WO2023124437A1 - Microfluidic chip, micro-reaction system, and quantum dot preparation method - Google Patents

Microfluidic chip, micro-reaction system, and quantum dot preparation method Download PDF

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Publication number
WO2023124437A1
WO2023124437A1 PCT/CN2022/126274 CN2022126274W WO2023124437A1 WO 2023124437 A1 WO2023124437 A1 WO 2023124437A1 CN 2022126274 W CN2022126274 W CN 2022126274W WO 2023124437 A1 WO2023124437 A1 WO 2023124437A1
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channel
reaction
sub
channels
microfluidic chip
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PCT/CN2022/126274
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French (fr)
Chinese (zh)
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王元
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Tcl科技集团股份有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/502707Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093Microreactors, e.g. miniaturised or microfabricated reactors
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers

Definitions

  • the present application relates to the field of microfluidic reactions, in particular to the preparation method of microfluidic chips, microreaction systems and quantum dots.
  • Microfluidic reactions are also known as microchannel reactions, fluid microreactions, or microfluidic reactions.
  • the microfluidic reaction replaces the traditional intermittent reaction with continuous flow, and reacts under the reaction conditions such as mixed reaction or heating in the microchannel through continuous fluid, and the target product is prepared by continuous synthesis, and the reaction can be precisely controlled on the microscopic scale, improving Reaction selectivity and operational safety. Due to its micron-sized channel structure, the microfluidic chip greatly improves the heat transfer and mass transfer performance of the reaction.
  • the time required for the precursor liquid to enter the heated state from the room temperature state in the chip is extremely short, indicating that in the microfluidic chip, the synthesis of quantum dots can be completed with an extremely short channel size.
  • the current traditional chip channel structure is a helical or serpentine winding channel covering the chip plane.
  • Such a single reaction channel not only wastes the chip space excessively, but also makes the synthesis efficiency of the reaction low.
  • the present application provides a method for preparing a microfluidic chip, a microreaction system and quantum dots.
  • An embodiment of the present application provides a microfluidic chip, including an injection channel, a mixing channel, a reaction channel, and an outflow channel connected in sequence; one end of the injection channel is a feed port, and the other end communicates with the mixing channel; One end of the mixing channel away from the injection channel is a split port, and the split port communicates with the reaction channel; the reaction channel includes a plurality of sub-reaction channels arranged in parallel, and one end of each sub-reaction channel is connected to the mixing channel.
  • the diverging port at the other end is connected, and the other end is connected with the confluence port of the outflow channel; one end of the outflow channel is the confluence port, and the other end is the discharge port.
  • At least some of the sub-reaction channels have substantially the same volume.
  • At least some of the sub-reaction channels have substantially the same length.
  • the central axis of each sub-reaction channel is located on the same plane;
  • the reference line in a direction away from the reference line, the length of the sub-reaction channel gradually increases, and the inner diameter of the sub-reaction channel gradually decreases.
  • the inner diameters of the multiple sub-reaction channels range from 450 ⁇ m to 650 ⁇ m.
  • the lengths of the multiple sub-reaction channels range from 80 mm to 167 mm.
  • each sub-reaction channel is formed by connecting multiple straight channels or is an arc channel.
  • the mixing channel is an S-shaped channel.
  • the inner diameter of the mixing channel is in a range of 3mm-5mm.
  • the microfluidic chip includes a plurality of injection channels, and the inner diameter of each injection channel ranges from 1 mm to 2 mm.
  • the inner diameter of the outflow channel is in the range of 3-5 mm.
  • the inner diameter of the outflow channel is the same as the inner diameter of the mixing channel.
  • the area where the reaction channel is located is a heating area.
  • the embodiment of the present application also provides a micro-reaction system, including a sampling device, a microfluidic chip, and a product collection device;
  • the microfluidic chip includes sequentially connected injection channels, mixing channels, reaction channels, and outflow channels
  • One end of the injection channel is a feed port, connected to the sampling device; the other end of the injection channel communicates with the mixing channel; the end of the mixing channel away from the injection channel is a split port, the The split port is communicated with the reaction channel;
  • the reaction channel includes a plurality of sub-reaction channels arranged in parallel, one end of each sub-reaction channel is communicated with the split port at the other end of the mixing channel, and the other end is connected with the outlet port of the outflow channel.
  • the confluence port is connected; one end of the outflow channel is the confluence port, and the other end of the outflow channel is a discharge port, which communicates with the product collection device.
  • At least some of the sub-reaction channels have substantially the same volume.
  • At least some of the sub-reaction channels have substantially the same length.
  • the central axis of each sub-reaction channel is located on the same plane;
  • the reference line in a direction away from the reference line, the length of the sub-reaction channel gradually increases, and the inner diameter of the sub-reaction channel gradually decreases.
  • the embodiment of the present application also provides a method for preparing quantum dots.
  • the quantum dots are prepared by using a microfluidic chip, and the microfluidic chip includes an injection channel, a mixing channel, a reaction channel, and an outflow channel connected in sequence;
  • the reaction channel includes a plurality of sub-reaction channels arranged in parallel;
  • the preparation method includes: the precursor solution flows in from the feed port of the injection channel, and flows through the mixing channel for mixing to obtain a mixed solution; the mixing The solution is divided into multiple sub-flows at the diversion port of the mixing channel, and flows into multiple sub-reaction channels arranged in parallel, and reacts in multiple sub-reaction channels to generate quantum dots; the multiple sub-flows flow through the confluence port for confluence , and flow through the outflow channel, and flow out of the microfluidic chip from the outlet of the outflow channel.
  • the times for the multiple branches to flow from the diversion port to the confluence port are the same.
  • the quantum dots are selected from at least one of single-structure quantum dots and core-shell structure quantum dots
  • the material of the single-structure quantum dots is selected from group II-VI compounds , III-V group compound and at least one of I-III-VI group compound
  • described II-VI group compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS , ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe at least one
  • the III-V group compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb At least one of , GaAl
  • the microfluidic chip of the present application supports the reaction solution to enter the microfluidic chip through the feed port of the injection channel, fully mix in the mixing channel, and flow into a plurality of parallel sub-reaction channels through the split port, and each sub-reaction channel
  • the reaction liquids in the flow reaction are combined at the confluence port at the same time, and flow out of the microfluidic chip through the outflow channel, so as to use the microfluidic chip to complete the synthesis and preparation of the product.
  • the micro-sized sub-reaction channel improves the heat transfer performance of the reaction solution and promotes the high-quality synthesis of products.
  • FIG. 1 is a schematic structural diagram of a microfluidic chip provided in an embodiment of the present application
  • Fig. 2 is a schematic structural view of a reaction channel provided in an embodiment of the present application.
  • Fig. 3 is the structural representation of a kind of micro-reaction system provided by the embodiment of the present application.
  • Fig. 4 is a schematic flow chart of a method for preparing quantum dots provided in an embodiment of the present application.
  • a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
  • At least one means one or more, and “multiple” means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • At least one means two or more.
  • the microfluidic chip in this application refers to a chip that can perform microfluidic reactions, that is, channels for containing fluids, mixing units, reaction units, and other functional components are integrated on a micron-scale chip to manipulate micron-volume fluids in a micron The movement process in space, so as to realize the fluid reaction on the chip, and realize the continuous preparation of products, such as the continuous preparation of nanocrystals or quantum dots.
  • FIG. 1 is a schematic structural diagram of a microfluidic chip provided in an embodiment of the present application.
  • the microfluidic chip 10 includes an injection channel 11 , a mixing channel 12 , a reaction channel 13 and an outflow channel 14 .
  • the injection channel 11 , the mixing channel 12 , the reaction channel 13 and the outflow channel 14 communicate in sequence.
  • one end of the injection channel 11 is a feed port (not shown in the figure), and the other end communicates with the mixing channel 12 .
  • the end of the mixing channel 12 away from the injection channel 11 is a split port 121 , and the split port 121 communicates with the reaction channel 13 .
  • the reaction channel 13 includes a plurality of sub-reaction channels 131 arranged in parallel, one end of each sub-reaction channel 131 communicates with the split port 121 at the other end of the mixing channel 12 , and the other end of each sub-reaction channel 131 communicates with the confluence port 141 of the outflow channel 14 .
  • One end of the outflow channel 14 is a confluence port 141, and the other end is a discharge port (not noted in the figure).
  • the reaction solution enters the microfluidic chip 10 through the feed port of the injection channel 11, is fully mixed in the mixing channel 12, and flows into a plurality of parallel sub-reaction channels 131 through the split port 121, and each sub-reaction
  • the reaction solution in the channel 131 is flowing and reacting at the same time and merged at the confluence port 141 , and flows out of the microfluidic chip 10 through the outflow channel 14 , so that the microfluidic chip 10 is used to complete the synthesis and preparation of the product.
  • the limited chip space is fully utilized, and the amount of the reaction liquid in the reaction state per unit time is increased, thereby increasing the yield of the generated product per unit time and improving the synthesis efficiency.
  • the micro-sized sub-reaction channel 131 improves the heat transfer performance of the reaction solution and promotes high-quality synthesis and preparation of products.
  • each sub-reaction channel 131 communicates with the diversion port 121 , and the other end of each sub-reaction channel 131 communicates with the confluence port 141 .
  • the volume of the sub-reaction channel 131 is the channel volume from the diversion port 121 to the confluence port 141
  • the length of the sub-reaction channel 131 is the corresponding channel length from the diversion port 121 to the confluence port 141 .
  • the volumes or volumes of at least some of the sub-reaction channels 131 are substantially the same, that is, the corresponding volumes of some of the sub-reaction channels 131 or all the sub-reaction channels 131 in the plurality of sub-reaction channels 131 are basically the same.
  • the length of the sub-reaction channel 131 is inversely proportional to the square of the internal diameter, so that the reaction time of the reaction solution in each sub-reaction channel 131 is close or equal, and the reaction solution is approximately synchronously flowing in all microchannels, so that in each sub-reaction channel 131
  • the reaction state is consistent, avoiding that the reaction solution of the sub-reaction channel 131 has not completely reacted, and the reaction solution of the sub-reaction channel 131 has completely reacted, thereby causing the outflow channel 14 to flow out.
  • the reaction stages of the mixed reaction solution are different, thus affecting the state and quality of the product.
  • the sub-reaction channels 131 have substantially the same volume or volume, and at least part of the sub-reaction channels 131 have the same length. Since the volume of the sub-reaction channels 131 is related to the length and inner diameter, the inner diameters of the plurality of sub-reaction channels 131 are also the same. At this time, multiple sub-reaction channels 131 may not be arranged on the same plane, that is, the microfluidic chip 10 has a three-dimensional structure, thereby improving the synthesis efficiency of the product prepared by using the microfluidic chip 10, while ensuring that the outflow channel 14 flows out and collects The reaction stages of the mixed reaction solution are the same, thereby improving the synthesis consistency and product quality of the product. For example, when synthesizing quantum dots, improve the concentration of quantum dot size distribution.
