CN110270284B - Fluid synthesis preparation device for preparing magnetic/precious metal composite nanoparticles - Google Patents

Fluid synthesis preparation device for preparing magnetic/precious metal composite nanoparticles Download PDF

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CN110270284B
CN110270284B CN201910573604.8A CN201910573604A CN110270284B CN 110270284 B CN110270284 B CN 110270284B CN 201910573604 A CN201910573604 A CN 201910573604A CN 110270284 B CN110270284 B CN 110270284B
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magnetic
pipe
mtio
component
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CN110270284A (en
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郭红燕
王儒敬
陈翔宇
魏圆圆
孙丙宇
黄河
刘宜
王大朋
王雪
王敏
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties

Abstract

The invention relates to a fluid synthesis preparation device for preparing magnetic/precious metal composite nano particles, which overcomes the defect that no synthesis device for preparing magnetic/precious metal composite nano materials exists in the prior art. The invention comprises Fe3O4Magnetic nanoparticle synthesis preparation component and Fe3O4@TiO2Synthesis preparation component of core-shell magnetic nanoparticles, Fe3O4@mTiO2Magnetic nanoparticle synthesis preparation component and Fe3O4@mTiO2Synthesizing and preparing a component from/noble metal magnetic composite nano particles. The invention designs a preparation device for synthesizing magnetic/precious metal composite nano particles, which can realize Fe by matching with a traditional control method based on a chemical process3O4@mTiO2The automatic preparation of the/noble metal nano material reduces the manual participation process, avoids the disturbance of manual operation, and has the characteristics of simple and convenient operation, less reagent demand and good repeatability.

Description

Fluid synthesis preparation device for preparing magnetic/precious metal composite nanoparticles
Technical Field
The invention relates to the technical field of chemical preparation devices, in particular to a fluid synthesis preparation device for preparing magnetic/precious metal composite nano particles.
Background
The microfluidic technology is a technology for processing or manipulating nano-liter fluid by using microchannels with the size of tens to hundreds of microns, and has the advantages of high surface area-to-volume ratio, accurate reaction parameter control, extremely short reaction time, extremely small solvent consumption and the like. The micro-fluidic chip of the main carrier is integrated with different functional operation units to quickly realize integration and automation, and the micro-fluidic chip is applied to the synthesis process of the multifunctional nano material, so that the process flows of preparation, cleaning and the like can be obviously simplified, and a large amount of materials can be saved.
Meanwhile, the Surface Enhanced Raman Scattering (SERS) technology is widely used in the fields of chemical industry, environment, food, biomedicine, public safety and the like due to the advantages of high detection sensitivity, fast detection time, simple sample pretreatment, nondestructive detection and the like. Various performance indexes of SERS depend on the effect of substrate preparation, and in order to better meet the application requirements of the SERS technology in various fields, the preparation of the SERS substrate with multiple functions and excellent performance becomes a key problem.
The nanometer material magnetic/noble metal complex not only has the inherent separation, enrichment and targeted tracing functions of the magnetic material, but also has the excellent optical performance of the noble metal, so that the nanometer material magnetic/noble metal complex becomes a multifunctional SERS substrate concerned by researchers.
Fe3O4@mTiO2The noble metal particles comprise nanoparticles such as Ag nanospheres (Ag NPs), gold nanospheres (Au NPs), silver-coated gold core-shell nanoparticles (Au @ Ag), gold nanorods (Au NR) and the like, and Fe is integrated3O4、TiO2And noble metals, and has wide application prospect. Fe3O4The nano particles are prepared by a hydrothermal method and used as a core, and the magnetic enrichment and recycling functions are achieved; mesoporous TiO 22The intermediate layer has large specific surface area and excellent adsorption performance, is used for enriching molecules to be detected, and also has catalytic activity, low cost, long-term stability and no toxicity; the introduction of the noble metal nano material endows the noble metal nano material with excellent optical performance。
However, the process of artificially synthesizing and preparing the nano material composite is extremely complex, the preparation and cleaning processes of the traditional artificial chemical method are complicated, the period is long, the consumption of the noble metal nano particles is large, the cost is too high, and the popularization and the use are not facilitated. Meanwhile, for those skilled in the chemical field, if a set of synthesis device hardware for preparing magnetic noble metal nanoparticles can be developed, a control method based on a chemical process flow can be proposed to realize automatic non-manual processing of magnetic noble metal nanoparticle preparation.
Therefore, how to incorporate Fe3O4@mTiO2The synthesis technology of the/noble metal is realized in automatic processing equipment, and the development of a set of hardware device for preparing the multifunctional magnetic/noble metal composite nano material, which is simple and convenient to operate, small in sample consumption and good in repeatability, is a technical problem which needs to be solved urgently.
Disclosure of Invention
The invention aims to solve the defect that no synthesis device for preparing magnetic/precious metal composite nano-materials exists in the prior art, and provides a fluid synthesis preparation device for preparing magnetic/precious metal composite nano-particles to solve the problems.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a fluid synthesis apparatus for preparing magnetic/noble metal composite nanoparticles comprises Fe3O4Magnetic nanoparticle synthesis preparation component and Fe3O4@TiO2Synthesis preparation component of core-shell magnetic nanoparticles, Fe3O4@mTiO2Magnetic nanoparticle synthesis preparation component and Fe3O4@mTiO2Synthesizing and preparing a component from a/noble metal magnetic composite nano particle;
said Fe3O4Synthetic product output port and Fe of magnetic nanoparticle preparation component3O4@TiO2Fe connected to the fluid inlet of the assembly for the synthesis of core-shell magnetic nanoparticles3O4@TiO2Synthesis preparation of core-shell magnetic nanoparticlesSynthesis product outlet and Fe of module3O4@mTiO2Fe connected to the fluid inlet of the assembly for the synthesis of magnetic nanoparticles3O4@mTiO2Synthetic product output port and Fe of magnetic nanoparticle synthesis preparation assembly3O4@mTiO2The fluid input ports of the/noble metal magnetic composite nanoparticle synthesis preparation component are connected.
Said Fe3O4The magnetic nanoparticle synthesis preparation assembly comprises a first micro-reaction cavity assembly and a second micro-reaction cavity assembly, wherein the first micro-reaction cavity assembly comprises a first micro-reaction cavity, the upper end of the first micro-reaction cavity is connected with an ethylene glycol supply pipe, the bottom of the first micro-reaction cavity is funnel-shaped, the first micro-reaction cavity is placed on a magnetic stirrer, a sieve plate is arranged in the first micro-reaction cavity, magnetons are placed on the sieve plate, the head end of a silica gel pipe is connected to the bottom of the first micro-reaction cavity, and the tail end of the silica gel pipe is connected to the upper end of the second micro-reaction cavity assembly;
the second micro-reaction cavity assembly comprises a second micro-reaction cavity and a magnet rotating assembly, the bottom of the second micro-reaction cavity is positioned above the radius of a magnet rotating track of the magnet rotating assembly, the bottom of the second micro-reaction cavity is funnel-shaped, a resistance heating wire is wound on the outer wall of the second micro-reaction cavity, a heat insulation asbestos sleeve is wrapped outside the second micro-reaction cavity, and a thermocouple is inserted into the heat insulation asbestos sleeve and is sleeved on the resistance heating wire;
the tail end of the silicone tube is also connected with a deionized water delivery pipe and an ethanol delivery pipe, the tail end of the silicone tube passes through a heat-insulating asbestos sleeve of the second micro-reaction cavity component to be inserted at the upper end of the second micro-reaction cavity, and Fe3O4The head end of the magnetic nano particle conveying pipe penetrates through a heat insulation asbestos sleeve of the second micro reaction cavity assembly to be connected to the bottom of the second micro reaction cavity.
