WO2020192575A1 - 多孔膜及其制备方法、使用方法 - Google Patents

多孔膜及其制备方法、使用方法 Download PDF

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Publication number
WO2020192575A1
WO2020192575A1 PCT/CN2020/080374 CN2020080374W WO2020192575A1 WO 2020192575 A1 WO2020192575 A1 WO 2020192575A1 CN 2020080374 W CN2020080374 W CN 2020080374W WO 2020192575 A1 WO2020192575 A1 WO 2020192575A1
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porous membrane
straight channel
straight
present disclosure
film
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English (en)
French (fr)
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曹留烜
郑志锋
李宁
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Xiamen University
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Xiamen University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material

Definitions

  • At least one embodiment of the present disclosure relates to a porous membrane and its preparation method and use method.
  • Membrane structure and materials are the key to membrane technology, and breakthroughs in key technologies of high-performance membrane structures and materials will directly affect the promotion of membrane technology in practical applications. This has prompted people to vigorously explore new high-performance separation membranes.
  • the core indicators of membrane performance are selectivity and flux, which are key common problems in many chemical processes. They are closely related to the separation effect and operating cost of the membrane.
  • selectivity and permeability (flux) are two mutually restrictive factors, and this problem limits the further improvement of membrane performance.
  • At least one embodiment of the present disclosure provides a porous membrane.
  • the porous membrane includes a plurality of straight channels arranged to have the same extension direction; the porous membrane includes two opposite channels for the ingress and egress of substances to be permeated.
  • the straight channels at both ends are arranged side by side in a direction perpendicular to the direction from one of the ends to the other.
  • a straight channel penetrates both ends of the porous membrane.
  • one of the two opposite ends is set as the liquid inlet surface and the other is set as the liquid outlet surface, and the straight channel penetrates the porous membrane to make the liquid inlet surface and the liquid outlet surface communicate.
  • the inner diameter of the straight channel is set to be smaller than the size of the substance to be blocked and greater than or equal to the size of the substance to be permeated.
  • the angle between the extending direction of the straight channel and the transmembrane direction from one of the two ends (for example, the liquid inlet surface) to the other (for example, the liquid outlet surface) Less than 90°.
  • the extending direction of the straight channel is parallel to the transmembrane direction.
  • the porous membrane provided by at least one embodiment of the present disclosure further includes a flow guiding structure, and the flow guiding structure is arranged to define the boundary of the straight channel.
  • the porous membrane provided by at least one embodiment of the present disclosure further includes a matrix membrane, and the flow guiding structure is embedded in the matrix membrane.
  • the flow guiding structure includes a plurality of tubular structures, and the pipe inside the tubular structure and the space between adjacent tubular structures are used to form a straight channel.
  • porous membrane provided by at least one embodiment of the present disclosure, at least two tubular structures are connected in sequence, so that the pipes therein are connected as a straight channel.
  • the material of the tubular structure includes one or a combination of carbon nanotubes, boron nitride tubes, and carbon fibers.
  • the tubular structure has a diameter of 0.1 nm to 10 ⁇ m and a length of 1 nm to 10 mm.
  • the separation distance between adjacent tubular structures is not more than 2 nm.
  • the flow guiding structure includes a plurality of sheet-layer structures, and the space between adjacent sheet-layer structures constitutes a straight channel.
  • porous membrane provided by at least one embodiment of the present disclosure, at least two sheet-layer structures are connected in sequence, so that the pipes therein are connected as a straight channel.
  • the material of the sheet structure includes one or a combination of ink, graphene, molybdenum disulfide, black phosphorus, boron nitride, silylene, and germanene .
  • the length and width of the sheet structure are 10 nm to 1 mm, and the interlayer spacing is 0.1 nm to 10 ⁇ m.
  • the distance between the liquid inlet surface and the liquid outlet surface is 5 nm-10 mm.
  • At least one embodiment of the present disclosure provides a method for preparing a porous membrane.
  • the porous membrane includes a plurality of straight channels arranged to have the same extending direction; the porous membrane includes a method for substances to be penetrated in and out.
  • the two opposite ends of the two opposite ends, the straight channels are arranged side by side in a direction perpendicular to the direction from one of the two ends to the other.
  • the preparation method includes: forming a stacked film; providing a packaging material to encapsulate and cure the film; cutting And grinding the packaging material to expose the two opposite surfaces of the film; and perform a thinning process on the film from the two opposite surfaces to obtain a porous film; wherein the two opposite surfaces respectively correspond to the opposite ends (into Liquid level and liquid level).
  • straight channels penetrate both ends of the porous membrane.
  • forming the stacked membrane includes: providing a bottom membrane and spreading it on the enamel filter element of a wet mobile phase filter and clamping; The liquid is subjected to vacuum filtration; and the film formed by the suction filtration is placed in an oven at 50° C. for further dehydration, and the dispersion liquid is dehydrated to form a thin film.
  • the dispersion liquid includes graphene oxide.
  • the packaging material includes epoxy resin.
  • the thinning process includes one or a combination of mechanical grinding and ion thinning.
  • At least one embodiment of the present disclosure provides a method for using a porous membrane.
  • the porous membrane includes a plurality of straight channels arranged to have the same extending direction; the porous membrane includes a porous membrane for substances to be penetrated in and out. Two opposite ends, straight channels are arranged side by side in a direction perpendicular to the direction from one of the ends to the other.
  • the method of use includes: placing the porous membrane in a solution tank containing positive and negative ions.