  • the microfluidic chip 10 is a planar structure, and among the plurality of sub-reaction channels 131 disposed on it, the central axis of each sub-reaction channel 131 is located on the same plane. At this time, all sub-reaction channels 131 are on the same plane. Taking the connection line between the diversion port 121 and the confluence port 141 as the reference line aa', in the directions X and X' away from the reference line aa', the length of the sub-reaction channel 131 gradually increases, and the length of the sub-reaction channel 131 The inner diameter gradually decreases.
  • Each sub-reaction channel 131 is on the microfluidic reaction chip 10 and is on the same plane, so the lengths may be different when they are connected in parallel.
  • the channel is the straight line connection between the diverging port 121 and the converging port 141 , that is, the reaction channel coincident with the reference line aa'.
  • the length of the sub-reaction channel 131 gradually increases, that is, the closer the sub-reaction channel 131 to the reference line aa'
  • the sub-reaction channel 131 coincident with the reference line a-a' may be provided, or the sub-reaction channel 131 coincident with the reference line a-a' may not be provided, which is not limited here.
  • the length of the sub-reaction channel 131 gradually increases, and the inner diameter of the sub-reaction channel 131 gradually decreases, and the decrease in the inner diameter will lead to an increase in the flow rate, so that the longer length
  • the flow velocity of the sub-reaction channel 131 is also relatively large, so that the reaction time of the reaction solution in each sub-reaction channel 131 is approximate, and the reaction solution flows and reacts approximately synchronously in all microchannels, so that the fluid in each sub-reaction channel 131 enters
  • the confluence port 141 of the outflow channel 14 the reaction state is consistent, avoiding that the reaction solution of the sub-sub-reaction channel 131 has not completely reacted, while the reaction solution of the sub-sub-reaction channel
  • FIG. 2 is a schematic structural diagram of a reaction channel provided in an embodiment of the present application.
  • the reaction channel 13 includes a first sub-reaction channel ACDB and a second sub-reaction channel AEFB.
  • the length of the first sub-reaction channel ACDB is denoted as L 1
  • the inner diameter is r 1 .
  • the length of the second sub-reaction channel AEFB is denoted as L 2
  • the inner diameter is r 2 .
  • the volumes of the first sub-reaction channel ACDB and the second sub-reaction channel AEFB are the same, and according to the volume formula, two sub-reaction channels 131 can be obtained to satisfy the formula (I):
  • the length of the sub-reaction channel 131 is inversely proportional to the square of the inner diameter.
  • each sub-reaction channel 131 may be formed by connecting multiple segments of straight channels.
  • the first sub-reaction channel ACDB includes section AC, section CD and section DB, the lengths of which are L 11 , L 12 and L 13 respectively.
  • the second sub-reaction channel AEFB includes an AE segment, an EF segment and a FB segment, and the lengths are L 21 , L 22 and L 23 respectively.
  • each sub-reaction channel 131 itself may be an axisymmetric structure.
  • the sub-reaction channel 131 can also be an arc-shaped channel, and the arc of the sub-reaction channel 131 is different according to the distance from the reference line a-a'.
  • the sub-reaction channel 131 closer to the reference line a-a' has a smaller arc
  • the sub-reaction channel 131 farther away from the reference line a-a' has a larger arc.
  • the inner diameters of the sub-reaction channels 131 range from 450 ⁇ m to 650 ⁇ m.
  • channels with inner diameters in this range are used for fluid reactions such as heating, it can avoid losing its advantages in heat and mass transfer as a microfluidic reaction when the inner diameter is too large, and it can also avoid large flow rates and small reaction volumes caused by too small inner diameters It is beneficial to the synthesis and preparation of products and ensures higher yield and synthesis efficiency.
  • the length of the sub-reaction channels 131 can be set correspondingly based on different fluid reactions. For example, nanocrystals or quantum dots are synthesized through the reaction channel 13 in the heating area, and the length range of each sub-reaction channel 131 in the reaction channel 13 is set according to the reaction requirements for synthesizing nanocrystals or quantum dots.
  • the length of the sub-reaction channel 131 is too short, the reaction liquid flows through for too short a time, and the reaction will be insufficient; if the purpose of increasing the reaction time is achieved by reducing the flow rate, the synthesis efficiency of the product will be reduced. After the reaction solution has been completely reacted in the channel, the too long length will not have a positive effect on the synthesis efficiency of the reaction, and will cause waste of the pipeline.
  • the mixing channel 12 may be a channel known in the art for mixing reactants.
  • the mixing channel 12 is an S-shaped channel or a serpentine channel, and may be a multi-segment bent S-shaped channel, so as to fully mix the reaction solution and reduce the occupied area of the mixing channel 12 .
  • the inner diameter of the serpentine mixing channel 12 may be 3-5mm.
  • the S-shaped section channel is only used as the reaction and also flows to the mixing before the heating area.
  • the inner diameter of the mixing channel 12 can satisfy the liquid flow of a relatively large flow rate, so as to provide sufficient reaction liquid for multiple sub-reaction channels 131 in the reaction area, so The inner diameter cannot be too small. However, if the inner diameter is too large, the liquid flow rate in this section of the channel will slow down due to the limited flow rate of the injection channel, and there may be an interference cavity in the mixing channel 12 to retain gas, which will affect the synthesis effect.
  • the microfluidic chip 10 may include a plurality of injection channels 11 for injecting different fluid reactants, so as to perform sufficient and uniform mixing in the subsequent mixing channel 12 and rapid and sufficient reaction in the reaction channel 13 .
  • the inner diameter range of each injection channel 11 is 1-2 mm. If the inner diameter of the injection channel 11 is too large, accompanied by an excessive liquid flow rate, it will generate a relatively large pressure and even block the flow of the smaller reaction channel 13 connected thereafter; if the inner diameter is too small, the flow rate will be seriously insufficient , it is difficult to achieve the purpose of efficiently synthesizing products.
  • the inner diameter of the outflow channel 14 is in the range of 3-5mm, which can adapt to the flow rate of the mixing channel 12 and the reaction channel 13 connected to the front end, without causing fluid congestion, and the inner diameter is too small to cause the entire microfluidic chip to 10 Channel pressure increases. Further, the inner diameter of the outflow channel 14 can be kept consistent with the inner diameter of the mixing channel 12 , so that the outflow channel 14 and the mixing channel 12 can meet the same flow rate of liquid.
  • the volumes of multiple sub-reaction channels 131 are controlled to be substantially the same, so that the reaction time of the reaction solution in each sub-reaction channel is approximate, and the reaction solution flows and reacts approximately synchronously in all micro-channels, so that the fluid in each sub-reaction channel 131 enters and flows out.
  • reaction state is consistent, avoids that the reaction liquid of partial sub-reaction passage 131 is not fully reacted, and the reaction liquid of partial sub-reaction passage 131 has reacted completely, thereby causes the mixed reaction liquid that flows out passage 14 to flow out
  • the reaction stages are different.
  • the area where the reaction channel 13 is located in the microfluidic chip is a heatable area.
  • This area can be in a heated state, so that the inflowing and uniformly mixed reaction solution is rapidly heated to the reaction temperature when it enters the reaction channel 13 , and the reaction is quickly completed in the shorter reaction channel 13 .
  • a heating device can be arranged outside the microfluidic chip to heat the region where the reaction channel 13 is located, or a heating layer can be arranged in the microfluidic chip, and the heating layer is arranged in the region corresponding to the reaction channel 13 .
  • the present application also provides a micro-reaction system, refer to FIG. 3 , which is a schematic structural diagram of a micro-reaction system provided in an embodiment of the present application.
  • the micro reaction system 100 includes a sampling device 20 , a microfluidic chip 10 and a product collection device 30 .
  • the sampling device 20, the microfluidic chip 10 and the product collection device 30 are connected in sequence, so as to realize the sampling of the reaction liquid, the mixed reaction and the collection of the product through the micro reaction system.
  • the microfluidic chip 10 includes an injection channel 11 , a mixing channel 12 , a reaction channel 13 and an outflow channel 14 connected in sequence.
  • One end of the injection channel 11 is a feed port, which is connected with a sampling device 20 .
  • the other end of the injection channel 11 communicates with the mixing channel 12 .
  • the end of the mixing channel 12 away from the injection channel 11 is a split port 121 , and the split port 121 communicates with the reaction channel 13 .
  • the reaction channel 13 includes a plurality of sub-reaction channels 131 arranged in parallel, one end of each sub-reaction channel 131 communicates with the split port 121 of the mixing channel 12 , and the other end communicates with the confluence port 141 of the outflow channel 14 .
  • One end of the outflow channel 14 is a confluence port 141 , and the other end of the outflow channel 14 is a discharge port, which communicates with the product collecting device 30 .
  • a confluence port 141 One end of the outflow channel 14 is a confluence port 141 , and the other end of the outflow channel 14 is a discharge port, which communicates with the product collecting device 30 .
  • the reaction raw materials in the sampling device 20 or various materials enter the microfluidic chip 10 through the feed port of the injection channel 11, fully mix in the mixing channel 12, and flow into the microfluidic chip 12 through the split port 121.
  • the reaction liquid in each sub-reaction channel 131 is flowing and reacting at the same time and converging at the confluence port 141, and flows out of the microfluidic chip 10 through the outflow channel 14, that is, the fluid flows through the outlet Enter the product collection device 30 to realize the collection of products.
  • the limited chip space is fully utilized, and the amount of the reaction liquid in the reaction state per unit time is increased, thereby increasing the yield of the generated product per unit time and improving the synthesis efficiency.
  • the micro-sized sub-reaction channel 131 improves the heat transfer performance of the reaction solution and promotes high-quality synthesis and preparation of products.
  • the present application also provides a method for preparing quantum dots, using a microfluidic chip to prepare quantum dots.
  • the microfluidic chip includes sequentially connected injection channels, mixing channels, reaction channels, and outflow channels; multiple sub-reaction channels.
  • injection channel, the mixing channel, the reaction channel and the outflow channel reference may be made to the relevant descriptions in the above embodiments, and details are not repeated here.
  • Quantum dots in the present application can be selected from at least one of single-structure quantum dots and core-shell structure quantum dots, and the materials of single-structure quantum dots are selected from II-VI group compounds, III-V group compounds and I-III- At least one of the group VI compounds, the group II-VI compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, At least one of CdZnSeTe and CdZnSTe, the III-V group compound is selected from at least one of InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP, I-
  • Fig. 4 is a schematic flow diagram of a quantum dot preparation method provided in the embodiment of the present application, which specifically includes the following steps:
  • Step S11 the precursor solution flows in from the feed port of the injection channel, and flows through the mixing channel for mixing to obtain a mixed solution.