The ethylene glycol supply pipe is provided with a first peristaltic pump and a first pinch valve, the silicone tube is provided with a second pinch valve, the deionized water conveying pipe is provided with a second peristaltic pump, the ethanol conveying pipe is provided with a third peristaltic pump, and the Fe conveying pipe is provided with a third peristaltic pump3O4The magnetic nano-particle delivery pipe is arrangedEquipped with a third pinch valve, Fe3O4A self-control drain pipe is connected between the third pinch valve and the second micro-reaction cavity on the magnetic nano-particle conveying pipe;
the magnet rotating assembly comprises a rotating rod, a clamp is fixedly mounted on the rotating rod, a magnet is clamped on the clamp, and the bottom of the second micro-reaction cavity is positioned above the radius of a rotating track of the magnet;
the temperature controller is characterized by further comprising a temperature controller, wherein one end of the temperature controller is connected to the thermocouple, and the other end of the temperature controller is connected to the resistance heating wire.
Fe3O4@TiO2The core-shell magnetic nano-particle synthesis preparation component comprises a magnet rotating component, a micro-fluidic chip and an ethanol solution cup, wherein Fe3O4The tail end of the magnetic nanoparticle conveying pipe is connected into the ethanol solution cup, one end of the first fluid conveying pipe is connected into the ethanol solution cup, the other end of the first fluid conveying pipe is connected to a first tee joint, one path of the first tee joint is connected to a second tee joint through a second fluid conveying pipe, the second fluid conveying pipe is connected to a self-control drain pipe, and the other path of the first tee joint is connected to a main inlet of the microfluidic chip; one path of the second tee joint is connected with Fe3O4@TiO2The head end of a core-shell magnetic nanoparticle conveying pipe, the other path of a second tee joint is connected to an outlet of a microfluidic chip, a first inlet of the microfluidic chip is connected with an acetonitrile conveying pipe, a second inlet of the microfluidic chip is connected with a concentrated ammonia water conveying pipe, and a third inlet of the microfluidic chip is connected with a tetrabutyl titanate conveying pipe; the bottom of the microfluidic chip is positioned above the radius of the magnet rotating track of the magnet rotating assembly.
The micro-fluidic chip comprises a bottom plate, wherein a mixing channel, micro-channels and a main channel are embedded in the bottom plate, the number of the micro-channels is 4, input ports of the 4 micro-channels are respectively communicated with a first inlet, a second inlet, a third inlet and the main inlet, output ports of the 4 micro-channels are converged on the main channel, the main channel is communicated with the inlets of the mixing channel, a plurality of arc-shaped bulges are arranged on the mixing channel, and an outlet of the mixing channel is communicated with one path of a second tee;
said Fe3O4@mTiO2Magnetic nanoparticle synthesis preparation assemblyThe structure of the third micro-reaction component is the same as that of the second micro-reaction cavity component;
said Fe3O4@TiO2The tail end of the core-shell magnetic nanoparticle conveying pipe is connected with an ethanol deionized water mixing agent cup, the head end of the third micro-reaction component conveying pipe is connected with the ethanol deionized water mixing agent cup, the tail end of the third micro-reaction component conveying pipe is connected with a third micro-reaction component, and the bottom of the third micro-reaction component is connected with Fe3O4@mTiO2Magnetic nanoparticle delivery tube, Fe3O4@mTiO2The magnetic nano particle delivery pipe is connected with a self-control drain pipe, and the tail end of the third micro reaction component delivery pipe is also connected with an ethanol delivery pipe, a concentrated ammonia water delivery pipe and a deionized water delivery pipe.
Said Fe3O4@mTiO2The synthetic preparation component of the/noble metal magnetic composite nano particles comprises a magnet rotating component and a synthetic micro-fluidic chip, the structure of the synthetic micro-fluidic chip is the same as that of the micro-fluidic chip, an electric heating sheet is attached to the bottom of the synthetic micro-fluidic chip, and the bottom of the synthetic micro-fluidic chip is positioned above the radius of a magnet rotating track of the magnet rotating component;
said Fe3O4@mTiO2The end of the magnetic nano-particle conveying pipe is inserted into the deionized water solution cup to synthesize the product Fe3O4@mTiO2The input end of the delivery pipe is inserted into the deionized water solution cup to synthesize the product Fe3O4@mTiO2The output end of the conveying pipe is connected to a fourth tee joint, one path of the fourth tee joint is communicated with the main inlet of the synthetic microfluidic chip, the other path of the fourth tee joint is connected with a fifth tee joint, one end of the fifth tee joint is connected to the outlet of the synthetic microfluidic chip, and the other end of the fifth tee joint passes through Fe3O4@mTiO2The output pipe of the/noble metal magnetic composite nano-particle is connected into a cup for synthesizing deionized water solution, Fe3O4@mTiO2The output pipe of the/noble metal magnetic composite nano-particles is provided with a self-control drain pipe, and the first inlet and the third inlet of the synthetic micro-fluidic chip are respectively connected with a polyelectrolyte solution pipe and a noble metal nano-particle input pipe.
The positive charge polyelectrolyte is introduced into the polyelectrolyte solution pipe, the silver nanosphere sol and Fe are introduced into the noble metal nanoparticle input pipe3O4@mTiO2Fe output in output pipe of magnetic composite nano particles of/noble metal3O4@mTiO2Ag composite nano-particles.
The positive charge polyelectrolyte is introduced into the polyelectrolyte solution pipe, the gold nanoparticle sol and Fe are introduced into the noble metal nanoparticle input pipe3O4@mTiO2Fe output in output pipe of magnetic composite nano particles of/noble metal3O4@mTiO2/Au composite nanoparticles.
The positive charge polyelectrolyte is introduced into the polyelectrolyte solution pipe, Au @ Ag core-shell nanoparticle sol and Fe are introduced into the noble metal nanoparticle input pipe3O4@mTiO2Fe output in output pipe of magnetic composite nano particles of/noble metal3O4@mTiO2the/Au @ Ag composite nano-particles.
The polyelectrolyte solution pipe is filled with negatively charged polyelectrolyte, the noble metal nanoparticle input pipe is filled with gold nanorod sol and Fe3O4@mTiO2Fe output in output pipe of magnetic composite nano particles of/noble metal3O4@mTiO2/AuNR composite nanoparticles.
Advantageous effects
Compared with the prior art, the fluid synthesis preparation device for preparing the magnetic/precious metal composite nano particles is designed, and can realize Fe by matching with a traditional control method based on a chemical process3O4@mTiO2The automatic preparation of the/noble metal nano material reduces the manual participation process, avoids the disturbance of manual operation, and has the characteristics of simple and convenient operation, less reagent demand and uniform nano particle products.