  • the porous membrane Under the action of the solution, the porous membrane is ionized, so that the surface of the straight channel is charged; the porous membrane transfers the ions in the solution tank that have the same charge as the straight channel and whose size is smaller than the inner diameter of the straight channel from one of the two ends ( Inlet surface) into the straight channel, and make the ions entering the straight channel leave from the other of the two ends (the outlet surface); the porous membrane blocks the charge in the solution tank and the straight channel is electrically different and the size is greater than or equal to the straight channel
  • the ions of the inner diameter of the channel enter the straight channel.
  • straight channels penetrate both ends of the porous membrane.
  • the method for making the surface of a straight channel charged includes using surface chemical groups to ionize in a solution to generate charges, chemical modification to form charges, or irradiation After treatment, an electric charge is formed.
  • FIG. 1A is a partial cross-sectional view of a porous membrane provided by some embodiments of the disclosure.
  • FIG. 1B is a partial cross-sectional view of another porous membrane provided by some embodiments of the disclosure.
  • 1C is a partial cross-sectional view of another porous membrane provided by some embodiments of the disclosure.
  • 1D is a schematic diagram of the working principle of the porous membrane provided by some embodiments of the disclosure.
  • Figure 2 is a schematic diagram of the structure of a porous membrane and its working principle
  • Figure 3 is a cross-sectional SEM photograph of a porous membrane provided by some embodiments of the present disclosure.
  • FIG. 4 is a process diagram of a method for preparing a porous membrane provided by some embodiments of the disclosure.
  • FIG. 5 is a process diagram of a method for using a porous membrane provided by some embodiments of the disclosure.
  • FIG. 6 is a schematic structural diagram of a salt difference energy conversion device including a porous membrane provided by some embodiments of the present disclosure
  • Fig. 7 is an output power diagram of the salt difference energy conversion device in the embodiment shown in Fig. 6;
  • FIG. 8 is a schematic structural diagram of a suction filtration device including a porous membrane provided by some embodiments of the present disclosure.
  • FIG. 9 is a schematic structural diagram of an ion trapping device including a porous membrane provided by some embodiments of the present disclosure.
  • selectivity and permeability are two mutually restrictive factors, and the upper limit of selectivity and permeability of the membrane does not change much if the membrane is made of current new materials.
  • the porous membrane provided by the embodiment of the present disclosure includes a plurality of straight channels, the porous membrane includes a plurality of straight channels, and the plurality of straight channels are arranged to have the same extending direction; the porous membrane includes a device for the substance to be permeated to enter and permeate Two opposite ends, the straight passages are arranged side by side in a direction perpendicular to the direction from one of the ends to the other.
  • the arrangement of straight channels provides extremely low transmembrane flow resistance for the substance to be permeated. When substances (such as ions) pass through the porous membrane, they will present short paths and low flow resistance. Friction, so that the porous membrane can have a higher selectivity while also having a higher permeability (flux).
  • the substance to be permeated and the substance to be blocked of the porous membrane may include one or a combination of atoms, molecules, ions, particles, and the like.
  • one of the opposite ends is the liquid inlet surface of the porous membrane, and the other of the opposite ends is the liquid outlet surface of the porous membrane.
  • the straight channels are arranged side by side in a direction perpendicular to the direction from the liquid inlet surface to the liquid outlet surface, and the straight channels penetrate the porous membrane to make the liquid inlet surface and the liquid outlet surface communicate.
  • the straight channel penetrates both ends of the porous membrane.
  • the substance to be permeated directly enters the corresponding straight channel at the liquid inlet level, and passes through the porous membrane along the straight channel, which will present a shorter path and lower friction, with higher Permeability (flux).
  • porous membrane according to at least one embodiment of the present disclosure and its preparation method and use method will be described with reference to the accompanying drawings.
  • the porous membrane 100 includes a plurality of straight channels 110, and the plurality of straight channels 110 are arranged to have the same extending direction to present an orderly arrangement.
  • the plurality of straight channels 110 are arranged substantially parallel to each other.
  • the porous membrane 100 includes a liquid inlet surface 101 and a liquid outlet surface 102 opposite to each other.
  • the straight channels 110 are arranged side by side in a direction perpendicular to the direction from the liquid inlet surface 101 to the liquid outlet surface 102.
  • the straight channels 110 penetrate the porous membrane 100 to allow the inlet The liquid surface 101 and the liquid outlet surface 102 are in communication.
  • the porous membrane 100 when used, substances (such as ions) can enter the straight channel 110 from the liquid inlet 101, then move along the straight channel 110 to the liquid outlet 102, and then leave the porous membrane 100 from the liquid outlet 102.
  • the shape of the straight channel is roughly straight.
  • the substance entering a straight channel 110 will move along the same straight channel 110, and there will be no increase in resistance (friction) and increase in the moving distance caused by disorderly movement.
  • the phenomenon, that is, the porous membrane 100 exhibits high permeability to the substance.
  • the inner diameter of the straight channel is set to be smaller than the size of the substance to be blocked and greater than or equal to the size of the substance to be permeated. .
  • the substance to be permeated for example, ions
  • the inner diameter of the straight channel is related to the specific structure used to form the straight channel in the porous membrane (for example, the tubular structure and the lamella structure in the following embodiments). You can refer to the relevant description in the following embodiments, and will not be repeated again.
  • a spatial rectangular coordinate system is established to describe the position and direction of each structure.
  • the X axis is parallel to the transmembrane direction of the porous membrane
  • the Y (not shown) axis and Z axis are parallel to the liquid inlet surface 101 and the liquid outlet surface 102. .
  • the angle between the extending direction of the straight channel and the transmembrane direction from the liquid inlet to the liquid outlet is less than 90°.
  • the angle between the extending direction (arrow " ⁇ " in the figure) of the straight channel 110a in the porous membrane 100a and the transmembrane direction (X axis) is an acute angle.