  • the precursor solution may be pre-mixed, injected through an injection channel, and further mixed in the mixing channel to obtain a mixed solution.
  • the precursor solutions may be of various types, such as an anion precursor solution and a cation precursor solution, which are respectively injected through different injection channels and mixed in the mixing channel to obtain a mixed solution.
  • Step S12 the mixed solution is divided into multiple branch streams at the split port of the mixing channel, and flows into multiple sub-reaction channels arranged in parallel, and reacts in the multiple sub-reaction channels to generate quantum dots.
  • the fully mixed mixed solution is obtained by flowing through the mixed solution, which is divided into multiple branch streams at the branch flow port, and flows into multiple sub-reaction channels for reactions to generate quantum dots.
  • the area corresponding to the reaction channel including multiple sub-reaction channels is a heating area.
  • Step S13 the multiple branches flow through the confluence port for confluence, flow through the outflow channel, and flow out of the microfluidic chip from the outlet of the outflow channel.
  • the quantum dots can be collected.
  • the mixed solution of the precursor can flow synchronously in multiple sub-reaction channels of the microfluidic chip for reaction, which increases the amount of reaction liquid for synchronous reaction and increases the amount of reaction liquid in the reaction state per unit time. amount, thereby increasing the yield of quantum dots per unit time and improving the synthesis efficiency of quantum dots.
  • the advantages of high heat and mass transfer of multiple micro-sized sub-reaction channels are used to improve the heat transfer performance of the reaction liquid and promote the high-quality synthesis and preparation of products.
  • the times for the multiple branch streams to flow from the diverging port to the converging port are the same.
  • the multiple sub-reaction channels in the multiple sub-reaction channels can be controlled to flow from the split port to the confluence port at the same time through the settings of the multiple sub-reaction channels of the above-mentioned microfluidic chip in the present application.
  • the multiple sub-reaction channels and the microfluidic chip including them reference may be made to the above, and details will not be repeated here.
  • the residence time of each branch stream in its corresponding sub-reaction channel is the same. Therefore, while improving the synthesis efficiency of quantum dots, it can ensure that the reaction stages of the mixed solutions flowing to the confluence port are the same or the state of the quantum dots is the same, thereby improving the synthesis consistency and product quality of quantum dots, and improving the quality of the microfluidics. Control the concentration of the quantum dot size distribution prepared by the chip.

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Abstract

A microfluidic chip, a micro-reaction system, and a quantum dot preparation method. A microfluidic chip (10) comprises an injection channel (11), a mixing channel (12), a reaction channel (13), and an outflow channel (14) communicated in sequence. A plurality of sub-reaction channels (131) are arranged in parallel so that the limited space of the chip is fully utilized, thereby increasing the amount of reaction liquid in a reaction state per unit time, increasing the yield of a generated product per unit time, and improving synthesis efficiency.

Description

微流控芯片、微反应系统和量子点的制备方法Preparation method of microfluidic chip, microreaction system and quantum dot
本申请要求于2021年12月27日在中国专利局提交的、申请号为202111619508.6、申请名称为“微流控芯片、微反应系统和量子点的制备方法”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application with the application number 202111619508.6 and the application name "Microfluidic chip, microreaction system and preparation method of quantum dots" filed at the China Patent Office on December 27, 2021, which The entire contents are incorporated by reference in this application.
技术领域technical field
本申请涉及微流反应领域,尤其涉及微流控芯片、微反应系统和量子点的制备方法。The present application relates to the field of microfluidic reactions, in particular to the preparation method of microfluidic chips, microreaction systems and quantum dots.
背景技术Background technique
微流反应又被称为微通道反应、流体微反应或微流控反应等。微流反应以连续流动代替传统间歇反应,通过连续的流体在微通道中混合反应或加热等反应条件下进行反应,连续合成制备出目标产物,且能对反应在微观尺度上实现精确控制,提高了反应选择性和操作安全性。微流控芯片因其微米尺寸的通道结构,极大的提高了反应的传热及传质性能。在制备纳米晶或量子点等材料时,前驱液在芯片中从室温状态进入加热状态需要的时间极短,表明在微流芯片中,极短的通道尺寸即可完成量子点的合成。Microfluidic reactions are also known as microchannel reactions, fluid microreactions, or microfluidic reactions. The microfluidic reaction replaces the traditional intermittent reaction with continuous flow, and reacts under the reaction conditions such as mixed reaction or heating in the microchannel through continuous fluid, and the target product is prepared by continuous synthesis, and the reaction can be precisely controlled on the microscopic scale, improving Reaction selectivity and operational safety. Due to its micron-sized channel structure, the microfluidic chip greatly improves the heat transfer and mass transfer performance of the reaction. When preparing materials such as nanocrystals or quantum dots, the time required for the precursor liquid to enter the heated state from the room temperature state in the chip is extremely short, indicating that in the microfluidic chip, the synthesis of quantum dots can be completed with an extremely short channel size.
技术问题technical problem
然而目前传统芯片通道结构为布满芯片平面的螺旋状或蛇形缠绕状通道,这样单一的反应通道不仅过度浪费了芯片空间,也使反应的合成效率较低。However, the current traditional chip channel structure is a helical or serpentine winding channel covering the chip plane. Such a single reaction channel not only wastes the chip space excessively, but also makes the synthesis efficiency of the reaction low.
技术解决方案technical solution
因此,本申请提供一种微流控芯片、微反应系统和量子点的制备方法。Therefore, the present application provides a method for preparing a microfluidic chip, a microreaction system and quantum dots.
本申请实施例提供一种微流控芯片,包括依次连通的注入通道、混合通道、反应通道和流出通道;所述注入通道的一端为进料口,另一端与所述混合通道连通;所述混合通道远离所述注入通道的一端为分流口,所述分流口与所述反应通道连通;所述反应通道包括并联设置多个子反应通道,每个所述子反应通 道的一端与所述混合通道另一端的分流口连通,另一端与所述流出通道的汇合口连通;所述流出通道的一端为所述汇合口,另一端为出料口。An embodiment of the present application provides a microfluidic chip, including an injection channel, a mixing channel, a reaction channel, and an outflow channel connected in sequence; one end of the injection channel is a feed port, and the other end communicates with the mixing channel; One end of the mixing channel away from the injection channel is a split port, and the split port communicates with the reaction channel; the reaction channel includes a plurality of sub-reaction channels arranged in parallel, and one end of each sub-reaction channel is connected to the mixing channel. The diverging port at the other end is connected, and the other end is connected with the confluence port of the outflow channel; one end of the outflow channel is the confluence port, and the other end is the discharge port.
可选的,在本申请的一些实施例中,至少部分所述子反应通道的容积基本相同。Optionally, in some embodiments of the present application, at least some of the sub-reaction channels have substantially the same volume.
可选的,在本申请的一些实施例中,至少部分所述子反应通道长度基本相同。Optionally, in some embodiments of the present application, at least some of the sub-reaction channels have substantially the same length.
可选的,在本申请的一些实施例中,所述多个子反应通道中,每个所述子反应通道的中轴线均位于同一平面;以所述分流口与所述汇合口的连线为基准线,远离所述基准线的方向上,所述子反应通道的长度逐渐增大,所述子反应通道的内径逐渐减小。Optionally, in some embodiments of the present application, among the plurality of sub-reaction channels, the central axis of each sub-reaction channel is located on the same plane; The reference line, in a direction away from the reference line, the length of the sub-reaction channel gradually increases, and the inner diameter of the sub-reaction channel gradually decreases.
可选的,在本申请的一些实施例中,多个所述子反应通道的内径范围为450μm-650μm。Optionally, in some embodiments of the present application, the inner diameters of the multiple sub-reaction channels range from 450 μm to 650 μm.
可选的,在本申请的一些实施例中,多个所述子反应通道的长度范围为80mm-167mm。Optionally, in some embodiments of the present application, the lengths of the multiple sub-reaction channels range from 80 mm to 167 mm.
可选的,在本申请的一些实施例中,每个所述子反应通道为包括多段直形通道连接而成或者为弧形通道。Optionally, in some embodiments of the present application, each sub-reaction channel is formed by connecting multiple straight channels or is an arc channel.
可选的,在本申请的一些实施例中,所述混合通道为S形通道。Optionally, in some embodiments of the present application, the mixing channel is an S-shaped channel.
可选的,在本申请的一些实施例中,所述混合通道的内径范围为3mm-5mm。Optionally, in some embodiments of the present application, the inner diameter of the mixing channel is in a range of 3mm-5mm.
可选的,在本申请的一些实施例中,所述微流控芯片包括多个所述注入通道,每个所述注入通道的内径范围为1mm-2mm。Optionally, in some embodiments of the present application, the microfluidic chip includes a plurality of injection channels, and the inner diameter of each injection channel ranges from 1 mm to 2 mm.
可选的,在本申请的一些实施例中,所述流出通道的内径范围为3-5mm。Optionally, in some embodiments of the present application, the inner diameter of the outflow channel is in the range of 3-5 mm.
可选的,在本申请的一些实施例中,所述流出通道的内径与所述混合通道的内径相同。Optionally, in some embodiments of the present application, the inner diameter of the outflow channel is the same as the inner diameter of the mixing channel.
可选的,在本申请的一些实施例中,所述反应通道所在的区域为加热区域。Optionally, in some embodiments of the present application, the area where the reaction channel is located is a heating area.
相应的,本申请实施例还提供一种微反应系统,包括进样装置、微流控芯片和产品收集装置;所述微流控芯片包括依次连通的注入通道、混合通道、反应通道和流出通道;所述注入通道的一端为进料口,连接所述进样装置;所述注入通道的另一端与所述混合通道连通;所述混合通道远离所述注入通道的一 端为分流口,所述分流口与所述反应通道连通;所述反应通道包括并联设置多个子反应通道,每个所述子反应通道的一端与所述混合通道另一端的分流口连通,另一端与所述流出通道的汇合口连通;所述流出通道的一端为所述汇合口,所述流出通道的另一端为出料口,与所述产品收集装置连通。Correspondingly, the embodiment of the present application also provides a micro-reaction system, including a sampling device, a microfluidic chip, and a product collection device; the microfluidic chip includes sequentially connected injection channels, mixing channels, reaction channels, and outflow channels One end of the injection channel is a feed port, connected to the sampling device; the other end of the injection channel communicates with the mixing channel; the end of the mixing channel away from the injection channel is a split port, the The split port is communicated with the reaction channel; the reaction channel includes a plurality of sub-reaction channels arranged in parallel, one end of each sub-reaction channel is communicated with the split port at the other end of the mixing channel, and the other end is connected with the outlet port of the outflow channel. The confluence port is connected; one end of the outflow channel is the confluence port, and the other end of the outflow channel is a discharge port, which communicates with the product collection device.