The fluid synthesis preparation device can realize Fe through related component equipment3O4@mTiO2Method for preparing/noble metal nano materialStep synthesis provides a hardware equipment foundation for non-artificial synthesis preparation. By Fe in the invention3O4Magnetic nano-particle synthesis preparation assembly equipment for synthesizing Fe3O4Magnetic nanoparticles; based on Fe3O4Magnetic nano-particles to synthesize Fe3O4@TiO2Core-shell magnetic nanoparticles; based on Fe3O4@TiO2Synthesis of Fe from core-shell magnetic nanoparticles3O4@mTiO2Mesoporous magnetic nanoparticles; finally based on Fe3O4@mTiO2The mesoporous magnetic nano-particles are synthesized into magnetic composite nano-particles so as to realize the synthesis and preparation of the magnetic/noble metal composite nano-particles.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 shows Fe in the present invention3O4A schematic diagram of a magnetic nanoparticle synthesis preparation assembly;
FIG. 3 shows Fe in the present invention3O4@TiO2A schematic of the structure of a core-shell magnetic nanoparticle synthesis preparation assembly;
FIG. 4 is a schematic structural diagram of a microfluidic chip according to the present invention;
FIG. 5 shows Fe in the present invention3O4@mTiO2A schematic diagram of a magnetic nanoparticle synthesis preparation assembly;
FIG. 6 shows Fe in the present invention3O4@mTiO2A structural schematic diagram of a component prepared by synthesizing/noble metal magnetic composite nano particles;
wherein, 1-Fe3O4Magnetic nanoparticle synthesis preparation component, 2-Fe3O4@TiO2Synthesis preparation component of core-shell magnetic nanoparticles, 3-Fe3O4@mTiO2Magnetic nanoparticle synthesis preparation component, 4-Fe3O4@mTiO2Synthetic preparation component of/noble metal magnetic composite nano-particles, 5-Fe3O4Magnetic nano particle conveying pipe, 6-magnet rotating component, 7-micro-fluidic chip, 8-electric heating plate and 9-Fe3O4@mTiO2A/noble metal magnetic composite nano particle output pipe, a 10-heat insulation asbestos sleeve, 11-a first micro reaction cavity, 12-ethylene glycol supply pipe, 13-a magnetic stirrer, 14-a sieve plate, 15-magnetons, 16-silica gel pipe, 17-a second micro reaction cavity, 18-a thermocouple, 19-a resistance heating wire, 21-an ethanol solution cup, 22-a first fluid conveying pipe, 23-a first tee joint, 24-a second fluid conveying pipe, 25-a second tee joint, 31-a third micro reaction component, 32-an ethanol deionized water mixing agent cup, 33-a third micro reaction component conveying pipe, 34-Fe3O4@mTiO2A magnetic nano particle delivery pipe, a 35-ethanol delivery pipe, a 36-concentrated ammonia water delivery pipe, a 37-deionized water delivery pipe, a 41-synthetic micro-fluidic chip, a 42-deionized water solution cup and a 44-synthetic product Fe3O4@mTiO2A delivery pipe, a 45-fourth tee joint, a 46-polyelectrolyte solution pipe, a 47-noble metal nanoparticle input pipe, a 48-fifth tee joint, a 49-deionized water solution cup, a 50-delivery pipe, a 51-first peristaltic pump, a 52-first pinch valve, a 53-second pinch valve, a 54-deionized water delivery pipe, a 55-ethanol delivery pipe, a 56-second peristaltic pump, a 57-third peristaltic pump, a 58-third pinch valve, a 59-rotating rod, a 60-clamp, a 61-magnet, a 62-temperature controller, a 70-tetrabutyl titanate delivery pipe, a 71-main inlet, a 72-outlet, a 73-first inlet, a 74-acetonitrile delivery pipe, a 75-second inlet, a 76-concentrated ammonia delivery pipe, a 77-third inlet, 78-bottom plate, 79-micro channel, 80-main channel, 81-mixing channel, 82-arc projection, 83-guide plate.
Detailed Description
So that the manner in which the above recited features of the present invention can be understood and readily understood, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings, wherein:
as shown in FIG. 1, a fluid synthesis preparation apparatus for preparing magnetic/noble metal composite nanoparticles comprises Fe3O4Magnetic nanoparticle synthesis preparation component 1, Fe3O4@TiO2Synthesis preparation of component 2, Fe, from core-shell magnetic nanoparticles3O4@mTiO2Magnetic nanoparticle synthesis preparation component 3 and Fe3O4@mTiO2Synthesis of/noble metal magnetic composite nanoparticles to prepare component 4, wherein Fe3O4Magnetic nanoparticle synthesis preparation assembly 1 for preparing Fe3O4Magnetic nanoparticles, Fe3O4@TiO2Core-shell magnetic nanoparticle synthesis preparation component 2 for use in Fe3O4Synthesizing Fe based on magnetic nano-particles3O4@TiO2Core-shell magnetic nanoparticles, Fe3O4@mTiO2Magnetic nanoparticle synthesis preparation component 3 for use in Fe3O4@TiO2Synthesis of Fe based on core-shell magnetic nanoparticles3O4@mTiO2Magnetic nanoparticles, finally, based on Fe3O4@mTiO2Magnetic nano-particles are prepared into Fe by matching with different addition synthesis reactions3O4@mTiO2@ Ag magnetic composite nanoparticles, i.e., magnetic/noble metal composite nanoparticles.
Fe3O4Synthetic product output port and Fe of magnetic nanoparticle production module 13O4@TiO2The fluid input ports of the core-shell magnetic nanoparticle synthesis preparation component 2 are connected, and Fe3O4@TiO2Synthesis product output port and Fe of core-shell magnetic nanoparticle synthesis preparation component 23O4@mTiO2The fluid input ports of the magnetic nanoparticle synthesis preparation component 3 are connected, and Fe3O4@mTiO2Synthetic product output port and Fe of magnetic nanoparticle synthesis preparation component 33O4@mTiO2The fluid input port of the/noble metal magnetic composite nano particle synthesis preparation component 4 is connected.
From the chemical field, Fe3O4The preparation process of the magnetic nanoparticles is as follows: 1.08g of FeCl3·6H2Dissolving O in 20ml of ethylene glycol, sequentially adding 0.2g of trisodium citrate and 1.2g of anhydrous sodium acetate, and magnetically stirring for half an hour to fully dissolve (realized by a first micro-reaction cavity component); transferring the mixture into a 40mL polytetrafluoroethylene reaction kettle, filling the kettle into a kettle sleeve, and placing the kettle sleeve in an oven to react for 10 hours at 200 DEG CAfter cooling at room temperature, a black product was obtained. And collecting the product under the action of an external magnet, sequentially cleaning the product with deionized water and ethanol (realized by a second micro-reaction cavity component), finally placing the product in a vacuum drying oven at 60 ℃, and taking out the product for later use after 6 hours.
As shown in FIG. 2, in order to incorporate Fe3O4Realization of magnetic nanoparticle chemical preparation method (control method), design of Fe3O4The magnetic nanoparticle synthesis preparation assembly 1 comprises a first micro-reaction cavity assembly and a second micro-reaction cavity assembly, the first micro-reaction cavity assembly comprises a first micro-reaction cavity 11, and the first micro-reaction cavity 11 is used for simulating Fe3O4Magnetic stirring process in the preparation process of the magnetic nano-particles.
The upper end of the first micro-reaction chamber 11 is connected to a glycol supply tube 12, and a first peristaltic pump 51 and a first pinch valve 52 can be added to the glycol supply tube 12 according to the conventional technology, so as to provide 20ml of glycol. The bottom of the first micro reaction chamber 11 is funnel-shaped to facilitate the collection of the powder sample. The first micro-reaction chamber 11 is placed on a magnetic stirrer 13 to achieve a magnetic stirring effect. A sieve plate 14 is arranged in the first micro-reaction chamber 11, and a magneton 15 is placed on the sieve plate 14 to be matched with magnetic stirring for use. The head end of the silicone tube 16 is connected to the bottom of the first micro-reaction cavity 11, and the tail end of the silicone tube 16 is connected to the upper end of the second micro-reaction cavity component, so that the first micro-reaction cavity 11 is transferred to the second micro-reaction cavity 17.