  • the substance for example, ions
  • the smaller the acute angle the smaller the distance the substance moves, and the higher the permeability of the porous membrane 100a.
  • the extending direction of the straight channel is parallel to the transmembrane direction.
  • the extension direction (arrow " ⁇ " in the figure) of the straight channel 110 in the porous membrane 100 is parallel to the transmembrane direction (X axis).
  • the substance such as ions
  • the distance of the movement of the substance is equal to the size of the porous membrane 100 along the transmembrane direction.
  • the porous membrane provided by at least one embodiment of the present disclosure further includes a flow guiding structure, and the flow guiding structure is arranged to define the boundary of the straight channel.
  • the flow guiding structures 120 and 120a are used to define the straight channels 110 and 110a, thereby defining the boundary of the movement of substances (eg ions).
  • the specific shape of the diversion structure is not limited, and it can be designed as required.
  • the flow guiding structure may be configured to include a plurality of tubular structures, and the flow boundary of the substance is defined by the tubular structure, thereby defining a straight channel.
  • the flow guiding structure may be configured to include a plurality of lamella structures, and the lamellae isolate the flow boundary of the substance, thereby defining a straight channel.
  • the structure of the porous membrane will be described for the case where the flow guiding structure includes a tubular structure and a sheet structure, respectively.
  • the flow guiding structure includes a plurality of sheet-layer structures, and the space between adjacent sheet-layer structures constitutes a straight channel.
  • the diversion structure 120 is composed of multiple lamella structures, and the straight channel 110 is located between adjacent lamella structures.
  • the porous membrane provided by at least one embodiment of the present disclosure, at least two sheet-layer structures are connected in sequence, so that the pipes therein are connected as a straight channel.
  • a plurality of lamella structures are arranged in a line, so that the spacing space defined by adjacent lamella structures along the Z-axis direction can form a straight channel 110.
  • a sheet structure can extend from the liquid surface to the liquid surface, eliminating the need for multiple sheets.
  • the layer structure is connected in sequence.
  • the material of the sheet structure includes one or a combination of ink, graphene, molybdenum disulfide, black phosphorus, boron nitride, silylene, and germanene It can also be other applicable materials, which are not limited in the embodiments of the present disclosure.
  • the length and width of the sheet structure are 10 nm to 1 mm, such as further 100 nm, 1 ⁇ m, 10 ⁇ m, 100 ⁇ m, etc.
  • the layer spacing is 0.1 nm to 10 ⁇ m, for example, further It is 1nm, 10nm, 100nm, 1 ⁇ m, etc.
  • the flow guiding structure includes a plurality of tubular structures, and the pipe inside the tubular structure and the space between adjacent tubular structures constitute a straight channel.
  • the flow guiding structure 120b in the porous membrane 100b is composed of a plurality of tubular structures, the space between adjacent tubular structures forms a straight channel 100b, and the pipe inside the tubular structure forms a straight channel 100c.
  • the porous membrane provided by at least one embodiment of the present disclosure, at least two tubular structures are connected in sequence, so that the pipes therein are connected as a straight channel.
  • the length of the tubular structure is less than the distance from the liquid inlet 101b to the liquid outlet 102b, and a plurality of tubular structures are arranged in a line and connected back and forth.
  • the pipes will also be connected to each other to form a straight channel 100c.
  • tubular structure can extend from the liquid inlet to the liquid outlet, eliminating the need for multiple tubular structures in sequence. Connected.
  • the material of the tubular structure includes one or a combination of carbon nanotubes, boron nitride tubes and carbon fibers, and may also be other suitable materials.
  • the diameter of the tubular structure is 0.1 nm to 10 ⁇ m, such as further 1 nm, 10 nm, 100 nm, 1 ⁇ m, etc.
  • the length is 1 nm to 10 mm, such as further 10 nm, 100 nm, 1 ⁇ m, 10 ⁇ m, 100 ⁇ m, 1mm, etc.
  • the spacing distance between adjacent tubular structures is not more than 2nm.
  • the distance between the liquid inlet surface and the liquid outlet surface is 5 nm-10 mm, such as further 10 nm, 100 nm, 1 ⁇ m, 10 ⁇ m, 100 ⁇ m, 1 mm, etc.
  • the porous membrane further includes a matrix membrane, and the flow guiding structure is embedded in the matrix membrane.
  • the matrix membrane can be used as the support material of the porous membrane, and can be combined to fix the flow guiding structure together.
  • the porous membrane 100 includes a matrix membrane 130, and the flow guiding structure 120 (for example, a sheet structure) is embedded in the matrix membrane 130.
  • the material of the matrix film may be epoxy resin or the like.
  • Figures 1D and 2 show schematic diagrams of the working principles of two porous membranes.
  • Figure 1D uses the porous membrane in the embodiment shown in Figure 1A of the present disclosure, and Figure 2 shows that the porous membrane does not fully use the technology of the present disclosure.
  • the scheme is designed, and the flow guiding structures of the two porous membranes are composed of a sheet structure (charged sheet in the figure).
  • the interval (inner diameter of the straight channel) between the lamella structures of different layers can be designed, but the interval between adjacent lamellas in the same layer is difficult to control.
  • a straight channel is formed between the charged sheets, and the straight channel is used to allow the substance (ions) to flow through.
  • the ions in Figure 2 need to move between multiple gaps in multiple layers to penetrate the porous membrane. If the path is too long, the permeability of the porous membrane shown in FIG. 1D will be much higher than that of the porous membrane shown in FIG. 2.
  • porous membrane shown in the drawings in the above examples of the present disclosure is a schematic diagram, and its real structure can be referred to the scanning electron microscope (Scanning electron microscope, referred to as "SEM") photo shown in FIG. 3 shown.
