thick bamboo is connected with first gear to the inside sliding connection who rotates a section of thick bamboo has the agitator, the three hornblocks of inside fixedly connected with of agitator to the inside sliding connection of agitator has the clearance board, fixedly connected with pulling rod on the clearance board, fixedly connected with support frame on the base plate, fixedly connected with driving motor on the support frame, driving motor's output fixedly connected with second gear.

Preferably, the rotating cylinder is rotatably connected to the base plate, and a surface of the first gear is engaged with a surface of the second gear.

Preferably, the bottom fixedly connected with dysmorphism piece of agitator, the inside fixedly connected with dysmorphism groove of a section of thick bamboo rotates, dysmorphism piece with dysmorphism groove looks adaptation.

Preferably, the triangular blocks are arranged in a plurality, and the triangular blocks are uniformly distributed in the stirring barrel.

Preferably, the support frame is U-shaped, and the agitator is located one side of the support frame.

Preferably, the cleaning plate is connected with the triangular block in a sliding mode.

Preferably, the base plate is provided with a feeding assembly, the feeding assembly comprises a supporting rod, one end of the supporting rod is rotatably connected with a rotating disc, the rotating disc is provided with a plurality of storage barrels, the bottoms of the storage barrels are provided with discharging pipes, and the supporting rod is fixedly connected with a rubber block.

Preferably, the rubber block is connected with the rotating disc in a sliding mode, the material storage barrels are uniformly distributed on the rotating disc, the supporting rod is fixedly connected with the base plate, and the discharging pipe is provided with a control valve.

Compared with the related technology, the rapid chemical plating method of the compact gold nanoparticles and the production equipment thereof provided by the invention have the following beneficial effects:

the invention provides a rapid chemical coating method of compact gold nanoparticles and production equipment thereof, the method can compact a gold film layer on the surface, the particle size of the gold film particles is 5-40nm nanometer, the mercury enrichment and desorption effects are good, the recovery rate of mercury determined by adopting a gold film enrichment-cold atom method can reach more than 96%, the recycling frequency reaches more than 3500 times, and the enrichment effect in the mercury determination process is improved; the product has stable performance and uniform surface.

Drawings

FIG. 1 is a schematic structural diagram of a first embodiment of a rapid electroless plating method for dense gold nanoparticles and a production apparatus thereof according to the present invention;

FIG. 2 is a perspective view of the mixing drum shown in FIG. 1;

fig. 3 is a schematic structural diagram of a second embodiment of the rapid electroless plating method for dense gold nanoparticles and a production apparatus thereof according to the present invention.

Reference numbers in the figures: 1. the device comprises a base plate, 2, a processing assembly, 21, a rotating cylinder, 22, a first gear, 23, a stirring barrel, 24, a triangular block, 25, a cleaning plate, 26, a pulling rod, 27, a supporting frame, 28, a driving motor, 29, a second gear, 3, a feeding assembly, 31, a supporting rod, 32, a rotating disc, 33, a storage cylinder, 34, a discharging pipe, 35 and a rubber block.

Detailed Description

The invention is further described with reference to the following figures and embodiments.

First embodiment

Referring to fig. 1 and fig. 2, fig. 1 is a schematic structural diagram of a first embodiment of a rapid electroless plating method for dense gold nanoparticles and a production apparatus thereof according to the present invention; fig. 2 is a perspective view of the rotary cylinder shown in fig. 1. A rapid chemical coating method for dense gold nanoparticles comprises the following steps:

And (3) adding the mixed solution and the reducing agent in the step (2) in the step (4), wherein the concentration of the mixed solution and the reducing agent is 0.5-1%, and the reducing agent can be any one of sodium citrate, tannic acid, ascorbic acid, white phosphorus and sodium borohydride.

The method is mainly characterized in that NHS/EDC coupling agent is used for coupling the carboxylated silicon dioxide particles A and the aminated gold nanoparticles B, so that a gold seed layer is formed on the silicon dioxide particles, and the subsequent gold plating is facilitated.

A rapid chemical plating production apparatus of compact gold nanoparticles comprising a rapid chemical plating method for compact gold nanoparticles in claims 1-2, comprising: a substrate 1; processing subassembly 2, processing subassembly 2 is fixed in on the base plate 1, processing subassembly 2 includes a rotary drum 21, the fixed surface of a rotary drum 21 is connected with first gear 22 to the inside sliding connection who rotates a rotary drum 21 has agitator 23, the inside fixedly connected with triangle block 24 of agitator 23 to the inside sliding connection of agitator 23 has cleaning panel 25, fixedly connected with pulling rod 26 on the cleaning panel 25, fixedly connected with support frame 27 on the base plate 1, fixedly connected with driving motor 28 on the support frame 27, driving motor 28's output fixedly connected with second gear 29.