The second micro-reaction cavity component is used for simulating and realizing processing links such as heating of the polytetrafluoroethylene reaction kettle, and comprises a second micro-reaction cavity 17 and a magnet rotating component 6.
The magnet rotating assembly 6 is used to achieve an external magnet effect to facilitate product collection. The magnet rotating assembly 6 comprises a rotating rod 59, a clamp 60 is fixedly mounted on the rotating rod 59, the clamp 60 can be driven by the rotating rod 59 to rotate, and a magnet 61 is clamped on the clamp 60, so that the magnet 61 rotates according to the rotation of the rotating rod 59. The bottom of second microreaction cavity 17 is located magnet 61's rotation orbit radius top, and magnet rotating assembly 6 installs on relevant equipment platform through traditional mode, when needs carry out the product with the help of magnetism and collect, and magnet 61 can rotate to the bottom of second microreaction cavity 17 under the control of rotary rod 59 to realize magnetism and collect the function.
Also, the bottom of the second micro-reaction chamber 17 is funnel-shaped to facilitate the collection of the composition. A resistance heating wire 19 is wound on the outer wall of the second micro-reaction cavity 17, a heat insulation asbestos sleeve 10 is wrapped outside the second micro-reaction cavity 17, and a thermocouple 18 is inserted into the heat insulation asbestos sleeve 10 and connected onto the resistance heating wire 19, so that the polytetrafluoroethylene reaction kettle is loaded into a kettle sleeve and placed in an oven at 200 ℃. The temperature is controlled by a conventional temperature controller 62, the temperature controller 62 being connected at one end to the thermocouple 18 and at the other end to the resistance heating wire 19. The tail end of the silicone tube 16 is also connected with a deionized water delivery pipe 54 and an ethanol delivery pipe 55, and similarly, the silicone tube 16 is provided with a second pinch valve 53, the second pinch valve 53 is used for controlling the delivery of the composition in the silicone tube 16, the deionized water delivery pipe 54 is provided with a second peristaltic pump 56, and the ethanol delivery pipe 55 is provided with a third peristaltic pump 57 which is respectively used for controlling the delivery of the deionized water and the delivery of the ethanol.
The tail end (output end) of the silicone tube 16 passes through the heat-insulating asbestos sleeve 10 of the second micro-reaction cavity component and is inserted at the upper end of the second micro-reaction cavity 17, and Fe3O4The head end of the magnetic nano particle conveying pipe 5 passes through a heat insulation asbestos sleeve 10 of the second micro reaction cavity component to be connected to the bottom of the second micro reaction cavity 17 at Fe3O4An automatic control drain pipe is connected between the third pinch valve 58 and the second micro-reaction cavity 17 on the magnetic nano-particle conveying pipe 5, the automatic control drain pipe is a traditional drain pipe additionally provided with an automatic control valve and used for discharging waste liquid in the treatment process, and an electric control valve is arranged on the automatic control drain pipe for drain switch control. Fe3O4The magnetic nano-particle conveying pipe 5 is used for synthesizing and preparing Fe3O4Magnetic nanoparticles are transported to the next processing assembly (Fe)3O4@TiO2Core-shell magnetic nanoparticle synthesis preparation component 2).
Fe3O4Working process of magnetic nanoparticle synthesis preparation assembly 1The following were used:
(1) weighing three powder samples of ferric chloride hexahydrate, trisodium citrate and anhydrous sodium acetate, putting the three powder samples into a cavity of a first micro-reaction cavity 11, starting a first peristaltic pump 51 and a first pinch valve 52, and injecting glycol into the cavity of the first micro-reaction cavity 11 through a glycol supply pipe 12;
(2) starting the magnetic stirrer 13, stirring the reaction solution by utilizing the magnetons 15 in the first micro reaction cavity 11, and closing the magnetic stirrer 13 after half an hour; opening a second pinch valve 53, introducing the liquid which is completely reacted in the silicone tube 16 into a second micro-reaction cavity component, and sending the liquid into a second micro-reaction cavity 17;
(3) starting the temperature controller 62 to control the resistance heating wire 19 to heat to 200 ℃, and after the heating wire is continuously heated for 10 hours, closing the heating wire 1, and after waiting for two hours, finishing natural cooling;
(4) the magnet rotating component 6 drives the magnet 61 to be placed below the second micro-reaction cavity 17, and the product Fe is obtained under the action of the magnet 613O4Collecting the magnetic nano particles, and depositing the magnetic nano particles at the bottom of the second micro-reaction cavity 17;
(5) by the traditional pipeline control flow technology, the third pinch valve 58 is closed, the self-control drain pipe is opened, and the liquid in the second micro-reaction cavity 17 is discharged through the self-control drain pipe;
(6) cleaning with deionized water: closing the automatic control drain pipe, driving the magnet 61 to reset by the magnet rotating assembly 6, moving out of the lower part of the second micro-reaction cavity 17, opening the second peristaltic pump 56, introducing deionized water through the deionized water conveying pipe 54, driving the magnet 61 to move to the lower part of the second micro-reaction cavity 17 by the magnet rotating assembly 6, opening the automatic control drain pipe, and discharging the deionized water; carrying out multiple deionized water cleaning steps;
(7) ethanol cleaning: resetting the magnet 61, starting the third peristaltic pump 57, introducing ethanol through the ethanol conveying pipe 55, repeating the displacement of the magnet 61 in the same way as the previous step, and starting to discharge the ethanol by matching with a self-control water discharge pipe; and ethanol cleaning is carried out for a plurality of times;
(8) finally, the third pinch valve 58 is opened to let Fe go3O4Magnetic nanoparticles to Fe3O4@TiO2Core-shell magnetic nanoparticle synthesis fabrication module 2 is processed.
From the chemical field, Fe3O4@TiO2The preparation process of the core-shell magnetic nanoparticles is as follows:
30mg of Fe prepared as described above3O4After ultrasonic dispersion in 90mL of ethanol and 30mL of acetonitrile, 0.5mL of concentrated ammonia water was added thereto after complete ultrasonic dispersion (about 30 minutes), and ultrasonic dispersion was continued for 15 minutes. Then 0.5mL of tetrabutyl titanate (TBOT) was added dropwise thereto, and after complete addition, mechanical stirring was carried out for 1.5 hours while applying ultrasound, and finally collection was carried out under the action of a magnet, and washing was carried out with absolute ethanol at least 6 times.
As shown in FIGS. 1 and 3, to incorporate Fe3O4@TiO2Realization of the chemical preparation method (control method) of core-shell magnetic nanoparticles, Fe3O4@TiO2The core-shell magnetic nano particle synthesis preparation component 2 comprises a magnet rotating component 6, a micro-fluidic chip 7 and an ethanol solution cup 21, wherein the magnet rotating component 6 and Fe3O4The magnet rotating assembly in the magnetic nanoparticle synthesis preparation assembly 1 is identical.
Said Fe3O4The tail end of the magnetic nano particle conveying pipe 5 is connected into an ethanol solution cup 21, and Fe is added3O4Fe prepared by magnetic nano-particle synthesis preparation component 13O4And (3) sending the magnetic nanoparticles into 90mL of ethanol for ultrasonic dispersion.
One end of the first fluid delivery pipe 22 is connected into the ethanol solution cup 21, and the other end is connected to a first tee 23 (a first path), wherein the first tee 23 is of a traditional pipeline tee structure, and one path (a second path) of the first tee 23 is connected to a second tee 25 through a second fluid delivery pipe 24 so as to realize a circulation effect; the other (third) of the first tee 23 is connected to the main inlet 71 of the microfluidic chip 7. In the same way, the second fluid delivery pipe 24 is also connected with a self-control drainage pipe for the relevant reagent discharge treatment.