  • SEM scanning electron microscope
  • the flow guide structure of the porous membrane is composed of a sheet structure.
  • At least one embodiment of the present disclosure provides a method for preparing a porous membrane, the porous membrane includes a plurality of straight channels, and the plurality of straight channels are arranged to have the same extending direction.
  • the porous membrane includes two opposite ends for the substance to be penetrated in and out, and the straight channels are arranged side by side in a direction perpendicular to the direction from one of the ends to the other.
  • straight channels penetrate both ends of the porous membrane.
  • One of the two opposite ends is the liquid inlet and the other is the liquid outlet.
  • the straight channels are arranged side by side in the direction perpendicular to the direction from the liquid inlet to the liquid outlet.
  • the preparation method includes: forming a stacked film; providing an encapsulating material to encapsulate and curing a single or multiple film arrays; cutting and grinding the encapsulating material to expose two opposite surfaces of the film; and Two opposing surfaces perform a thinning process on the film to obtain a porous membrane; wherein, the two opposing surfaces correspond to the liquid inlet surface and the liquid outlet surface.
  • the straight channel penetrates through the two ends of the porous membrane, providing extremely low transmembrane flow resistance.
  • substances such as ions
  • Friction so that the porous membrane can have a higher selectivity while also having a higher permeability (flux).
  • forming the stacked membrane includes: providing a bottom membrane and spreading it on the enamel filter element of a wet mobile phase filter and clamping; The liquid is subjected to vacuum filtration; and the film formed by the suction filtration is placed in an oven at 50° C. for further dehydration, and the dispersion liquid is dehydrated to form a thin film.
  • a film composed of horizontally stacked Graphene Oxide ("GO") sheets is prepared by a vacuum filtration method: a base film (for example, a mixed cellulose ester film or a polycarbonate film, etc.) Spread it flat on the enamel filter element of the wet mobile phase filter, then cover the upper matching device and clamp it with a clamp (or other fixing device). Then inject a suitable amount of GO dispersion liquid for vacuum filtration, and put the film formed by the suction filtration into an oven at 50°C for further dehydration to form a densely arranged material.
  • a base film for example, a mixed cellulose ester film or a polycarbonate film, etc.
  • the GO content in the GO dispersion may be 0.01 mg/ml-50 mg/ml, for example, further 0.1 mg/ml, 1 mg/ml, 10 mg/ml, 20 mg/ml, 30 mg/ml. ml, 40mg/ml, etc.
  • the dispersion liquid includes graphene oxide or other suitable materials.
  • the packaging material includes epoxy resin or other suitable materials.
  • the prepared material is cut into a strip with a suitable width (1mm to 4mm), and the cut sheet is vertically erected in the epoxy resin with the aid of an acrylic board. It can be cured after 5 minutes of exposure to ultraviolet light.
  • the packaging material is used to form a matrix film of a porous film (see matrix film 130 in FIG. 1A).
  • the excess part of the material is cut, the package is wet polished with sandpaper, and both ends are exposed to the air. At this time, a high-flux graphene oxide membrane with GO sheets vertically arranged is prepared.
  • the thinning process may include mechanical grinding, ion thinning or other suitable thinning methods. Using an ion thinner to further reduce the thickness of the membrane (porous membrane) can increase its flux.
  • the porosity of the high-flux porous membrane obtained by the above-mentioned preparation method can reach 20% to 90%, for example, further. It should be noted that in the embodiments of the present disclosure, the requirement for porosity can be reduced while maintaining the high flux of the porous membrane.
  • the substance mainly moves in the straight channel of the porous membrane. From an ideal state, the substance may not need to move between different straight channels. Therefore, even if the porosity of the porous membrane is not high, it is different from the current one. Compared with porous membranes, it also exhibits higher flux performance.
  • the porous membrane includes a plurality of straight channels arranged to have the same extending direction.
  • the porous membrane includes two opposite ends for the substance to be penetrated in and out, and the straight channels are arranged side by side in a direction perpendicular to the direction from one of the ends to the other.
  • straight channels penetrate both ends of the porous membrane.
  • One of the two opposite ends is the liquid inlet and the other is the liquid outlet.
  • the straight channels are arranged side by side in the direction perpendicular to the direction from the liquid inlet to the liquid outlet.
  • the straight channels penetrate the porous membrane to make the inlet The liquid surface and the liquid outlet surface are connected.
  • the method of use includes: placing the porous membrane in a solution tank containing positively and negatively charged ions, and under the action of the solution, the porous membrane is ionized, so that the surface of the straight channel is charged;
  • the porous membrane introduces the ions in the solution tank with the same charge and electrical property as the straight channel and whose size is smaller than the inner diameter of the straight channel into the straight channel from the liquid inlet surface, and makes the ions entering the straight channel leave from the liquid outlet surface;
  • the porous membrane blocks the solution tank
  • the ions in which the electric charge of the electric charge is different from the straight channel and the size is greater than or equal to the inner diameter of the straight channel enter the straight channel.
  • the porous membrane In the method of using the porous membrane, because the straight channel runs through the two ends of the porous membrane, it provides extremely low transmembrane flow resistance. When substances (such as ions) pass through the porous membrane, they will present short paths and low friction. , So that while the porous membrane has a higher selectivity, it can also have a higher permeability (flux).
  • the method for making the surface of a straight channel charged includes using surface chemical groups to ionize in a solution to generate charges, chemical modification to form charges, or irradiation After treatment, an electric charge is formed.
  • At least one embodiment of the present disclosure provides a high-throughput porous membrane design method.