可选的,在本申请的一些实施例中,至少部分所述子反应通道的容积基本相同。Optionally, in some embodiments of the present application, at least some of the sub-reaction channels have substantially the same volume.
可选的,在本申请的一些实施例中,至少部分所述子反应通道长度基本相同。Optionally, in some embodiments of the present application, at least some of the sub-reaction channels have substantially the same length.
可选的,在本申请的一些实施例中,所述多个子反应通道中,每个所述子反应通道的中轴线均位于同一平面;以所述分流口与所述汇合口的连线为基准线,远离所述基准线的方向上,所述子反应通道的长度逐渐增大,所述子反应通道的内径逐渐减小。Optionally, in some embodiments of the present application, among the plurality of sub-reaction channels, the central axis of each sub-reaction channel is located on the same plane; The reference line, in a direction away from the reference line, the length of the sub-reaction channel gradually increases, and the inner diameter of the sub-reaction channel gradually decreases.
相应的,本申请实施例还提供一种量子点的制备方法,采用微流控芯片制备所述量子点,所述微流控芯片包括依次连通的注入通道、混合通道、反应通道和流出通道;其中,所述反应通道包括并联设置的多个子反应通道;所述制备方法包括:前驱体溶液由所述注入通道的进料口流入,流经所述混合通道进行混合得到混合溶液;所述混合溶液在所述混合通道的分流口分成多路支流,流入并联设置的多个所述子反应通道中,在多个所述子反应通道中反应生成量子点;多路支流流经汇合口进行汇合,并流经所述流出通道,由所述流出通道的出料口流出所述微流控芯片。Correspondingly, the embodiment of the present application also provides a method for preparing quantum dots. The quantum dots are prepared by using a microfluidic chip, and the microfluidic chip includes an injection channel, a mixing channel, a reaction channel, and an outflow channel connected in sequence; Wherein, the reaction channel includes a plurality of sub-reaction channels arranged in parallel; the preparation method includes: the precursor solution flows in from the feed port of the injection channel, and flows through the mixing channel for mixing to obtain a mixed solution; the mixing The solution is divided into multiple sub-flows at the diversion port of the mixing channel, and flows into multiple sub-reaction channels arranged in parallel, and reacts in multiple sub-reaction channels to generate quantum dots; the multiple sub-flows flow through the confluence port for confluence , and flow through the outflow channel, and flow out of the microfluidic chip from the outlet of the outflow channel.
可选的,在本申请的一些实施例中,所述多路支流由所述分流口流至所述汇合口的时间相同。Optionally, in some embodiments of the present application, the times for the multiple branches to flow from the diversion port to the confluence port are the same.
可选的,在本申请的一些实施例中,所述量子点选自单一结构量子点及核壳结构量子点中的至少一种,所述单一结构量子点的材料选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的至少一种,所述II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe及CdZnSTe中的至少一种,所述III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的至少一种, 所述I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的至少一种;所述核壳结构的量子点的核选自上述单一结构量子点中的任意一种,所述核壳结构的量子点的壳层材料选自CdS、CdTe、CdSeTe、CdZnSe、CdZnS、CdSeS、ZnSe、ZnSeS和ZnS中的至少一种。 Optionally, in some embodiments of the present application, the quantum dots are selected from at least one of single-structure quantum dots and core-shell structure quantum dots, and the material of the single-structure quantum dots is selected from group II-VI compounds , III-V group compound and at least one of I-III-VI group compound, and described II-VI group compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS , ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe at least one, the III-V group compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb At least one of , GaAlNP and InAlNP, the I-III-VI group compound is selected from at least one of CuInS 2 , CuInSe 2 and AgInS 2 ; the core of the quantum dot with the core-shell structure is selected from the above-mentioned single structure Any one of the quantum dots, the shell material of the quantum dots with core-shell structure is selected from at least one of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS and ZnS.
有益效果Beneficial effect
本申请的微流控芯片,支持反应液经过注入通道的进料口进入微流控芯片,在混合通道中进行充分混合,并通过分流口流入多个并联的子反应通道中,各个子反应通道中的反应液同时在流动反应并在汇合口进行汇合,经流出通道流出此微流控芯片,以利用此微流控芯片完成产物的合成制备。通过设置多个子反应通道,充分利用有限的芯片空间,增加了单位时间内处在反应状态的反应液的量,从而增加了单位时间内的生成产物的产量,提高了合成效率。同时,微小尺寸的子反应通道提高了反应液的热传递性能,促进产物的高质量合成制备。The microfluidic chip of the present application supports the reaction solution to enter the microfluidic chip through the feed port of the injection channel, fully mix in the mixing channel, and flow into a plurality of parallel sub-reaction channels through the split port, and each sub-reaction channel The reaction liquids in the flow reaction are combined at the confluence port at the same time, and flow out of the microfluidic chip through the outflow channel, so as to use the microfluidic chip to complete the synthesis and preparation of the product. By setting multiple sub-reaction channels and making full use of the limited chip space, the amount of the reaction solution in the reaction state per unit time is increased, thereby increasing the yield of the generated product per unit time and improving the synthesis efficiency. At the same time, the micro-sized sub-reaction channel improves the heat transfer performance of the reaction solution and promotes the high-quality synthesis of products.
附图说明Description of drawings
为了更清楚地说明本申请实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的一些实施例,对于本领域技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.
图1是本申请实施例提供的一种微流控芯片的结构示意图;FIG. 1 is a schematic structural diagram of a microfluidic chip provided in an embodiment of the present application;
图2是本申请实施例提供的一种反应通道的结构示意图;Fig. 2 is a schematic structural view of a reaction channel provided in an embodiment of the present application;
图3是本申请实施例提供的一种微反应系统的结构示意图;Fig. 3 is the structural representation of a kind of micro-reaction system provided by the embodiment of the present application;
图4是本申请实施例提供的一种量子点制备方法的流程示意图。Fig. 4 is a schematic flow chart of a method for preparing quantum dots provided in an embodiment of the present application.
本申请的实施方式Embodiment of this application
下面将结合本申请实施例中的附图,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是 全部的实施例。基于本申请中的实施例,本领域技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本申请保护的范围。The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts belong to the scope of protection of this application.
此外,应当理解的是,此处所描述的具体实施方式仅用于说明和解释本申请,并不用于限制本申请。在本申请中,在未作相反说明的情况下,使用的方位词如“上”和“下”具体为附图中的图面方向。另外,在本申请的描述中,术语“包括”是指“包括但不限于”。本发明的各种实施例可以以一个范围的形式存在;应当理解,以一范围形式的描述仅仅是因为方便及简洁,不应理解为对本发明范围的硬性限制;因此,应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如,应当认为从1到6的范围描述已经具体公开子范围,例如从1到3,从1到4,从1到5,从2到4,从2到6,从3到6等,以及所述范围内的单一数字,例如1、2、3、4、5及6,此不管范围为何皆适用。另外,每当在本文中指出数值范围,是指包括所指范围内的任何引用的数字(分数或整数)。In addition, it should be understood that the specific implementations described here are only used to illustrate and explain the present application, and are not intended to limit the present application. In the present application, unless otherwise stated, the used orientation words such as "upper" and "lower" specifically refer to the direction of the drawings in the drawings. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be construed as a rigid limitation on the scope of the present invention; therefore, the stated range should be considered The description has specifically disclosed all possible subranges as well as individual values within that range. For example, a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range. Additionally, whenever a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
在本申请中,“和/或”,描述关联对象的关联关系,表示可以存在三种关系,例如,A和/或B,可以表示:单独存在A,同时存在A和B,单独存在B的情况。其中A,B可以是单数或者复数。In this application, "and/or" describes the association relationship of associated objects, indicating that there may be three types of relationships, for example, A and/or B, which may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural.
在本申请中,“至少一个”是指一个或者多个,“多个”是指两个或两个以上。“至少一种”、“以下至少一项(个)”或其类似表达,是指的这些项中的任意组合,包括单项(个)或复数项(个)的任意组合。例如,“a,b,或c中的至少一项(个)”,或,“a,b,和c中的至少一项(个)”,均可以表示:a,b,c,a-b(即a和b),a-c,b-c,或a-b-c,其中a,b,c分别可以是单个,也可以是多个。In this application, "at least one" means one or more, and "multiple" means two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of a single item or a plurality of items. For example, "at least one item (unit) of a, b, or c", or "at least one item (unit) of a, b, and c" can mean: a, b, c, a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.
本申请的微流控芯片,是指可以进行微流反应的芯片,即在一块微米尺度的芯片上集成有容纳流体的通道、混合单元、反应单元和其它功能部件,操控微米体积的流体在微小空间中的运动过程,从而实现在芯片上进行流体反应,实现连续制备产物,比如可以实现连续制备纳米晶或量子点。The microfluidic chip in this application refers to a chip that can perform microfluidic reactions, that is, channels for containing fluids, mixing units, reaction units, and other functional components are integrated on a micron-scale chip to manipulate micron-volume fluids in a micron The movement process in space, so as to realize the fluid reaction on the chip, and realize the continuous preparation of products, such as the continuous preparation of nanocrystals or quantum dots.
请参阅图1,图1是本申请实施例提供的一种微流控芯片的结构示意图。微流控芯片10包括注入通道11、混合通道12、反应通道13和流出通道14。注入通道11、混合通道12、反应通道13和流出通道14依次连通。Please refer to FIG. 1 . FIG. 1 is a schematic structural diagram of a microfluidic chip provided in an embodiment of the present application. The microfluidic chip 10 includes an injection channel 11 , a mixing channel 12 , a reaction channel 13 and an outflow channel 14 . The injection channel 11 , the mixing channel 12 , the reaction channel 13 and the outflow channel 14 communicate in sequence.
具体地,注入通道11的一端为进料口(图未注),另一端与混合通道12 连通。混合通道12远离注入通道11的一端为分流口121,分流口121与反应通道13连通。反应通道13包括并联设置多个子反应通道131,每个子反应通道131的一端与混合通道12另一端的分流口121连通,每个子反应通道131的另一端与流出通道14的汇合口141连通。流出通道14的一端为汇合口141,另一端为出料口(图未注)。Specifically, one end of the injection channel 11 is a feed port (not shown in the figure), and the other end communicates with the mixing channel 12 . The end of the mixing channel 12 away from the injection channel 11 is a split port 121 , and the split port 121 communicates with the reaction channel 13 . The reaction channel 13 includes a plurality of sub-reaction channels 131 arranged in parallel, one end of each sub-reaction channel 131 communicates with the split port 121 at the other end of the mixing channel 12 , and the other end of each sub-reaction channel 131 communicates with the confluence port 141 of the outflow channel 14 . One end of the outflow channel 14 is a confluence port 141, and the other end is a discharge port (not noted in the figure).