One path of the second tee joint 25 is connected with Fe3O4@TiO2Core-shell magnetic nanoparticlesHead end of delivery pipe for Fe after production3O4@TiO2Core-shell magnetic nanoparticles to Fe3O4@mTiO2The magnetic nano-particle synthesis preparation component 3 is used for synthesis treatment, and the other path of the second tee 25 is connected to the outlet 72 of the microfluidic chip 7 and is used for circulation treatment matched with the microfluidic chip 7.
An acetonitrile delivery pipe 74 is connected to a first inlet 73 of the microfluidic chip 7, a concentrated ammonia water delivery pipe 76 is connected to a second inlet 75, and a tetrabutyl titanate delivery pipe 70 is connected to a third inlet 77 and is used for injecting acetonitrile, concentrated ammonia water and tetrabutyl titanate respectively. The bottom of the microfluidic chip 7 is positioned above the radius of the magnet rotating track of the magnet rotating component 6, and particles are also adsorbed by magnetism in the circulating cleaning process so as to facilitate the discharge of related lotion.
As shown in fig. 4, the microfluidic chip 7 includes a bottom plate 78, a mixing channel 81, a micro channel 79 and a main channel 80 embedded in the bottom plate 78, and the number of the micro channels 79 is 4. The input ports of the 4 micro-channels 79 are respectively communicated with the first inlet 73, the second inlet 75, the third inlet 77 and the main inlet 71, the output ports of the 4 micro-channels 79 are converged on the main channel 80, and the main channel 80 is communicated with the inlet of the mixing channel 81.
Here, the micro-fluidic chip 7 is provided with three sample inlets and a main inlet, the three sample inlets can satisfy the mixing requirement of two to three solutions, and simultaneously, the three sample inlets and the main inlet converge at the first narrow convergence port (main channel 80) of the main channel, and the narrow convergence port (main channel 80) is used for converging the solution in the micro-channel, thereby disturbing laminar flow and improving hydraulic pressure.
The plurality of arc-shaped protrusions 82 are divided into two array combination modes: the two guide plates 83 are arranged at the tail end of the first array of the arc-shaped bulges 82 and the tail end of the second array of the arc-shaped bulges 82, the two guide plates 83 are in a shape like a Chinese character 'ba', wide openings of the two guide plates 83 face the incoming flow direction, narrow openings of the two guide plates 83 face the outgoing flow direction, one sides of the two guide plates 83 are respectively connected with the side wall of the mixing channel 81, and the extension lines of the other sides of the two guide plates 83 form an included angle of 45-60 degrees. The baffle 83 is a rectangular microstructure, the height of the arc-shaped protrusions 82 and the height of the baffle 83 are the same as the height of the mixing channel 81, the width of the narrowest opening of the main channel 80 is less than hundred micrometers, and the arc-shaped protrusions 82 in adjacent rows in the first array of the arc-shaped protrusions 82 are arranged in a staggered manner.
The mixing channel 81 is provided with a plurality of arc-shaped protrusions 82, the arc-shaped protrusions 82 are in a fish scale shape from a top view angle, the plurality of arc-shaped protrusions 82 form a fish scale-shaped microstructure array, the fish scale-shaped microstructure array has a strong micro mixing function, the microfluidic laminar flow is difficult to mix, and the mixing effect is enhanced by arranging the fish scale array. Meanwhile, the circulation can be carried out through an external peristaltic pump, so that repeated mixing is realized. Meanwhile, the height of the mixing channel 81, the micro channel 79 and the main channel 80 is in the micrometer scale, and the bottom plate 78 is made of PTFE/PEEK or PDMS. The outlet 72 of the mixing channel 81 is communicated with one path of the second tee 25 for water path circulation or Fe after synthesis3O4@TiO2And (4) outputting the core-shell magnetic nanoparticles.
The design of the micro-fluidic chip 7 simulates the ultrasonic dispersion effect in a chemical processing method, a first fish scale micro-structure array is arranged close to a first narrow convergence port, the height of the first fish scale micro-structure array is equal to that of a channel, three rows of fish scale micro-structures are arranged along the direction of a main channel, and two adjacent rows of micro-structures are arranged in an alternating mode. The individual microstructures are semi-circular in configuration with the first distance slot being less than one hundred microns. The solution passes through a narrow gathering port with high hydraulic pressure and then immediately collides with the first scaly microstructure to completely disturb laminar flow, and the mixing is completed under micro disturbance. The rear end of the first scaly microstructure array is provided with a first flow guide block, the flow guide block is a rectangular microstructure, and the height of the flow guide block is equal to the height of the microchannel. The guide block is arranged on the side wall of the main channel, forms an included angle of 45-60 degrees with the main channel, and plays a role of a second narrow gathering port. A second scaly microstructure array and a second flow guide block are arranged behind the first flow guide block, the structure of the second flow guide block is the same as that of the first flow guide block, and the mixing effect is further improved in a single circulation.
Fe3O4@TiO2The working process for the synthesis of core-shell magnetic nanoparticles to prepare the component 2 is as follows:
(1) dissolving Fe in ethanol3O4Magnetic nano particles are sent into the micro-fluidic chip 7, and simultaneously, concentrated ammonia water and tetrabutyl titanate (TBOT) are controlled to be introduced;
(2) fe mixed with ethanol, concentrated ammonia water and tetrabutyl titanate (TBOT)3O4The magnetic nano particles are mixed and synthesized on the micro-fluidic chip 7 and fully react, and in practical application, if the synthetic effect is increased, a peristaltic pump can be additionally arranged on the micro-fluidic chip 7 in a traditional mode;
(3) the magnet rotating component 6 moves the magnet above the microfluidic chip 7, and the product Fe is obtained through the action of the magnet3O4@TiO2Collecting the core-shell magnetic nanoparticles, and depositing the core-shell magnetic nanoparticles at the bottom of the microfluidic chip 7;
(4) introducing ethanol again, performing circulating flushing for 10 seconds, discharging waste liquid, and repeating for five times;
(5) the magnet rotating assembly 6 is reset to enable Fe3O4@TiO2Core-shell magnetic nanoparticles delivered to Fe3O4@TiO2Core-shell magnetic nanoparticle delivery tube for Fe3O4@mTiO2The magnetic nanoparticle synthesis preparation component 3 is subjected to synthesis treatment.
In the same way as before, the pipeline control in the above process is regulated and controlled by adopting the traditional peristaltic pump, the electromagnetic valve and the like and the traditional pipeline control technology.
From the chemical field, Fe3O4@mTiO2The preparation process of the magnetic nanoparticles is as follows:
the product Fe collected in the previous step3O4@TiO2The core-shell magnetic nanoparticles are ultrasonically dispersed in 20mL of ethanol and 10mL of deionized water (2:1, V/V), and are transferred to a 40mL of polytetrafluoroethylene reaction kettle after being completely dispersed, then 2mL of concentrated ammonia water is rapidly added into the kettle, and the kettle is packaged into a stainless steel kettle sleeve and placed in an oven to keep the temperature at 160 ℃ for reaction for 20 hours. After the reaction is finished, naturally cooling to room temperature, collecting the product by means of a magnet, washing for at least 6 times by using ethanol, and drying for 6 hours in a vacuum drying oven at 60 ℃ for later use.
Note that: (1) wholly coated TiO2The process of (2) avoids water because tetrabutyl titanate is very easily hydrolyzed. (2) Whether the kettle cover is tightly covered is checked before the kettle is burnt every time, so that the kettle is prevented from being burnt dry in high-temperature reaction.