  • the specific steps of the method may be as follows:
  • the porous membrane structure is composed of a tubular structure or a sheet structure.
  • the tubular structure or sheet structure is oriented along the transmembrane direction to form a straight channel that penetrates both ends of the porous membrane.
  • the straight channel provides a fluid transport path and a transmembrane flow resistance.
  • the flat interface at the atomic level of the tubular structure or the sheet structure (the porous membrane is a nanoporous membrane, and the straight channel allows the fluid to move in an orderly manner and exhibits high smoothness) and high porosity (20% to 90%) for fluid transportation.
  • the straight channel can adopt the shortest fluid transport path (refer to the relevant description in the previous embodiment, for example, the distance from the liquid surface to the liquid surface); the fluid is in the pore (such as a pipe with a tubular structure) Or the direction of interlayer transmission (the gap between adjacent tubular structures or adjacent sheet structures) is consistent with the transmembrane direction, and the extension direction of the straight channel is less than 90° to the transmembrane direction.
  • a single straight channel does not need to completely penetrate the porous
  • the two ends of the membrane can be connected by multiple straight channels to form a transmembrane transport channel.
  • the lamella structure adopts a two-dimensional lamella structure
  • the tubular structure adopts a one-dimensional tubular structure.
  • the one-dimensional tubular structure forms a porous membrane.
  • the fluid is transmitted inside or between the pipes.
  • the fluid is a two-dimensional receiver in the three dimensions of space.
  • a porous membrane is composed of a two-dimensional lamella structure.
  • the fluid is transported or flows between the lamella (lamellar structure) and the lamella, and the fluid is transported in a one-dimensional confined space; penetrates the porous membrane
  • the straight channels at both ends are composed of a one-dimensional tubular structure or a two-dimensional lamella structure, forming a straight channel penetrating both ends of the porous membrane.
  • the diameter of the one-dimensional tubular structure is 0.1 nm to 10 ⁇ m, and the length is 1 nm to 10 mm; the diameter of the two-dimensional lamella structure is 10 nm to 1 mm, and the interlayer spacing is 0.1 nm to 10 ⁇ m.
  • the thickness of the straight channels penetrating both ends of the porous membrane is 5nm-10mm.
  • One-dimensional tubular structures include but are not limited to carbon nanotubes, boron nitride tubes, carbon fibers, etc.; two-dimensional sheet structures include, but are not limited to, graphene, graphene oxide, molybdenum disulfide, black phosphorus, boron nitride, silylene, and Germanene and so on.
  • the preparation methods of the one-dimensional tubular structure and the two-dimensional sheet structure include, but are not limited to, physical peeling, electrostatic self-assembly, sheet-layer stacking, chemical self-assembly, interface and multiphase self-assembly, spinning One of coating method, vacuum filtration, inkjet and spray method, sol-gel method, gas-solution-solid phase method, sonic degradation method, solvothermal method, template method, chemical vapor deposition method, etc.
  • the ion selection mode of the charged straight channel structure on the inner wall of the transmembrane includes anion selectivity and cation selectivity.
  • the selectivity includes various components such as ions, molecules, and particles.
  • the porous membrane is placed in the solution tank, and under the action of the aqueous solution, the porous membrane is ionized, causing the surface of the pores to be charged.
  • the ionized nanochannels repel the ions carrying the same kind of charge, thereby preventing ions from entering the pores; extremely narrow (for example, no more than 2nm) interlayer spacing is greater than the interlayer spacing size of hydrated ions (the solvent of the solution is water) For example, the space size is restricted to restrict its passage.
  • Solvent molecules, ions, and particles in the aqueous solution are driven by driving forces (such as the attraction between opposite charges, the force under the influence of electric fields, or others).
  • the charge carried on the inner surface of a nanochannel can be the charge carried on the surface of the material itself, or the charge formed after chemical modification or irradiation treatment.
  • the charge carried can be positive or negative. .
  • the porosity of the high flux porous membrane can be 20% to 90%.
  • the high-flux porous membranes in the embodiments of the present disclosure all have high ion selectivity.
  • the porous membrane is placed in a specific solution tank (the type of solution tank is determined according to specific embodiments). Under the action of the aqueous solution, the porous membrane will be ionized to make the surface of the pores (pores, including straight channels) charged. According to the Coulomb effect, the ionized nanochannels (straight channels) will repel ions carrying the same kind of charge, thereby preventing ions from entering the pores; extremely narrow (for example, no more than 2nm) interlayer spacing can be effective for those with a size larger than the interlayer spacing. Hydrated ions produce a restriction on the size of the space, thereby restricting their passage.
  • the solvent molecules, ions and particles in the solution are driven by the driving force (such as the attraction between the opposite charges, the force under the influence of the electric field, or others), from one side of the membrane (such as the liquid surface) along the straight channel that penetrates. When reaching the other side (for example, the liquid surface), it can be completed by only passing a distance in a limited space, which greatly improves the transport speed of the fluid.
  • 1D and FIG. 2 show a nanoporous membrane with two-dimensional sheets oriented along the transmembrane direction
  • Figure 2 shows a nanoporous membrane with two-dimensional sheets arranged perpendicular to the transmembrane direction. It can be seen that The structure of Figure 1D is more conducive to fluid transportation.
  • the invention utilizes two-dimensional material sheets or one-dimensional pipes to prepare nanoporous membranes in which two-dimensional sheets or one-dimensional pipes are oriented and arranged along the transmembrane direction.