本实施例中,反应液经过注入通道11的进料口进入微流控芯片10,在混合通道12中进行充分混合,并通过分流口121流入多个并联的子反应通道131中,各个子反应通道131中的反应液同时在流动反应并在汇合口141进行汇合,经流出通道14流出此微流控芯片10,以利用此微流控芯片10完成产物的合成制备。通过设置多个子反应通道131,充分利用有限的芯片空间,增加了单位时间内处在反应状态的反应液的量,从而增加了单位时间内的生成产物的产量,提高了合成效率。同时,微小尺寸的子反应通道131提高了反应液的热传递性能,促进产物的高质量合成制备。In this embodiment, the reaction solution enters the microfluidic chip 10 through the feed port of the injection channel 11, is fully mixed in the mixing channel 12, and flows into a plurality of parallel sub-reaction channels 131 through the split port 121, and each sub-reaction The reaction solution in the channel 131 is flowing and reacting at the same time and merged at the confluence port 141 , and flows out of the microfluidic chip 10 through the outflow channel 14 , so that the microfluidic chip 10 is used to complete the synthesis and preparation of the product. By arranging a plurality of sub-reaction channels 131, the limited chip space is fully utilized, and the amount of the reaction liquid in the reaction state per unit time is increased, thereby increasing the yield of the generated product per unit time and improving the synthesis efficiency. At the same time, the micro-sized sub-reaction channel 131 improves the heat transfer performance of the reaction solution and promotes high-quality synthesis and preparation of products.
每个子反应通道131的一端与分流口121连通,每个子反应通道131的另一端与汇合口141连通,则每个流出通道14由分流口121到汇合口141的通道即对应各个流出通道14。子反应通道131的容积为由分流口121到汇合口141的通道容积,子反应通道131的长度为由分流口121到汇合口141对应的通道长度。One end of each sub-reaction channel 131 communicates with the diversion port 121 , and the other end of each sub-reaction channel 131 communicates with the confluence port 141 . The volume of the sub-reaction channel 131 is the channel volume from the diversion port 121 to the confluence port 141 , and the length of the sub-reaction channel 131 is the corresponding channel length from the diversion port 121 to the confluence port 141 .
具体的,至少部分子反应通道131的容积或者体积基本相同,即多个子反应通道131中的部分子反应通道131或者全部的子反应通道131对应的容积基本相同。子反应通道131的长度与内径的平方成反比,使反应液在各个子反应通道131中的反应时间相近或相等,反应液在所有微通道内近似同步流动反应,从而使各个子反应通道131中的流体进入流出通道14的汇合口141时,反应状态一致,避免部分子反应通道131的反应液还未完全反应,而部分子反应通道131的反应液已完全反应,从而导致流出通道14流出的混合反应液的反应阶段不同,从而影响产物的状态和产品质量。Specifically, the volumes or volumes of at least some of the sub-reaction channels 131 are substantially the same, that is, the corresponding volumes of some of the sub-reaction channels 131 or all the sub-reaction channels 131 in the plurality of sub-reaction channels 131 are basically the same. The length of the sub-reaction channel 131 is inversely proportional to the square of the internal diameter, so that the reaction time of the reaction solution in each sub-reaction channel 131 is close or equal, and the reaction solution is approximately synchronously flowing in all microchannels, so that in each sub-reaction channel 131 When the fluid of the fluid enters the confluence port 141 of the outflow channel 14, the reaction state is consistent, avoiding that the reaction solution of the sub-reaction channel 131 has not completely reacted, and the reaction solution of the sub-reaction channel 131 has completely reacted, thereby causing the outflow channel 14 to flow out. The reaction stages of the mixed reaction solution are different, thus affecting the state and quality of the product.
进一步的,至少部分子反应通道131的容积或者体积基本相同,且至少部分子反应通道131长度相同。由于子反应通道131的容积与长度和内径相关,则多个子反应通道131的内径也相同。此时多个子反应通道131可以不设置在 同一平面,即微流控芯片10为三维结构,从而提高使用此微流控芯片10制备产物的合成效率的同时,能够保证流出通道14流出并进行收集的混合反应液的反应阶段相同,从而提高产物的合成一致性和产品质量。比如合成量子点时,提高量子点尺寸分布的集中性。Further, at least part of the sub-reaction channels 131 have substantially the same volume or volume, and at least part of the sub-reaction channels 131 have the same length. Since the volume of the sub-reaction channels 131 is related to the length and inner diameter, the inner diameters of the plurality of sub-reaction channels 131 are also the same. At this time, multiple sub-reaction channels 131 may not be arranged on the same plane, that is, the microfluidic chip 10 has a three-dimensional structure, thereby improving the synthesis efficiency of the product prepared by using the microfluidic chip 10, while ensuring that the outflow channel 14 flows out and collects The reaction stages of the mixed reaction solution are the same, thereby improving the synthesis consistency and product quality of the product. For example, when synthesizing quantum dots, improve the concentration of quantum dot size distribution.
在另一个实施例中,微流控芯片10是平面结构,其上设置的多个子反应通道131中,每个所述子反应通道131的中轴线均位于同一平面。此时全部的子反应通道131均在同一平面。以分流口121与汇合口141的连线为基准线a-a’,在远离基准线a-a’的方向X和X’上,子反应通道131的长度逐渐增大,子反应通道131的内径逐渐减小。In another embodiment, the microfluidic chip 10 is a planar structure, and among the plurality of sub-reaction channels 131 disposed on it, the central axis of each sub-reaction channel 131 is located on the same plane. At this time, all sub-reaction channels 131 are on the same plane. Taking the connection line between the diversion port 121 and the confluence port 141 as the reference line aa', in the directions X and X' away from the reference line aa', the length of the sub-reaction channel 131 gradually increases, and the length of the sub-reaction channel 131 The inner diameter gradually decreases.
各个子反应通道131均在微流控反应芯片10上,处于同一平面,因此在并联时可能长度不同,比如,每个子反应通道131两端均分别连接分流口121与汇合口141,那么最短的通道即为分流口121与汇合口141的直线连接,即与基准线a-a’重合的反应通道。而沿远离基准线a-a’的方向上,即垂直于基准线a-a’的方向上,子反应通道131的长度逐渐增大,即越靠近基准线a-a’的子反应通道131越短,越远离基准线a-a’的子反应通道131越长。当然,可以设置与基准线a-a’重合的子反应通道131,也可以不设置与基准线a-a’重合的子反应通道131,此处不进行限制。而在远离基准线a-a’的方向上,子反应通道131的长度逐渐增大,子反应通道131的内径逐渐减小,而内径减小会导致流速增大,在从而使长度较大的子反应通道131的流速也相应较大,从而使反应液在各个子反应通道131中的反应时间近似,反应液在所有微通道内近似同步流动反应,从而使各个子反应通道131中的流体进入流出通道14的汇合口141时,反应状态一致,避免部分子反应通道131的反应液还未完全反应,而部分子反应通道131的反应液已完全反应,从而导致流出通道14流出的混合反应液的反应阶段不同,从而影响产物的状态和产品质量。Each sub-reaction channel 131 is on the microfluidic reaction chip 10 and is on the same plane, so the lengths may be different when they are connected in parallel. The channel is the straight line connection between the diverging port 121 and the converging port 141 , that is, the reaction channel coincident with the reference line aa'. And along the direction away from the reference line aa', that is, in the direction perpendicular to the reference line aa', the length of the sub-reaction channel 131 gradually increases, that is, the closer the sub-reaction channel 131 to the reference line aa' The shorter the sub-reaction channel 131 is, the farther away from the reference line aa' is the longer. Certainly, the sub-reaction channel 131 coincident with the reference line a-a' may be provided, or the sub-reaction channel 131 coincident with the reference line a-a' may not be provided, which is not limited here. In the direction away from the reference line a-a', the length of the sub-reaction channel 131 gradually increases, and the inner diameter of the sub-reaction channel 131 gradually decreases, and the decrease in the inner diameter will lead to an increase in the flow rate, so that the longer length The flow velocity of the sub-reaction channel 131 is also relatively large, so that the reaction time of the reaction solution in each sub-reaction channel 131 is approximate, and the reaction solution flows and reacts approximately synchronously in all microchannels, so that the fluid in each sub-reaction channel 131 enters When the confluence port 141 of the outflow channel 14, the reaction state is consistent, avoiding that the reaction solution of the sub-sub-reaction channel 131 has not completely reacted, while the reaction solution of the sub-sub-reaction channel 131 has completely reacted, resulting in the mixed reaction solution flowing out of the outflow channel 14. The reaction stage is different, which affects the state of the product and product quality.
进一步地,多个子反应通道131的容积可以相同。参阅图2,图2是本申请实施例提供的一种反应通道的结构示意图。反应通道13包括第一子反应通道ACDB和第二子反应通道AEFB。第一子反应通道ACDB的长度记为L 1,内径为r 1。第二子反应通道AEFB,长度为记为L 2,内径为r 2。第一子反应通道ACDB和第二子反应通道AEFB的容积相同,根据容积公式,可以得到两 个子反应通道131满足式(I): Further, the volumes of the sub-reaction channels 131 may be the same. Referring to FIG. 2, FIG. 2 is a schematic structural diagram of a reaction channel provided in an embodiment of the present application. The reaction channel 13 includes a first sub-reaction channel ACDB and a second sub-reaction channel AEFB. The length of the first sub-reaction channel ACDB is denoted as L 1 , and the inner diameter is r 1 . The length of the second sub-reaction channel AEFB is denoted as L 2 , and the inner diameter is r 2 . The volumes of the first sub-reaction channel ACDB and the second sub-reaction channel AEFB are the same, and according to the volume formula, two sub-reaction channels 131 can be obtained to satisfy the formula (I):
r 1 2L 1=r 2 2L 2           式(I) r 1 2 L 1 =r 2 2 L 2 formula (I)
即子反应通道131的长度与内径的平方成反比。That is, the length of the sub-reaction channel 131 is inversely proportional to the square of the inner diameter.