As shown in FIG. 5, to incorporate Fe3O4@mTiO2Realization of the chemical preparation method (control method) of magnetic nanoparticles, Fe3O4@mTiO2The magnetic nano-particle synthesis preparation component 3 comprises a third micro-reaction component 31, the structure of the third micro-reaction component 31 is the same as that of the second micro-reaction cavity component, and the third micro-reaction component is provided with device components such as a reaction kettle, an electric heating wire, a magnet rotating component 6 and the like.
Fe3O4@TiO2The tail end of the core-shell magnetic nanoparticle conveying pipe is connected with the ethanol deionized water mixing agent cup 32, the head end of the third micro-reaction component conveying pipe 33 is connected into the ethanol deionized water mixing agent cup 32, and the tail end of the third micro-reaction component conveying pipe is connected with the third micro-reaction component 31. (to realize the product Fe collected in the previous step in the chemical process3O4@TiO2Step of ultrasonic dispersing core-shell magnetic nanoparticles in 20mL of ethanol and 10mL of deionized water (2:1, V/V)
The bottom of the third micro-reaction component 31 is connected with Fe3O4@mTiO2Magnetic nanoparticle delivery tube 34 for post-synthesis Fe3O4@mTiO2The/noble metal magnetic composite nano particle synthesis preparation component 4 is conveyed, and meanwhile, Fe3O4@mTiO2The magnetic nanoparticle delivery pipe 34 is connected with a self-control drainage pipe according to the prior art.
The end of the third micro-reaction assembly delivery pipe 33 is also connected with an ethanol delivery pipe 35, a concentrated ammonia water delivery pipe 36 and a deionized water delivery pipe 37 to match the input of ethanol, concentrated ammonia water and deionized water.
Fe3O4@mTiO2The working flow of the magnetic nanoparticle synthesis preparation component 3 is as follows:
(1) dissolving Fe in ethanol3O4@TiO2The core-shell magnetic nano-particles are introduced into a third micro-reaction component 31, and deionized water and concentrated ammonia water are input;
(2) starting a heating wire of the third micro-reaction component 31, heating to 160 ℃, continuing for 20 hours, closing the heating wire, and naturally cooling after waiting for two hours;
(3) the magnet rotating unit 6 moves the magnet to the bottom of the third micro-reaction unit 31, and the product Fe is generated by the action of the magnet3O4@mTiO2Collecting the magnetic nanoparticles, and depositing the magnetic nanoparticles on the bottom of the third micro-reaction component 31;
(4) passing the liquid in the third micro-reaction module 31 through Fe3O4@mTiO2The magnetic nanoparticle delivery tube 34 discharges;
(5) introducing ethanol, repeatedly performing the ethanol cleaning step, cleaning for six times and respectively discharging water;
(6) a small amount of deionized water is introduced to synthesize the product Fe in the third micro-reaction component 313O4@mTiO2Magnetic nanoparticles are charged with Fe3O4@mTiO2The component 4 is prepared by synthesizing/noble metal magnetic composite nano particles.
The pipeline control in the process is regulated and controlled by adopting a traditional peristaltic pump, a traditional solenoid valve and the like and a traditional pipeline control technology.
From the chemical field, for Fe3O4@mTiO2After the surface of the noble metal is subjected to charge modification, the nano particles of the noble metal are directly captured to the outer layer of the noble metal through electrostatic interaction. Gold and silver sols and Au @ Ag core-shell nanoparticles, which are generally obtained by reduction with sodium citrate, have negative charges on the surface, and gold nanorods prepared using cetyltrimethylammonium bromide (CTAB) have positive charges on the surface.
Conclusion of Fe3O4@mTiO2The preparation process of the/noble metal magnetic composite nano-particles comprises the following steps:
10mg of freshly prepared Fe are weighed3O4@mTiO2Magnetic nano-particle ultrasonic dispersion in AgNO3In the solution (15mL of 0.02mol/L), the ultrasonic is stopped after 30 minutes, and the mechanical stirring is changed; then 20 mul of butylamine is added into the mixture, and the mixture is mechanically stirred for 60 minutes at 50 ℃ to fully react; finally, the external magnet is used asThe product obtained is Fe3O4@mTiO2The noble metal particles were collected from the reaction solution, washed with deionized water several times, and redispersed in 4mL of deionized water for further use.
For Fe3O4@mTiO2The Ag synthesis steps are as follows:
(1) introduction of positively charged polyelectrolytes [ branched Polyetherimides (PEI) or polydiallyldimethylammonium chloride (PDDA)]Aqueous solution of Fe3O4@mTiO2Fully dispersing;
(2) fully cleaning with deionized water;
(3) introducing deionized water to disperse, introducing silver sol, and reacting completely;
(4) and (5) cleaning.
For Fe3O4@mTiO2The synthesis steps of Au (nanosphere) are as follows:
(1) introduction of positively charged polyelectrolytes [ branched Polyetherimides (PEI) or polydiallyldimethylammonium chloride (PDDA)]Aqueous solution of Fe3O4@mTiO2Fully dispersing;
(2) fully cleaning with deionized water;
(3) introducing deionized water to disperse, introducing gold sol, and fully reacting;
(4) and (5) cleaning.
For Fe3O4@mTiO2The synthesis steps of/Au @ Ag are as follows:
(1) introduction of positively charged polyelectrolytes [ branched Polyetherimides (PEI) or polydiallyldimethylammonium chloride (PDDA)]Aqueous solution of Fe3O4@mTiO2Fully dispersing;
(2) fully cleaning with deionized water;
(3) introducing deionized water to disperse the nano particles, and introducing Au @ Ag core-shell nano particles to fully react;
(4) and (5) cleaning.
For Fe3O4@mTiO2The synthesis steps of the/AuNR rod are as follows:
(1) Introducing negatively charged polyelectrolyte [ sodium polystyrene sulfonate (PSS) or sodium Polymethacrylate (PMAA) and the like]Aqueous solution of Fe3O4@mTiO2Fully dispersing;
(2) fully cleaning with deionized water;
(3) introducing deionized water to disperse the gold nanorods, and introducing the gold nanorods for full reaction;
(4) and (5) cleaning.
As shown in FIG. 6, to incorporate Fe3O4@mTiO2Realization of chemical preparation method (control method) of/noble metal magnetic composite nano-particles, Fe3O4@mTiO2The/noble metal magnetic composite nano particle synthesis preparation component 4 comprises a magnet rotating component 6 and a synthetic micro-fluidic chip 41, and the structure of the synthetic micro-fluidic chip 41 is the same as that of the micro-fluidic chip 7.
Here, an electric heating plate 8 is attached to the bottom of the composite microfluidic chip 41 to meet the chemical process requirement of maintaining the temperature at 50 ℃. Similarly, the bottom of the composite microfluidic chip 41 is located above the radius of the magnet rotation trajectory of the magnet rotating assembly 6, and the composite is magnetically adsorbed by the magnet rotating assembly 6.
In the same way, Fe3O4@mTiO2The end of the magnetic nanoparticle delivery pipe 34 is inserted into the deionized water solution cup 42, and the product Fe is synthesized3O4@mTiO2The input end of the delivery tube 44 is inserted into the deionized water solution cup 42. Synthesis of product Fe3O4@mTiO2The output end of the delivery pipe 44 is connected to a fourth tee 45, one path of the fourth tee 45 is communicated with the main inlet of the synthetic microfluidic chip 41, the other path of the fourth tee 45 is connected with a fifth tee 48, one end of the fifth tee 48 is connected to the outlet of the synthetic microfluidic chip 41, and the other end of the fifth tee 48 passes through Fe3O4@mTiO2The output pipe 9 of the/noble metal magnetic composite nano-particle is connected into a cup 49 of synthetic deionized water solution, Fe3O4@mTiO2An automatic control drain pipe is arranged on the output pipe 9 of the/noble metal magnetic composite nano-particles. The first inlet and the third inlet of the synthetic micro-fluidic chip 41 are respectively connected with a polyelectrolyte solution tube 46 and a noble metal nano tubeA rice grain input pipe 47.