  • Such nanostructures have uniform interlayer spacing and abundant surface charges (greater than 0.1mC m -2 ), providing high ion selectivity, and at the same time, two-dimensional sheet atomic level flat interfaces, penetrating straight channels and high porosity are fluid Transport provides extremely low flow resistance, which is expected to break through the limitations of permeability-selectivity in existing materials. Its selectivity comes from the steric hindrance of the pore size or interlayer spacing, physical size effects, surface charge effects, and chemical interactions ( Including hydrogen bonds, the formation of new chemical coordination bonds, etc.).
  • the present invention provides a high-flux porous membrane structure.
  • the porous membrane is composed of a tubular structure or a sheet-layer structure, which constitutes straight channels penetrating both ends of the membrane, providing extremely low transmembrane flow resistance; these straight channels have very narrow.
  • the distribution of pore size or interlayer spacing provides high selectivity of the porous membrane; the porous membrane also has a very high porosity and provides high flux.
  • the high flux porous membrane structure can be widely used in forward osmosis process, reverse osmosis process, pervaporation process, electrodialysis process, and can also be used for gas, liquid, solid filtration, separation, detection, salt difference energy conversion, battery Membrane, proton exchange membrane, electrodialysis, membrane absorption, membrane extraction, membrane distillation, membrane reactor and other systems; its high flux properties are of great significance in the above fields.
  • At least one embodiment of the present disclosure provides a device including the porous membrane in the foregoing embodiment.
  • the embodiments of the present disclosure do not limit the specific application of the device, and can be designed according to requirements. In the following, in several examples, several types of devices are described.
  • the device may be a salt differential energy-electric energy conversion device.
  • the porous membrane in the salt differential energy-electric energy conversion device is a molybdenum disulfide high flux selective membrane, and its material can be molybdenum disulfide.
  • the preparation of molybdenum disulfide high-throughput selective membranes can include: using an ultrasonic cell pulverizer to prepare a molybdenum disulfide dispersion with a uniform sheet diameter, and using vacuum filtration to filter the molybdenum disulfide dispersion on a cellulose membrane or a nuclear porous membrane. The required two-dimensional layered film is formed on it.
  • the molybdenum disulfide sheet layer Due to the negative charge of the molybdenum disulfide sheet layer, during the deposition process, the molybdenum disulfide sheet layer self-assembles into a porous film material with a layer spacing of 0.8-1.1 nm under the action of electrostatic repulsion.
  • a nuclear porous membrane-molybdenum disulfide composite material is prepared.
  • the sample was embedded with epoxy resin, and the embedded single molybdenum disulfide nanoporous material was processed into a suitable size by slicing, and assembled into a large area sample. Finally, the surface of the membrane was ground and reduced. Thinly prepare a sample (porous membrane) that requires an area and thickness.
  • the high flux molybdenum disulfide membrane is encapsulated in a solution tank, 500mM NaCl solution is added to the left solution tank, and 10mM NaCl solution is added to the right solution tank; driven by the ion concentration gradient, ions are formed across The net diffusion of the membrane results in net current and electromotive force, and can output electrical energy to the external circuit.
  • the solutions in the solution tanks on the left and right sides are not limited to the NaCl solution, and the types of solutions in the two solution tanks may also be different, which is not limited in the embodiments of the present disclosure.
  • P out I 2.
  • R the output power of the system (device) can be calculated.
  • P out is the output power of the system
  • I is the current in the system
  • R is the load resistance in the external circuit.
  • the maximum output power in the system can be obtained by adjusting the load resistance in the external circuit.
  • the thickness of the molybdenum disulfide mixed film used (in the direction perpendicular to the paper surface) is 250 ⁇ m, and the effective film area (the area along the cross section parallel to the paper surface) is 1 mm*6 ⁇ m.
  • the output power can be up to 6.03W m -2 by adjusting the external resistance.
  • the device may be a seawater desalination device.
  • the porous membrane in the seawater desalination device is a graphene oxide high flux selective membrane.
  • the preparation of the graphene oxide high-flux selective membrane may include: uniformly spreading the graphene oxide suspension on the cellulose membrane by a spin coating method, and obtaining a porous membrane structure of graphene oxide after heat treatment.
  • the cross-sectional transmission electron microscope photo of the prepared graphene oxide film is shown in Figure 3.
  • the sample is embedded with plexiglass, and the embedded single nanoporous material is processed into a suitable size by slicing, and assembled into a large area sample, and finally the required area is obtained by grinding and thinning the surface And the thickness of the sample; after thinning, the exposed end of the graphene oxide high-flux membrane presents the sheet structure in Figure 3.
  • the graphene oxide porous membrane is encapsulated in a suction filter tank, and NaCl solutions of different salinities (salt solutions) are added to the inlet chamber of the tank, and vacuum is drawn at the suction port (as shown in the figure) As shown, the air pressure is changed by pumping). Under the action of the external atmospheric pressure, water molecules pass through the graphene oxide membrane to reach the other side of the membrane, forming liquid water such as shown in Figure 8, while hydrated ions such as Na + and Cl - are limited by the space between the graphene oxide layers. The function is blocked outside the porous membrane. During this test, the effective area of the graphene oxide film was 4 cm 2 . When the concentration of NaCl is 0.8wt%, 3.5wt%, 4wt%, and 10wt%, the corresponding rejection rates are 99.3%, 98%, 97.5%, and 96%, respectively.
  • the device may be a molecular sieve device, which has a sieving effect on different ions.
  • the porous membrane in the molecular sieve device is a high flux graphene oxide membrane.
  • the high-flux graphene oxide membrane is placed between two solution tanks, and the cross-sectional transmission electron microscope photo of the graphene oxide membrane is shown in Figure 3.
  • the solution tank on the left (feeding end) was filled with 30 mM NaCl and MgCl 2 mixed solution, and the solution tank on the right (screening end) was filled with pure water.