进一步地,每个子反应通道131可以包括多段直形通道连接而成。参阅图2,以三段直形通道为例,第一子反应通道ACDB包括AC段,CD段和DB段,长度分别为L 11、L 12和L 13。第二子反应通道AEFB包括AE段、EF段和FB段,长度分别为L 21、L 22和L 23。则式(I)相应变换为r 1 2(L 11+L 12+L 13)=r 2 2(L 21+L 22+L 23)。进一步的,可以使每个子反应通道131中的每一段容积相同,即满足r 1 2L 11=r 2 2L 21,r 1 2L 12=r 2 2L 22,r 1 2L 13=r 2 2L 23。且每一子反应通道131自身可以为轴对称结构。比如,第一子反应通道ACDB,以CD段的中线作为轴线,呈轴对称结构。此时,AC段和DB段呈轴对称分布,长度相等,即满足L 11=L 13Further, each sub-reaction channel 131 may be formed by connecting multiple segments of straight channels. Referring to Fig. 2, taking the three-section straight channel as an example, the first sub-reaction channel ACDB includes section AC, section CD and section DB, the lengths of which are L 11 , L 12 and L 13 respectively. The second sub-reaction channel AEFB includes an AE segment, an EF segment and a FB segment, and the lengths are L 21 , L 22 and L 23 respectively. Then formula (I) is correspondingly transformed into r 1 2 (L 11 +L 12 +L 13 )=r 2 2 (L 21 +L 22 +L 23 ). Further, the volume of each section in each sub-reaction channel 131 can be made the same, that is, r 1 2 L 11 =r 2 2 L 21 , r 1 2 L 12 =r 2 2 L 22 , r 1 2 L 13 =r 2 2 L 23 . And each sub-reaction channel 131 itself may be an axisymmetric structure. For example, the first sub-reaction channel ACDB has an axisymmetric structure with the midline of the CD segment as the axis. At this time, the AC segment and the DB segment are axisymmetrically distributed and have the same length, that is, L 11 =L 13 is satisfied.
当然,子反应通道131也可以为弧形通道,根据与基准线a-a’的远近不同,子反应通道131的弧度不同。比如越靠近基准线a-a’的子反应通道131弧度较小,而越远离基准线a-a’的子反应通道131弧度较大。Of course, the sub-reaction channel 131 can also be an arc-shaped channel, and the arc of the sub-reaction channel 131 is different according to the distance from the reference line a-a'. For example, the sub-reaction channel 131 closer to the reference line a-a' has a smaller arc, while the sub-reaction channel 131 farther away from the reference line a-a' has a larger arc.
在一实施例中,多个子反应通道131的内径范围为450μm-650μm。此范围内径的通道用于加热等流体反应时,避免内径尺寸过大丧失其作为微流反应在传热传质方面的优势,也能够避免内径过小造成较大流速及反应量较小,不利于产物的合成制备以及保证较高的产量和合成效率。In one embodiment, the inner diameters of the sub-reaction channels 131 range from 450 μm to 650 μm. When channels with inner diameters in this range are used for fluid reactions such as heating, it can avoid losing its advantages in heat and mass transfer as a microfluidic reaction when the inner diameter is too large, and it can also avoid large flow rates and small reaction volumes caused by too small inner diameters It is beneficial to the synthesis and preparation of products and ensures higher yield and synthesis efficiency.
子反应通道131的长度可以基于不同的流体反应进行相应的设置。比如通过加热区域的反应通道13合成纳米晶或量子点,反应通道13中各个子反应通道131的长度范围根据合成纳米晶或量子点的反应需求进行设定。当子反应通道131长度过短,反应液流经时间太短,反应会不充分;若通过降低流速达到增长反应时间的目的,则会降低的产品的合成效率。反应液在通道内已经完全反应后,过长的长度对反应的合成效率不会产生积极效果,会造成管道的浪费。The length of the sub-reaction channels 131 can be set correspondingly based on different fluid reactions. For example, nanocrystals or quantum dots are synthesized through the reaction channel 13 in the heating area, and the length range of each sub-reaction channel 131 in the reaction channel 13 is set according to the reaction requirements for synthesizing nanocrystals or quantum dots. When the length of the sub-reaction channel 131 is too short, the reaction liquid flows through for too short a time, and the reaction will be insufficient; if the purpose of increasing the reaction time is achieved by reducing the flow rate, the synthesis efficiency of the product will be reduced. After the reaction solution has been completely reacted in the channel, the too long length will not have a positive effect on the synthesis efficiency of the reaction, and will cause waste of the pipeline.
具体的,混合通道12可以为本领域已知的用于反应物混合的通道。在一具体实施例中,混合通道12为S形通道或者蛇形通道,且可以为多段弯折的S形通道,以能使反应液充分混合的同时,减小混合通道12的占用面积。进一步的,蛇形的混合通道12的内径范围可以为3-5mm。该S形段通道仅作为反应也流向加热区域前的混合,该混合通道12的内径能够满足于较大流量的 液体流动,以在反应区域中给多个子反应通道131提供足够的反应液,因此内径尺寸不能过小。而内径尺寸过大会因注入通道流量有限而导致该段通道液体流速变慢,以及混合通道12内可能会有过盈空腔存留气体,影响合成效果。Specifically, the mixing channel 12 may be a channel known in the art for mixing reactants. In a specific embodiment, the mixing channel 12 is an S-shaped channel or a serpentine channel, and may be a multi-segment bent S-shaped channel, so as to fully mix the reaction solution and reduce the occupied area of the mixing channel 12 . Further, the inner diameter of the serpentine mixing channel 12 may be 3-5mm. The S-shaped section channel is only used as the reaction and also flows to the mixing before the heating area. The inner diameter of the mixing channel 12 can satisfy the liquid flow of a relatively large flow rate, so as to provide sufficient reaction liquid for multiple sub-reaction channels 131 in the reaction area, so The inner diameter cannot be too small. However, if the inner diameter is too large, the liquid flow rate in this section of the channel will slow down due to the limited flow rate of the injection channel, and there may be an interference cavity in the mixing channel 12 to retain gas, which will affect the synthesis effect.
在一实施例中,微流控芯片10中可以包括多个注入通道11,分别注入不同的流体反应物,以在后续混合通道12中进行充分均匀混合以及在反应通道13中进行快速充分反应。其中,每个注入通道11的内径范围为1-2mm。注入通道11的内径尺寸过大,伴随着的是过大的液体流量,会对其之后连通的较小尺寸的反应通道13产生较大压力甚至流量拥堵;内径尺寸过小,会造成流量严重不足,难以达到高效合成产物的目的。In one embodiment, the microfluidic chip 10 may include a plurality of injection channels 11 for injecting different fluid reactants, so as to perform sufficient and uniform mixing in the subsequent mixing channel 12 and rapid and sufficient reaction in the reaction channel 13 . Wherein, the inner diameter range of each injection channel 11 is 1-2 mm. If the inner diameter of the injection channel 11 is too large, accompanied by an excessive liquid flow rate, it will generate a relatively large pressure and even block the flow of the smaller reaction channel 13 connected thereafter; if the inner diameter is too small, the flow rate will be seriously insufficient , it is difficult to achieve the purpose of efficiently synthesizing products.
在一实施例中,流出通道14的内径范围为3-5mm,能够与其前端连通的混合通道12和反应通道13的流量相适应,不会造成流体拥堵,以及内径过小导致整个微流控芯片10中通道压力增加。进一步的,流出通道14的内径尺寸可以与混合通道12的内径保持一致,使流出通道14与混合通道12满足同等大小流量液体流动。In one embodiment, the inner diameter of the outflow channel 14 is in the range of 3-5mm, which can adapt to the flow rate of the mixing channel 12 and the reaction channel 13 connected to the front end, without causing fluid congestion, and the inner diameter is too small to cause the entire microfluidic chip to 10 Channel pressure increases. Further, the inner diameter of the outflow channel 14 can be kept consistent with the inner diameter of the mixing channel 12 , so that the outflow channel 14 and the mixing channel 12 can meet the same flow rate of liquid.
但控制多个子反应通道131的容积基本相同,使反应液在各个子反应通道中的反应时间近似,反应液在所有微通道内近似同步流动反应,从而使各个子反应通道131中的流体进入流出通道14的汇合口141时,反应状态一致,避免部分子反应通道131的反应液还未完全反应,而部分子反应通道131的反应液已完全反应,从而导致流出通道14流出的混合反应液的反应阶段不同。However, the volumes of multiple sub-reaction channels 131 are controlled to be substantially the same, so that the reaction time of the reaction solution in each sub-reaction channel is approximate, and the reaction solution flows and reacts approximately synchronously in all micro-channels, so that the fluid in each sub-reaction channel 131 enters and flows out. When the confluence port 141 of passage 14, reaction state is consistent, avoids that the reaction liquid of partial sub-reaction passage 131 is not fully reacted, and the reaction liquid of partial sub-reaction passage 131 has reacted completely, thereby causes the mixed reaction liquid that flows out passage 14 to flow out The reaction stages are different.
在本申请中,微流控芯片中反应通道13所在的区域,为可加热区域。此区域可以处于被加热状态,从而使流入且混合均匀的反应液在进入反应通道13中时迅速加热至反应温度,并在较短的反应通道13迅速完成反应。可以理解的,可以在此微流控芯片的外部设置加热装置对反应通道13所在的区域进行加热,也可以在此微流控芯片内设置加热层,加热层设置在与反应通道13对应的区域。In this application, the area where the reaction channel 13 is located in the microfluidic chip is a heatable area. This area can be in a heated state, so that the inflowing and uniformly mixed reaction solution is rapidly heated to the reaction temperature when it enters the reaction channel 13 , and the reaction is quickly completed in the shorter reaction channel 13 . It can be understood that a heating device can be arranged outside the microfluidic chip to heat the region where the reaction channel 13 is located, or a heating layer can be arranged in the microfluidic chip, and the heating layer is arranged in the region corresponding to the reaction channel 13 .
本申请还提供一种微反应系统,参阅图3,图3是本申请实施例提供的一种微反应系统的结构示意图。微反应系统100包括进样装置20、微流控芯片10和产品收集装置30。进样装置20、微流控芯片10和产品收集装置30依次连通,以通过此微反应系统,实现反应液进样、混合反应以及产品收集。The present application also provides a micro-reaction system, refer to FIG. 3 , which is a schematic structural diagram of a micro-reaction system provided in an embodiment of the present application. The micro reaction system 100 includes a sampling device 20 , a microfluidic chip 10 and a product collection device 30 . The sampling device 20, the microfluidic chip 10 and the product collection device 30 are connected in sequence, so as to realize the sampling of the reaction liquid, the mixed reaction and the collection of the product through the micro reaction system.