Fe3O4@mTiO2The working process of synthesizing and preparing the component 4 by the/noble metal magnetic composite nano particles is as follows:
(1) partially synthesizing product Fe dissolved in deionized water3O4@mTiO2The magnetic nanoparticles are sent to the synthetic microfluidic chip 41;
(2) introducing AgNO3The solution is mixed and fully reacted in the synthetic micro-fluidic chip 41;
(3) butylamine is pumped into the synthetic micro-fluidic chip 41 to be mixed and fully reacted;
(4) fully circulating by matching with the fourth tee joint 45 and the fifth tee joint 48, starting the electric heating sheet to heat for 50 ℃ and continuing for 60 minutes;
(5) the magnet rotating assembly 6 moves the magnet to the lower part of the synthetic microfluidic chip 41 for particle collection;
(6) deionized water is introduced for 30 seconds, waste liquid is discharged, and after the deionized water is continuously introduced for 5 times, the magnet rotating assembly 6 is reset;
(7) synthesized Fe3O4@mTiO2The/noble metal magnetic composite nano-particles are put into 4ml of deionized water for standby.
The pipeline control in the process is regulated and controlled by adopting a traditional peristaltic pump, a traditional solenoid valve and the like and a traditional pipeline control technology.
As a first embodiment of the present invention, when it is desired to produce Fe3O4@mTiO2When the/Ag composite nano particles are prepared, positive charge polyelectrolyte is introduced into a polyelectrolyte solution pipe 46, silver sol is introduced into a noble metal nano particle input pipe 47, and after the synthesis treatment of the synthetic micro-fluidic chip 41, Fe is added3O4@mTiO2Fe is output from a/noble metal magnetic composite nano-particle output pipe 93O4@mTiO2the/Ag composite nano particles are dispersed in 4ml of deionized water for standby.
As a second embodiment of the present invention, when it is desired to produce Fe3O4@mTiO2In the case of Au composite nano-particles, in the polyelectrolyte solution tube 46Positive charge polyelectrolyte is introduced into the reaction chamber, gold sol is introduced into the noble metal nanoparticle input tube 47, and after the synthesis treatment of the synthetic microfluidic chip 41, Fe is obtained3O4@mTiO2Fe is output from a/noble metal magnetic composite nano-particle output pipe 93O4@mTiO2the/Au composite nano particles are dispersed in 4ml of deionized water for standby.
As a third embodiment of the present invention, when it is desired to produce Fe3O4@mTiO2when/Au @ Ag core-shell composite nano-particles are used, positive charge polyelectrolyte is introduced into a polyelectrolyte solution pipe 46, Au @ Ag core-shell nano-particles are introduced into a noble metal nano-particle input pipe 47, and similarly, after the Au @ Ag core-shell nano-particles are subjected to synthesis treatment by a synthetic micro-fluidic chip 41, Fe3O4@mTiO2Fe is output from a/noble metal magnetic composite nano-particle output pipe 93O4@mTiO2the/Au @ Ag composite nano-particles are dispersed in 4ml of deionized water for later use.
As a fourth embodiment of the present invention, when it is desired to produce Fe3O4@mTiO2When the/AuNR composite nano-particles are prepared, the negative charge polyelectrolyte is introduced into a polyelectrolyte solution pipe 46, the gold nano-rods are introduced into a noble metal nano-particle input pipe 47, and the Fe is obtained after the synthesis treatment of the synthetic micro-fluidic chip 413O4@mTiO2Fe is output from a/noble metal magnetic composite nano-particle output pipe 93O4@mTiO2the/AuNR composite nanoparticles were dispersed in 4ml of deionized water for use.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. A fluid synthesis preparation device for preparing magnetic/precious metal composite nano particles is characterized in that: including Fe3O4Magnetic nanoparticle synthesis preparation component (1), Fe3O4@TiO2Synthesis preparation of component (2) from core-shell magnetic nanoparticles, Fe3O4@mTiO2Magnetic nanoparticle synthesis preparation component (3) and Fe3O4@mTiO2Synthesizing and preparing a component (4) by using the precious metal magnetic composite nano particles;
said Fe3O4Synthetic product output port and Fe of magnetic nanoparticle preparation component (1)3O4@TiO2The fluid input ports of the core-shell magnetic nanoparticle synthesis preparation component (2) are connected, and Fe3O4@TiO2Synthesis product outlet and Fe of core-shell magnetic nanoparticle synthesis preparation component (2)3O4@mTiO2The fluid input ports of the magnetic nano-particle synthesis preparation component (3) are connected, and Fe3O4@mTiO2Synthetic product output port and Fe of magnetic nanoparticle synthesis preparation component (3)3O4@mTiO2The fluid input ports of the precious metal magnetic composite nano particle synthesis preparation component (4) are connected;
said Fe3O4The magnetic nanoparticle synthesis preparation assembly (1) comprises a first micro-reaction cavity assembly and a second micro-reaction cavity assembly, the first micro-reaction cavity assembly comprises a first micro-reaction cavity (11), an ethylene glycol supply pipe (12) is connected to the upper end of the first micro-reaction cavity (11), the bottom of the first micro-reaction cavity (11) is funnel-shaped, the first micro-reaction cavity (11) is placed on a magnetic stirrer (13), a sieve plate (14) is arranged in the first micro-reaction cavity (11), a magneton (15) is placed on the sieve plate (14), the head end of a silicone tube (16) is connected to the bottom of the first micro-reaction cavity (11), and the tail end of the silicone tube (16) is connected to the upper end of the second micro-reaction cavity assembly;
the second micro-reaction cavity component comprises a second micro-reaction cavity (17) and a magnet rotating component (6), the bottom of the second micro-reaction cavity (17) is located above the radius of a magnet rotating track of the magnet rotating component (6), the bottom of the second micro-reaction cavity (17) is funnel-shaped, a resistance heating wire (19) is wound on the outer wall of the second micro-reaction cavity (17), a heat insulation asbestos sleeve (10) is wrapped outside the second micro-reaction cavity (17), and a thermocouple (18) is inserted into the heat insulation asbestos sleeve (10) and connected onto the resistance heating wire (19);
the tail end of the silicone tube (16) is also connected with a deionized water delivery pipe (54) and an ethanol delivery pipe (55), the tail end of the silicone tube (16) passes through a heat-insulating asbestos sleeve (10) of the second micro-reaction cavity component to be inserted at the upper end of the second micro-reaction cavity (17), and Fe3O4The head end of the magnetic nano particle conveying pipe (5) penetrates through a heat insulation asbestos sleeve (10) of the second micro reaction cavity assembly to be connected to the bottom of the second micro reaction cavity (17).