  • the effective area of the graphene oxide film is 1 mm 2 .
  • a voltage source is applied to the graphene oxide membrane at a transmembrane voltage of 0.01V, while a pressure difference of 1 atmosphere is applied across the membrane (the pressure application position can be shown in Figure 9).
  • the measured concentration of Mg 2+ in the solution tank on the right was 1 mM and the concentration of Na + was 0.01 mM, indicating that the graphene oxide membrane can screen different ions with the help of an electric field.

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Abstract

一种多孔膜及其制备方法、使用方法，该多孔膜(100)包括多个直通道(110)，该多个直通道(110)设置为具有同一延伸方向，多孔膜(100)包括用于待透过物质进入和透出的两个相对的两端，直通道(110)沿与该两端之一至另一的方向垂直的方向并列排布。该多孔膜(100)具有高通量。

Description

多孔膜及其制备方法、使用方法
本申请要求于2019年3月22日递交的中国专利申请第201910221565.5号的优先权，在此全文引用上述中国专利申请公开的内容以作为本申请的一部分。
技术领域
本公开至少一个实施例涉及一种多孔膜及其制备方法、使用方法。
背景技术
从水净化到石油精炼、化学品生产和碳捕获等应用领域都存在对高效分离的需求。膜结构和材料是膜技术的关键，高性能膜结构和材料的关键技术突破将直接影响膜技术在实际应用中的推广。这促使人们对新型高性能分离膜的大力探索。膜性能的核心指标是选择性和通量，是许多化工过程中的关键共性问题，它们与膜的分离效果和运行成本密切相关。但是，选择性和渗透性(通量)是两个相互制约的因素，该问题限制了对膜的性能的进一步提高。
发明内容
本公开至少一个实施例提供一种多孔膜，该多孔膜包括多个直通道，该多个直通道设置为具有同一延伸方向；多孔膜包括用于待透过物质进入和透出的两个相对的两端直通道沿与两端之一至另一的方向垂直的方向并列排布。
例如，在本公开至少一个实施例提供的多孔膜中，直通道贯穿多孔膜的两端。
例如，将该两个相对的两端之一设为入液面，另一设为出液面，直通道贯穿多孔膜以使得入液面和出液面连通。
例如，在本公开至少一个实施例提供的多孔膜中，直通道的内径尺寸设置为小于待阻隔物质的尺寸且大于或等于待透过物质的尺寸。
例如，在本公开至少一个实施例提供的多孔膜中，直通道的延伸方向与从所述两端之一(例如入液面)至另一(例如出液面)的跨膜方向的夹角小于90°。
例如，在本公开至少一个实施例提供的多孔膜中，直通道的延伸方向与跨膜方向平行。
例如，本公开至少一个实施例提供的多孔膜中还包括导流结构，导流结构设置为限定出直通道的边界。
例如，本公开至少一个实施例提供的多孔膜中还包括基质膜，导流结构 嵌入在该基质膜中。
例如，在本公开至少一个实施例提供的多孔膜中，导流结构包括多个管状结构，管状结构的内部的管道和相邻的管状结构之间的间隔空间用于构成直通道。
例如，在本公开至少一个实施例提供的多孔膜中，至少两个管状结构依次相连，以使得其中的管道连接为一个直通道。
例如，在本公开至少一个实施例提供的多孔膜中，管状结构的材料包括碳纳米管、氮化硼管和碳纤维中的一种或组合。
例如，在本公开至少一个实施例提供的多孔膜中，管状结构的直径为0.1nm～10μm，长度为1nm～10mm。例如，相邻管状结构之间的间隔距离不大于2nm。
例如，在本公开至少一个实施例提供的多孔膜中，导流结构包括多个片层结构，相邻的片层结构之间的间隔空间构成直通道。
例如，在本公开至少一个实施例提供的多孔膜中，至少两个片层结构依次相连，以使得其中的管道连接为一个直通道。
例如，在本公开至少一个实施例提供的多孔膜中，片层结构的材料包括墨烯、氧化石墨烯、二硫化钼、黑磷、氮化硼、硅烯和锗烯中的一种或组合。
例如，在本公开至少一个实施例提供的多孔膜中，片层结构的长、宽尺寸为10nm～1mm，层间距为0.1nm～10μm。
例如，在本公开至少一个实施例提供的多孔膜中，入液面和出液面的间距为5nm～10mm。
本公开至少一个实施例提供一种根据多孔膜的制备方法，该多孔膜包括多个直通道，该多个直通道设置为具有同一延伸方向；多孔膜包括用于待透过物质进入和透出的两个相对的两端，直通道沿与两端之一至另一的方向垂直的方向并列排布，该制备方法包括：形成堆叠的薄膜；提供封装材料以对薄膜进行封装和固化处理；切割并研磨封装材料以暴露薄膜的两个相对的表面；以及从两个相对的表面对薄膜执行减薄工艺，以获得多孔膜；其中，两个相对的表面分别对应于上述相对的两端(入液面和出液面)。例如，在该多孔膜中，直通道贯穿多孔膜的两端。
例如，在本公开至少一个实施例提供的多孔膜的制备方法中，形成堆叠的薄膜包括：提供底膜并将其平铺到润湿的流动相过滤器的珐琅滤芯上并夹紧；注入分散液以进行抽真空过滤；以及将抽滤形成的膜放入50℃烘箱内使其进一步脱水，分散液脱水后形成薄膜。