其中,微流控芯片10包括依次连通的注入通道11、混合通道12、反应通道13和流出通道14。注入通道11的一端为进料口,连接进样装置20。注入通道11的另一端与混合通道12连通。混合通道12远离注入通道11的一端为分流口121,分流口121与反应通道13连通。反应通道13包括并联设置的多个子反应通道131,每个子反应通道131的一端与混合通道12的分流口121连通,另一端与流出通道14的汇合口141连通。流出通道14的一端为汇合口141,流出通道14的另一端为出料口,与产品收集装置30连通。其中,微流控芯片10可以参考上文中的相关描述,此处不进行赘述。Wherein, the microfluidic chip 10 includes an injection channel 11 , a mixing channel 12 , a reaction channel 13 and an outflow channel 14 connected in sequence. One end of the injection channel 11 is a feed port, which is connected with a sampling device 20 . The other end of the injection channel 11 communicates with the mixing channel 12 . The end of the mixing channel 12 away from the injection channel 11 is a split port 121 , and the split port 121 communicates with the reaction channel 13 . The reaction channel 13 includes a plurality of sub-reaction channels 131 arranged in parallel, one end of each sub-reaction channel 131 communicates with the split port 121 of the mixing channel 12 , and the other end communicates with the confluence port 141 of the outflow channel 14 . One end of the outflow channel 14 is a confluence port 141 , and the other end of the outflow channel 14 is a discharge port, which communicates with the product collecting device 30 . Wherein, for the microfluidic chip 10, reference may be made to relevant descriptions above, and details are not repeated here.
本实施例中微反应系统100,进样装置20中的反应原料或者各个物料经过注入通道11的进料口进入微流控芯片10,在混合通道12中进行充分混合,并通过分流口121流入多个并联的子反应通道131中,各个子反应通道131中的反应液同时在流动反应并在汇合口141进行汇合,经流出通道14流出此微流控芯片10,即流体流经出料口进入产品收集装置30中,实现产品的收集。通过设置多个子反应通道131,充分利用有限的芯片空间,增加了单位时间内处在反应状态的反应液的量,从而增加了单位时间内的生成产物的产量,提高了合成效率。同时,微小尺寸的子反应通道131提高了反应液的热传递性能,促进产物的高质量合成制备。In the micro reaction system 100 in this embodiment, the reaction raw materials in the sampling device 20 or various materials enter the microfluidic chip 10 through the feed port of the injection channel 11, fully mix in the mixing channel 12, and flow into the microfluidic chip 12 through the split port 121. In a plurality of sub-reaction channels 131 connected in parallel, the reaction liquid in each sub-reaction channel 131 is flowing and reacting at the same time and converging at the confluence port 141, and flows out of the microfluidic chip 10 through the outflow channel 14, that is, the fluid flows through the outlet Enter the product collection device 30 to realize the collection of products. By arranging a plurality of sub-reaction channels 131, the limited chip space is fully utilized, and the amount of the reaction liquid in the reaction state per unit time is increased, thereby increasing the yield of the generated product per unit time and improving the synthesis efficiency. At the same time, the micro-sized sub-reaction channel 131 improves the heat transfer performance of the reaction solution and promotes high-quality synthesis and preparation of products.
本申请还提供一种量子点的制备方法,采用微流控芯片制备量子点,微流控芯片包括依次连通的注入通道、混合通道、反应通道和流出通道;其中,所述反应通道包括并联设置的多个子反应通道。其中,注入通道、混合通道、反应通道和流出通道可以参考上文实施例中的相关描述,此处不进行赘述。The present application also provides a method for preparing quantum dots, using a microfluidic chip to prepare quantum dots. The microfluidic chip includes sequentially connected injection channels, mixing channels, reaction channels, and outflow channels; multiple sub-reaction channels. For the injection channel, the mixing channel, the reaction channel and the outflow channel, reference may be made to the relevant descriptions in the above embodiments, and details are not repeated here.
本申请中的量子点,可以选自单一结构量子点及核壳结构量子点中的至少一种,单一结构量子点的材料选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的至少一种,II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe及CdZnSTe中的至少一种,III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的至少一种,I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的至少一种;核壳结构的量子点的核选自上述单一结构量子点中的任 意一种,核壳结构的量子点的壳层材料选自CdS、CdTe、CdSeTe、CdZnSe、CdZnS、CdSeS、ZnSe、ZnSeS和ZnS中的至少一种。 Quantum dots in the present application can be selected from at least one of single-structure quantum dots and core-shell structure quantum dots, and the materials of single-structure quantum dots are selected from II-VI group compounds, III-V group compounds and I-III- At least one of the group VI compounds, the group II-VI compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, At least one of CdZnSeTe and CdZnSTe, the III-V group compound is selected from at least one of InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, GaAlNP and InAlNP, I-III-VI The family compound is selected from at least one of CuInS 2 , CuInSe 2 and AgInS 2 ; the core of the quantum dot with the core-shell structure is selected from any of the above-mentioned single-structure quantum dots, and the shell material of the quantum dot with the core-shell structure is selected from At least one selected from CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS and ZnS.
参阅图4,图4是本申请实施例提供的一种量子点制备方法的流程示意图,具体包括如下步骤:Referring to Fig. 4, Fig. 4 is a schematic flow diagram of a quantum dot preparation method provided in the embodiment of the present application, which specifically includes the following steps:
步骤S11:前驱体溶液由注入通道的进料口流入,流经混合通道进行混合得到混合溶液。Step S11: the precursor solution flows in from the feed port of the injection channel, and flows through the mixing channel for mixing to obtain a mixed solution.
本步骤中,前驱体溶液可以是预先混合后,由一个注入通道注入,在混合通道中进行进一步混合得到混合溶液。或者,前驱体溶液可以为多种,比如阴离子前驱体溶液和阳离子前驱体溶液,分别由不同的注入通道注入,在混合通道中进行混合得到混合溶液。In this step, the precursor solution may be pre-mixed, injected through an injection channel, and further mixed in the mixing channel to obtain a mixed solution. Alternatively, the precursor solutions may be of various types, such as an anion precursor solution and a cation precursor solution, which are respectively injected through different injection channels and mixed in the mixing channel to obtain a mixed solution.
步骤S12:混合溶液在混合通道的分流口分成多路支流,流入并联设置的多个子反应通道中,在多个子反应通道中反应生成量子点。Step S12: the mixed solution is divided into multiple branch streams at the split port of the mixing channel, and flows into multiple sub-reaction channels arranged in parallel, and reacts in the multiple sub-reaction channels to generate quantum dots.
在上一步骤中流经混合溶液得到充分混合的混合溶液,在分流口分成了多路支流,流入多个子反应通道中进行反应,生成量子点。进一步的,包括多个子反应通道的反应通道对应的区域,为加热区域。通过在对反应通道进行加热达到反应所需的温度,各路支流进入各个子反应通道后,由于通道尺寸较小,具有较好的传热性能,因此各个支流中的混合液可以迅速升温达到反应温度,从而快速完成量子点的合成制备。In the previous step, the fully mixed mixed solution is obtained by flowing through the mixed solution, which is divided into multiple branch streams at the branch flow port, and flows into multiple sub-reaction channels for reactions to generate quantum dots. Further, the area corresponding to the reaction channel including multiple sub-reaction channels is a heating area. By heating the reaction channel to reach the temperature required for the reaction, after each branch flow enters each sub-reaction channel, due to the small size of the channel, it has better heat transfer performance, so the mixed liquid in each branch flow can quickly heat up to reach the reaction temperature. temperature, so as to quickly complete the synthesis and preparation of quantum dots.
步骤S13:多路支流流经汇合口进行汇合,并流经流出通道,由流出通道的出料口流出微流控芯片。Step S13: the multiple branches flow through the confluence port for confluence, flow through the outflow channel, and flow out of the microfluidic chip from the outlet of the outflow channel.
在本步骤,包含量子点的溶液流出微流控芯片之后,可以进行量子点的收集。In this step, after the solution containing the quantum dots flows out of the microfluidic chip, the quantum dots can be collected.
本实施例中,前驱体的混合溶液在微流控芯片的多个子反应通道中可以同步流动进行反应,增加了同步反应的反应液的量,增加了单位时间内处在反应状态的反应液的量,从而增加了单位时间内的生成量子点的产量,提高了量子点合成效率。同时,通过多路支流的反应,利用多个微小尺寸的子反应通道的高传热传质优势,也提高了反应液的热传递性能,促进产物的高质量合成制备。In this embodiment, the mixed solution of the precursor can flow synchronously in multiple sub-reaction channels of the microfluidic chip for reaction, which increases the amount of reaction liquid for synchronous reaction and increases the amount of reaction liquid in the reaction state per unit time. amount, thereby increasing the yield of quantum dots per unit time and improving the synthesis efficiency of quantum dots. At the same time, through the reaction of multiple branch streams, the advantages of high heat and mass transfer of multiple micro-sized sub-reaction channels are used to improve the heat transfer performance of the reaction liquid and promote the high-quality synthesis and preparation of products.
进一步的,在一实施例中,多路支流由分流口流至汇合口的时间相同。具体的,可以通过本申请上述微流控芯片的多个子反应通道的设置,控制多个子 反应通道中的多路支流由分流口流至汇合口的时间相同。多个子反应通道以及包括其的微流控芯片的相关描述,可以参考上文,此处不进行赘述。当然,还可以通过对多路支流中的至少一个支流设置阀门等方式,控制由分流口流至汇合口的时间相同。Further, in one embodiment, the times for the multiple branch streams to flow from the diverging port to the converging port are the same. Specifically, the multiple sub-reaction channels in the multiple sub-reaction channels can be controlled to flow from the split port to the confluence port at the same time through the settings of the multiple sub-reaction channels of the above-mentioned microfluidic chip in the present application. For the relevant description of the multiple sub-reaction channels and the microfluidic chip including them, reference may be made to the above, and details will not be repeated here. Of course, it is also possible to control the flow time from the diverging port to the converging port to be the same by setting a valve for at least one of the multiple branch streams.
即混合溶液在分流口分成多路支流后,各路支流在其对应的子反应通道中的停留时间相同。从而在提高量子点合成效率的同时,能够保证流至汇合口的各个支流的混合溶液的反应阶段相同或者说量子点的状态相同,从而提高量子点的合成一致性和产品质量,提高经过微流控芯片制备得到的量子点尺寸分布的集中性。That is to say, after the mixed solution is divided into multiple branch streams at the split port, the residence time of each branch stream in its corresponding sub-reaction channel is the same. Therefore, while improving the synthesis efficiency of quantum dots, it can ensure that the reaction stages of the mixed solutions flowing to the confluence port are the same or the state of the quantum dots is the same, thereby improving the synthesis consistency and product quality of quantum dots, and improving the quality of the microfluidics. Control the concentration of the quantum dot size distribution prepared by the chip.