2. The fluid synthesis preparation device for preparing magnetic/noble metal composite nano-particles according to claim 1, characterized in that: the device is characterized in that a first peristaltic pump (51) and a first pinch valve (52) are installed on the ethylene glycol supply pipe (12), a second pinch valve (53) is installed on the silicone tube (16), a second peristaltic pump (56) is installed on the deionized water conveying pipe (54), a third peristaltic pump (57) is installed on the ethanol conveying pipe (55), and Fe3O4A third pinch valve (58) is arranged on the magnetic nano particle conveying pipe (5), and Fe3O4A self-control drain pipe is connected between the third pinch valve (58) and the second micro-reaction cavity (17) on the magnetic nano-particle conveying pipe (5);
the magnet rotating assembly (6) comprises a rotating rod (59), a clamp (60) is fixedly mounted on the rotating rod (59), a magnet (61) is clamped on the clamp (60), and the bottom of the second micro-reaction cavity (17) is positioned above the radius of a rotating track of the magnet (61);
the device also comprises a temperature controller (62), wherein one end of the temperature controller (62) is connected to the thermocouple (18), and the other end of the temperature controller is connected to the resistance heating wire (19).
3. The fluid synthesis preparation device for preparing magnetic/noble metal composite nano-particles according to claim 1, characterized in that: said Fe3O4@TiO2The core-shell magnetic nano-particle synthesis preparation component (2) comprisesA magnet rotating component (6), a micro-fluidic chip (7) and an ethanol solution cup (21), wherein the Fe is3O4The tail end of the magnetic nanoparticle conveying pipe (5) is connected into the ethanol solution cup (21), one end of the first fluid conveying pipe (22) is connected into the ethanol solution cup (21), the other end of the first fluid conveying pipe is connected onto the first tee joint (23), one path of the first tee joint (23) is connected onto the second tee joint (25) through the second fluid conveying pipe (24), the second fluid conveying pipe (24) is connected with the automatic control drain pipe, and the other path of the first tee joint (23) is connected onto the main inlet (71) of the microfluidic chip (7); one path of the second tee joint (25) is connected with Fe3O4@TiO2The head end of the core-shell magnetic nanoparticle conveying pipe is provided, the other path of the second tee joint (25) is connected to an outlet (72) of the microfluidic chip (7), a first inlet (73) of the microfluidic chip (7) is connected with an acetonitrile conveying pipe (74), a second inlet (75) is connected with a concentrated ammonia water conveying pipe (76), and a third inlet (77) is connected with a tetrabutyl titanate conveying pipe (70); the bottom of the micro-fluidic chip (7) is positioned above the radius of a magnet rotating track of the magnet rotating assembly (6);
the micro-fluidic chip (7) comprises a bottom plate (78), wherein a mixing channel (81), micro-channels (79) and a main channel (80) are embedded in the bottom plate (78), the number of the micro-channels (79) is 4, input ports of the 4 micro-channels (79) are respectively communicated with a first inlet (73), a second inlet (75), a third inlet (77) and a main inlet (71), output ports of the 4 micro-channels (79) are collected on the main channel (80), the main channel (80) is communicated with an inlet of the mixing channel (81), a plurality of arc-shaped protrusions (82) are arranged on the mixing channel (81), and an outlet (72) of the mixing channel (81) is communicated with one path of a second tee joint (25).
4. The fluid synthesis preparation device for preparing magnetic/noble metal composite nano-particles according to claim 3, characterized in that: said Fe3O4@mTiO2The magnetic nano particle synthesis preparation assembly (3) comprises a third micro reaction assembly (31), and the structure of the third micro reaction assembly (31) is the same as that of the second micro reaction cavity assembly;
said Fe3O4@TiO2The tail end of the conveying pipe of the core-shell magnetic nano particles is connected with an ethanol deionized water mixing agent cup (32), andthe head end of the three micro-reaction component conveying pipe (33) is connected into the ethanol deionized water mixing agent cup (32), the tail end is connected with the third micro-reaction component (31), and the bottom of the third micro-reaction component (31) is connected with Fe3O4@mTiO2Magnetic nanoparticle delivery tube (34), Fe3O4@mTiO2The magnetic nano particle delivery pipe (34) is connected with a self-control drainage pipe, and the tail end of the third micro reaction component delivery pipe (33) is also connected with an ethanol delivery pipe (35), a concentrated ammonia water delivery pipe (36) and a deionized water delivery pipe (37).
5. The fluid synthesis preparation device for preparing magnetic/noble metal composite nano-particles according to claim 4, characterized in that: said Fe3O4@mTiO2The precious metal magnetic composite nano particle synthesis preparation component (4) comprises a magnet rotating component (6) and a synthesis micro-fluidic chip (41), the structure of the synthesis micro-fluidic chip (41) is the same as that of the micro-fluidic chip (7), an electric heating sheet (8) is attached to the bottom of the synthesis micro-fluidic chip (41), and the bottom of the synthesis micro-fluidic chip (41) is located above the radius of a magnet rotating track of the magnet rotating component (6);
said Fe3O4@mTiO2The end of the magnetic nano-particle delivery pipe (34) is inserted into a deionized water solution cup (42) to synthesize a product Fe3O4@mTiO2The input end of the delivery pipe (44) is inserted into the deionized water solution cup (42) to synthesize the product Fe3O4@mTiO2The output end of the delivery pipe (44) is connected with a fourth tee joint (45), one path of the fourth tee joint (45) is communicated with the main inlet of the synthetic micro-fluidic chip (41), the other path of the fourth tee joint (45) is connected with a fifth tee joint (48), one end of the fifth tee joint (48) is connected with the outlet of the synthetic micro-fluidic chip (41), and the other end of the fifth tee joint (48) passes through Fe3O4@mTiO2A noble metal magnetic composite nano particle output pipe (9) is connected into a cup (49) for synthesizing deionized water solution, and Fe3O4@mTiO2A self-control drain pipe is arranged on the noble metal magnetic composite nano particle output pipe (9), and a polyelectrolyte solution pipe (46) and a noble metal solution pipe are respectively connected with a first inlet and a third inlet of the synthetic micro-fluidic chip (41)Belongs to a nanoparticle input tube (47).
6. The fluid synthesis preparation device for preparing magnetic/noble metal composite nano-particles according to claim 5, characterized in that: the positive charge polyelectrolyte is introduced into the polyelectrolyte solution pipe (46), and the silver nanosphere sol and Fe are introduced into the noble metal nanoparticle input pipe (47)3O4@mTiO2Fe output from noble metal magnetic composite nano particle output pipe (9)3O4@mTiO2Ag composite nano-particles.
7. The fluid synthesis preparation device for preparing magnetic/noble metal composite nano-particles according to claim 5, characterized in that: the positive charge polyelectrolyte is introduced into the polyelectrolyte solution pipe (46), and the gold nanoparticle sol and Fe are introduced into the noble metal nanoparticle input pipe (47)3O4@mTiO2Fe output from noble metal magnetic composite nano particle output pipe (9)3O4@mTiO2/Au composite nanoparticles.
8. The fluid synthesis preparation device for preparing magnetic/noble metal composite nano-particles according to claim 5, characterized in that: the positive charge polyelectrolyte is introduced into the polyelectrolyte solution pipe (46), and Au @ Ag core-shell nanoparticle sol and Fe are introduced into the noble metal nanoparticle input pipe (47)3O4@mTiO2Fe output from noble metal magnetic composite nano particle output pipe (9)3O4@mTiO2the/Au @ Ag composite nano-particles.
9. The fluid synthesis preparation device for preparing magnetic/noble metal composite nano-particles according to claim 5, characterized in that: the polyelectrolyte solution pipe (46) is filled with negatively charged polyelectrolyte, the noble metal nanoparticle input pipe (47) is filled with gold nanorod sol and Fe3O4@mTiO2Fe output from noble metal magnetic composite nano particle output pipe (9)3O4@mTiO2/AuNR composite nanoparticles.
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