The driving motor 28 is powered by an external power supply, a control switch is arranged between the external power supply and the driving motor 28, the driving motor 28 adopts a servo motor, and the driving motor 28 can rotate in the reverse direction and the forward direction.

The method also comprises a rapid coating process, so that the enrichment effect in the mercury determination process is improved; the product has stable performance and uniform surface, and comprises the following steps:

the rotary cylinder 21 is rotatably connected to the base plate 1, and a surface of the first gear 22 is engaged with a surface of the second gear 29.

The rotation of the first gear 22 will cause the second gear 29 to rotate synchronously.

The bottom fixedly connected with dysmorphism piece of agitator 23, the inside fixedly connected with dysmorphism groove of a rotary drum 21, dysmorphism piece with dysmorphism groove looks adaptation.

Dysmorphism piece and dysmorphism groove are carried on spacingly to agitator 23 for agitator 23 can synchronous rotation when rotating a section of thick bamboo 21 rotation, and agitator 23 can be taken out by the inside that rotates a section of thick bamboo 21, and the bottom of agitator 23 is provided with the control valve, and the control can be discharged the principle, perhaps can take out agitator 23 by the inside that rotates a section of thick bamboo 21, emptys the raw materials.

The triangular blocks 24 are arranged in a plurality, and the triangular blocks 24 are uniformly distributed in the stirring barrel 23.

The triangular blocks 24 allow the liquid to collide when rotated, in the same principle as the washing machine.

The support frame 27 is U-shaped, and the stirring barrel 23 is located on one side of the support frame 27.

The cleaning plate 25 is connected with the triangular block 24 in a sliding mode.

The contact position of the cleaning plate 25 and the stirring barrel 23 is provided with a sealing gasket, so that the liquid can be prevented from flowing out.

When needs mix the raw materials, pour the raw materials into the inside of agitator 23, then it is rotatory by control switch control driving motor 28's output, driving motor 28's output rotation can drive second gear 29 rotatory, second gear 29 is rotatory can drive first gear 22 rotatory, first gear 22 is rotatory can drive a rotation section of thick bamboo 21 rotatory, it is rotatory that a rotation section of thick bamboo 21 is rotatory can drive agitator 23, thereby it is rotatory to make agitator 23 drive the inside raw materials of agitator 23, make the raw materials mix, and when needs carry out thorough clearance to the raw materials of the inside of agitator 23, upwards pulling rod 26, pulling rod 26 upwards removes and can drive clearance board 25 and upwards remove, make clearance board 25 can clear up the raw materials on the inner wall of agitator 23.

Carry out forward and reverse rotation through control switch control driving motor 28's output for can drive agitator 23 and the inside raw materials of agitator 23 and carry out forward and reverse rotation, make the inside raw materials of agitator 23 and three hornblocks 24 collisions, the mobility of raw materials has been increased, thereby reach the purpose that the raw materials mixes, the stirring through the puddler has been avoided, can make adhesion raw materials on the puddler, make to be difficult to clear up, the waste of raw materials also can be caused to the while.

the method can ensure that the surface gold film layer is compact, the particle size of gold film particles is 5-40nm nanoscale, the mercury enrichment and desorption effects are good, the recovery rate of mercury determined by adopting a gold film enrichment-cold atom method can reach more than 96%, the recycling frequency reaches more than 3500, and the enrichment effect in the mercury determination process is improved; the product has stable performance and uniform surface.

Second embodiment

Referring to fig. 3, based on a rapid chemical plating method for dense gold nanoparticles and a production apparatus thereof provided in the first embodiment of the present application, a second embodiment of the present application provides another rapid chemical plating method for dense gold nanoparticles and a production apparatus thereof. The second embodiment is only the preferred mode of the first embodiment, and the implementation of the second embodiment does not affect the implementation of the first embodiment alone.

Specifically, the difference between the rapid chemical plating method for dense gold nanoparticles and the production equipment thereof provided by the second embodiment of the present application lies in that the rapid chemical plating method for dense gold nanoparticles and the production equipment thereof are provided with the feeding assembly 3 on the substrate 1, the feeding assembly 3 includes the support rod 31, one end of the support rod 31 is rotatably connected with the rotating disc 32, the rotating disc 32 is provided with a plurality of storage barrels 33, the bottom of the storage barrels 33 is provided with the discharging pipe 34, and the support rod 31 is fixedly connected with the rubber block 35.

The rubber block 35 positions the rotating disk 32 so that the rotating disk 32 does not rotate without an external force.