以上对本申请实施例所提供的微流控芯片、微反应系统以及量子点的制备方法进行了详细介绍,本文中应用了具体个例对本申请的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本申请的方法及其核心思想;同时,对于本领域的技术人员,依据本申请的思想,在具体实施方式及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本申请的限制。The preparation method of the microfluidic chip, the microreaction system and the quantum dots provided by the embodiments of the present application have been introduced in detail above. In this paper, specific examples have been used to illustrate the principles and implementation methods of the present application. The description of the above embodiments It is only used to help understand the method of the present application and its core idea; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation and application scope. In summary, this The content of the description should not be understood as limiting the application.

Claims (20)

  1. 一种微流控芯片,其中,包括依次连通的注入通道、混合通道、反应通道和流出通道;A microfluidic chip, which includes sequentially connected injection channels, mixing channels, reaction channels and outflow channels;
    所述注入通道的一端为进料口,另一端与所述混合通道连通;One end of the injection channel is a feed port, and the other end communicates with the mixing channel;
    所述混合通道远离所述注入通道的一端为分流口,所述分流口与所述反应通道连通;The end of the mixing channel away from the injection channel is a split port, and the split port communicates with the reaction channel;
    所述反应通道包括并联设置多个子反应通道,每个所述子反应通道的一端与所述混合通道另一端的分流口连通,另一端与所述流出通道的汇合口连通;The reaction channel includes a plurality of sub-reaction channels arranged in parallel, one end of each sub-reaction channel communicates with the split port at the other end of the mixing channel, and the other end communicates with the confluence port of the outflow channel;
    所述流出通道的一端为所述汇合口,另一端为出料口。One end of the outflow channel is the confluence port, and the other end is the discharge port.
  2. 根据权利要求1所述的微流控芯片,其中,至少部分所述子反应通道的容积基本相同。The microfluidic chip according to claim 1, wherein at least some of the sub-reaction channels have substantially the same volume.
  3. 根据权利要求2所述的微流控芯片,其中,至少部分所述子反应通道长度基本相同。The microfluidic chip according to claim 2, wherein at least some of the sub-reaction channels have substantially the same length.
  4. 根据权利要求1-3任一项所述的微流控芯片,其中,所述多个子反应通道中,每个所述子反应通道的中轴线均位于同一平面;The microfluidic chip according to any one of claims 1-3, wherein, among the plurality of sub-reaction channels, the central axes of each of the sub-reaction channels are located on the same plane;
    以所述分流口与所述汇合口的连线为基准线,远离所述基准线的方向上,所述子反应通道的长度逐渐增大,所述子反应通道的内径逐渐减小。Taking the connection line between the diversion port and the confluence port as a reference line, the length of the sub-reaction channels gradually increases and the inner diameter of the sub-reaction channels gradually decreases in a direction away from the reference line.
  5. 根据权利要求4所述的微流控芯片,其中,多个所述子反应通道的内径范围为450μm-650μm。The microfluidic chip according to claim 4, wherein the inner diameters of the plurality of sub-reaction channels range from 450 μm to 650 μm.
  6. 根据权利要求4所述的微流控芯片,其中,多个所述子反应通道的长度范围为80mm-167mm。The microfluidic chip according to claim 4, wherein the lengths of the multiple sub-reaction channels range from 80 mm to 167 mm.
  7. 根据权利要求1所述的微流控芯片,其中,每个所述子反应通道为包括多段直形通道连接而成或者为弧形通道。The microfluidic chip according to claim 1, wherein each of the sub-reaction channels is formed by connecting a plurality of straight channels or is an arc channel.
  8. 根据权利要求1所述的微流控芯片,其中,所述混合通道为S形通道。The microfluidic chip according to claim 1, wherein the mixing channel is an S-shaped channel.
  9. 根据权利要求8所述的微流控芯片,其中,所述混合通道的内径范围为3mm-5mm。The microfluidic chip according to claim 8, wherein the inner diameter of the mixing channel is in the range of 3mm-5mm.
  10. 根据权利要求1-9任一项所述的微流控芯片,其中,所述微流控芯片包括多个所述注入通道,每个所述注入通道的内径范围为1mm-2mm。The microfluidic chip according to any one of claims 1-9, wherein the microfluidic chip comprises a plurality of injection channels, each of which has an inner diameter ranging from 1 mm to 2 mm.
  11. 根据权利要求1-10任一项所述的微流控芯片,其中,所述流出通道的内径范围为3-5mm。The microfluidic chip according to any one of claims 1-10, wherein the inner diameter of the outflow channel is in the range of 3-5mm.
  12. 根据权利要求11所述的微流控芯片,其中,所述流出通道的内径与所述混合通道的内径相同。The microfluidic chip according to claim 11, wherein the inner diameter of the outflow channel is the same as that of the mixing channel.
  13. 根据权利要求1-12任一项所述的微流控芯片,其中,所述反应通道所在的区域为加热区域。The microfluidic chip according to any one of claims 1-12, wherein the area where the reaction channel is located is a heating area.
  14. 一种微反应系统,其中,包括进样装置、微流控芯片和产品收集装置;A micro-reaction system, including a sampling device, a microfluidic chip and a product collection device;
    所述微流控芯片包括依次连通的注入通道、混合通道、反应通道和流出通道;The microfluidic chip includes an injection channel, a mixing channel, a reaction channel and an outflow channel connected in sequence;
    所述注入通道的一端为进料口,连接所述进样装置,所述注入通道的另一端与所述混合通道连通;One end of the injection channel is a feed port connected to the sampling device, and the other end of the injection channel communicates with the mixing channel;
    所述混合通道远离所述注入通道的一端为分流口,所述分流口与所述反应通道连通;The end of the mixing channel away from the injection channel is a split port, and the split port communicates with the reaction channel;
    所述反应通道包括并联设置多个子反应通道,每个所述子反应通道的一端与所述混合通道另一端的分流口连通,另一端与所述流出通道的汇合口连通;The reaction channel includes a plurality of sub-reaction channels arranged in parallel, one end of each sub-reaction channel communicates with the split port at the other end of the mixing channel, and the other end communicates with the confluence port of the outflow channel;
    所述流出通道的一端为所述汇合口,所述流出通道的另一端为出料口,与所述产品收集装置连通。One end of the outflow channel is the confluence port, and the other end of the outflow channel is a discharge port, which communicates with the product collecting device.
  15. 根据权利要求14所述的微反应系统,其中,至少部分所述子反应通道的容积基本相同。The micro-reaction system according to claim 14, wherein at least some of the sub-reaction channels have substantially the same volume.
  16. 根据权利要求15所述的微反应系统,其中,至少部分所述子反应通道长度基本相同。The micro-reaction system according to claim 15, wherein at least some of the sub-reaction channels have substantially the same length.
  17. 根据权利要求14-16任一项所述的微反应系统,其中,所述多个子反应通道中,每个所述子反应通道的中轴线均位于同一平面;The micro-reaction system according to any one of claims 14-16, wherein, among the plurality of sub-reaction channels, the central axis of each sub-reaction channel is located on the same plane;
    以所述分流口与所述汇合口的连线为基准线,远离所述基准线的方向上,所述子反应通道的长度逐渐增大,所述子反应通道的内径逐渐减小。Taking the connection line between the diversion port and the confluence port as a reference line, the length of the sub-reaction channels gradually increases and the inner diameter of the sub-reaction channels gradually decreases in a direction away from the reference line.
  18. 一种量子点的制备方法,其中,采用微流控芯片制备所述量子点,所述微流控芯片包括依次连通的注入通道、混合通道、反应通道和流出通道;其中,所述反应通道包括并联设置的多个子反应通道;A method for preparing quantum dots, wherein the quantum dots are prepared using a microfluidic chip, and the microfluidic chip includes sequentially connected injection channels, mixing channels, reaction channels and outflow channels; wherein the reaction channels include Multiple sub-reaction channels arranged in parallel;
    所述制备方法包括:Described preparation method comprises:
    前驱体溶液由所述注入通道的进料口流入,流经所述混合通道进行混合得到混合溶液;The precursor solution flows in from the feed port of the injection channel, and flows through the mixing channel for mixing to obtain a mixed solution;
    所述混合溶液在所述混合通道的分流口分成多路支流,流入并联设置的多个所述子反应通道中,在多个所述子反应通道中反应生成量子点;The mixed solution is divided into multiple branches at the split port of the mixing channel, and flows into a plurality of sub-reaction channels arranged in parallel, and reacts in a plurality of sub-reaction channels to generate quantum dots;
    多路支流流经汇合口进行汇合,并流经所述流出通道,由所述流出通道的出料口流出所述微流控芯片。The multiple branches flow through the confluence port for confluence, flow through the outflow channel, and flow out of the microfluidic chip through the outlet of the outflow channel.
  19. 根据权利要求18所述的制备方法,其中,所述多路支流由所述分流口流至所述汇合口的时间相同。The preparation method according to claim 18, wherein the times of the multiple branch streams flowing from the diverging port to the converging port are the same.
  20. 根据权利要求18所述的制备方法,其中,所述量子点选自单一结构量子点及核壳结构量子点中的至少一种,所述单一结构量子点的材料选自II-VI族化合物、III-V族化合物和I-III-VI族化合物中的至少一种,所述II-VI族化合物选自CdSe、CdS、CdTe、ZnSe、ZnS、CdTe、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe及CdZnSTe中的至少一种,所述III-V族化合物选自InP、InAs、GaP、GaAs、GaSb、AlN、AlP、InAsP、InNP、InNSb、GaAlNP及InAlNP中的至少一种,所述I-III-VI族化合物选自CuInS 2、CuInSe 2及AgInS 2中的至少一种;所述核壳结构的量子点的核选自上述单一结构量子点中的任意一种,所述核壳结构的量子点的壳层材料选自CdS、CdTe、CdSeTe、CdZnSe、CdZnS、CdSeS、ZnSe、ZnSeS和ZnS中的至少一种。 The preparation method according to claim 18, wherein the quantum dots are selected from at least one of single-structure quantum dots and core-shell structure quantum dots, and the material of the single-structure quantum dots is selected from group II-VI compounds, At least one of the III-V group compound and the I-III-VI group compound, the II-VI group compound is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdTe, ZnTe, CdZnS, CdZnSe, CdZnTe, ZnSeS, At least one of ZnSeTe, ZnTeS, CdSeS, CdSeTe, CdTeS, CdZnSeS, CdZnSeTe and CdZnSTe, the III-V group compound is selected from InP, InAs, GaP, GaAs, GaSb, AlN, AlP, InAsP, InNP, InNSb, At least one of GaAlNP and InAlNP, the I-III-VI group compound is selected from at least one of CuInS 2 , CuInSe 2 and AgInS 2 ; the core of the quantum dot with the core-shell structure is selected from the above-mentioned single-structure quantum Any one of the dots, the shell material of the core-shell quantum dot is selected from at least one of CdS, CdTe, CdSeTe, CdZnSe, CdZnS, CdSeS, ZnSe, ZnSeS and ZnS.
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