The rubber block 35 is connected with the rotating disc 32 in a sliding mode, the storage barrels 33 are evenly distributed on the rotating disc 32, the supporting rod 31 is fixedly connected with the base plate 1, and the discharging pipe 34 is provided with a control valve.

The control valve seals the blanking pipe 34, so that the material in the blanking pipe 34 cannot flow out randomly, the blanking speed of the principle can be controlled by controlling the size of the control valve, and the principle can be controlled to be poured completely or be poured in a titration mode according to the requirement.

The working principle is as follows:

through the inside of pouring into storage cylinder 33 with the raw materials that will need to add, when one of them raw materials adds, rotatory rolling disc 32, the rolling disc 32 is rotatory can drive storage cylinder 33 rotatory, when the raw materials that needs to add is rotatory to storage cylinder 33's top, opens the control valve for the raw materials flows into the inside of agitator 23 through unloading pipe 34, thereby can accomplish the quick interpolation to the raw materials.

Has the advantages that:

through set up a plurality of storage barrels 33 on rolling disc 32 for can prepare the raw materials that need add, only need rotatory rolling disc 32 when needs add, make rolling disc 32 drive storage barrel 33 rotatory, thereby can add the top that the raw materials is rotatory to agitator 23 with needs, make and adjust the raw materials, need get the trouble of material and weighing when having avoided adding the raw materials.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims

1. A rapid chemical coating method for compact gold nanoparticles is characterized by comprising the following steps:

B. step 2: adding 1 optional reducing agent and aminosilane coupling agent in chloroauric acid solution, and cetyl trimethyl ammonium bromide as stabilizer, and reacting for 1-2h in ultrasonic water bath at pH4-5 to obtain 5-20nm particle size of aminogold nanoparticle sol B;

C. and step 3: mixing the carboxylated silicon dioxide particles A obtained in the step 1 with the amino gold nanoparticle sol B obtained in the step 2, simultaneously adding a coupling agent N-hydroxysuccinimide and water-soluble carbodiimide to couple carboxyl in the A with amino in the B to generate stable amido bond, in the process, firstly adding the water-soluble carbodiimide to activate the carboxyl in the A for 30min, then adding the coupling agent N-hydroxysuccinimide, and mixing for 10-20h at the temperature of 40-60 ℃ to generate stable amido bond, wherein the main purpose of the process is to graft a compact gold nanoparticle seed growth layer on the surface of the silicon dioxide particles, so that a thicker gold film plating layer can be formed in the following step;

2. The method for rapid electroless plating of gold-dense nanoparticles as claimed in claim 1, wherein the mixed solution and the reducing agent in step 2 are added in step 4 at a concentration of 0.5% to 1%, and optionally one of them is selected, wherein the reducing agent can be sodium citrate, tannic acid, ascorbic acid, white phosphorus, and sodium borohydride.

3. A rapid electroless plating production apparatus of densified gold nanoparticles for use in the rapid electroless plating method of densified gold nanoparticles claimed in any one of claims 1 to 2, comprising: a substrate;

4. The apparatus for rapid chemical plating production of densified gold nanoparticles according to claim 3, wherein the rotating cylinder is rotatably connected to the substrate, and the surface of the first gear is engaged with the surface of the second gear.

5. The equipment for producing dense gold nanoparticles through rapid chemical plating according to claim 3, wherein a special-shaped block is fixedly connected to the bottom of the stirring barrel, a special-shaped groove is fixedly connected to the inside of the rotating barrel, and the special-shaped block is matched with the special-shaped groove.

6. The equipment for producing the dense gold nanoparticles through the rapid chemical plating according to claim 3, wherein the triangular blocks are arranged in a plurality, and the triangular blocks are uniformly distributed in the stirring barrel.

7. The equipment for producing the dense gold nanoparticles through the rapid chemical plating according to claim 3, wherein the support frame is U-shaped, and the stirring barrel is positioned on one side of the support frame.

8. The apparatus for rapid electroless deposition of densified gold nanoparticles according to claim 3, wherein the cleaning plate is slidably connected to the triangular block.

9. The equipment for producing dense gold nanoparticles through rapid chemical plating according to claim 3, wherein a feeding assembly is arranged on the base plate, the feeding assembly comprises a supporting rod, one end of the supporting rod is rotatably connected with a rotating disc, a plurality of storage barrels are arranged on the rotating disc, a discharging pipe is arranged at the bottom of each storage barrel, and a rubber block is fixedly connected to the supporting rod.

10. The apparatus for rapid chemical plating production of gold nanoparticles as claimed in claim 9, wherein the rubber block is slidably connected to the rotating disc, the plurality of storage barrels are uniformly distributed on the rotating disc, the support rod is fixedly connected to the base plate, and the discharge tube is provided with a control valve.