例如，在本公开至少一个实施例提供的多孔膜的制备方法中，分散液包括氧化石墨烯。
例如，在本公开至少一个实施例提供的多孔膜的制备方法中，封装材料包括环氧树脂。
例如，在本公开至少一个实施例提供的多孔膜的制备方法中，减薄工艺包括机械研磨和离子减薄的一种或组合。
本公开至少一个实施例提供一种多孔膜的使用方法，该多孔膜包括多个直通道，该多个直通道设置为具有同一延伸方向；多孔膜包括用于待透过物质进入和透出的两个相对的两端，直通道沿与两端之一至另一的方向垂直的方向并列排布，该使用方法包括：将多孔膜置于包括正电荷和负电荷的离子的溶液槽中，在溶液的作用下，多孔膜发生电离，以使得直通道的表面带有电荷；多孔膜将溶液槽中的与直通道的电荷电性相同且尺寸小于直通道的内径的离子从两端之一(入液面)导入直通道，并使得进入直通道的离子从两端之另一(出液面)离开；多孔膜阻挡溶液槽中的与直通道的电荷电性相异且尺寸大于或等于直通道的内径的离子进入直通道。例如，在该多孔膜中，直通道贯穿多孔膜的两端。
例如，在本公开至少一个实施例提供的多孔膜的使用方法中，使得直通道的表面带有电荷的方法包括利用表面化学基团在溶液中电离产生电荷、通过化学修饰形成电荷或者通过辐照处理之后形成电荷。
附图说明
通过结合附图对本申请实施例进行更详细的描述，本申请的上述以及其他目的、特征和优势将变得更加明显。附图用来提供对本申请实施例的进一步理解，并且构成说明书的一部分，与本申请实施例一起用于解释本申请，并不构成对本申请的限制。在附图中，相同的参考标号通常代表相同部件或步骤。
图1A为本公开一些实施例提供的一种多孔膜的局部截面图；
图1B为本公开一些实施例提供的另一种多孔膜的局部截面图；
图1C为本公开一些实施例提供的另一种多孔膜的局部截面图；
图1D为本公开一些实施例提供的多孔膜的工作原理的示意图；
图2是一种多孔膜的结构及其工作原理的示意图；
图3是本公开一些实施例提供的多孔膜的截面SEM照片；
图4为本公开一些实施例提供的一种多孔膜的制备方法的过程图；
图5为本公开一些实施例提供的一种多孔膜的使用方法的过程图；
图6是本公开一些实施例提供的包括多孔膜的盐差能转化装置的结构示意图；
图7是图6所示实施例中的盐差能转化装置的输出功率图；
图8是本公开一些实施例提供的包括多孔膜的抽滤装置的结构示意图；以及
图9是本公开一些实施例提供的包括多孔膜的离子截留装置的结构示意图。
具体实施方式
为使本公开实施例的目的、技术方案和优点更加清楚，下面将结合本公开 实施例的附图，对本公开实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本公开的一部分实施例，而不是全部的实施例。基于所描述的本公开的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本公开保护的范围。
在纳米多孔膜中，选择性和渗透性(通量)是两个相互制约的因素，而且通过当前的新材料来制造膜的话，膜的选择性和渗透性的上限变化也并不大。
本公开至少一个实施例提供一种多孔膜及其制备方法、使用方法，至少可以解决上述技术问题。本公开的实施例提供的多孔膜包括多个直通道，该多孔膜包括多个直通道，该多个直通道设置为具有同一延伸方向；多孔膜包括用于待透过物质进入和透出的两个相对的两端，直通道沿与两端之一至另一的方向垂直的方向并列排布。在该多孔膜中，对待透过的物质而言，直通道的排布方式提供了极低的跨膜流阻，在物质(例如离子)透过多孔膜的过程中，会呈现短路径和低摩擦，从而使得多孔膜在具有较高的选择性的同时，还可以有较高的渗透性(通量)。
在本公开的实施例中，多孔膜的待透过物质、待阻隔物质可以包括原子、分子、离子、颗粒等的一种或组合。
例如，该相对的两端之一为多孔膜的入液面，该相对的两端之另一为多孔膜的出液面。直通道沿与从入液面至出液面的方向垂直的方向并列排布，直通道贯穿多孔膜以使得入液面和出液面连通。
在本公开至少一个实施例中，直通道贯穿多孔膜的两端。在该情况下，待透过的物质在入液面处即直接进入对应的直通道，且沿着该直通道穿过多孔膜，会呈现更短的路径和更低的摩擦，具有更高的渗透性(通量)。
下面，以直通道贯穿多孔膜的两端为例，结合附图对根据本公开至少一个实施例中的多孔膜及其制备方法、使用方法进行说明。
在本公开至少一个实施例中，如图1A所示，多孔膜100包括多个直通道110，多个直通道110设置为具有同一延伸方向，以呈现有序排布。例如，多个直通道110排布为大致彼此平行。多孔膜100包括相对的入液面101和出液面102，直通道110沿与从入液面101至出液面102的方向垂直的方向并列排布，直通道110贯穿多孔膜100以使得入液面101和出液面102连通。如此，在使用多孔膜100时，物质(例如离子)可以从入液面101进入直通道110，然后沿着直通道110移动至出液面102，然后从出液面102离开多孔膜100，由于直通道的形状大致为直线形，在该过程中，进入一个直通道110的物质会沿着同一个直通道110移动，不会出现因无序运动造成的阻力(摩擦)增大和移动距离增加的现象，即，多孔膜100对该物质呈现高的渗透性。
需要说明的是，在本公开的实施例中，物质能否通过多孔膜还需要考虑直通道的尺寸，直通道的内径尺寸设置为小于待阻隔物质的尺寸且大于或等于待透过物质的尺寸。如此，可以使得待透过的物质(例如离子)进入直通道。直通道的内径与多孔膜中用于形成直通道的具体结构(例如下述实施例中的管状结构、片层结构)有关，可以参见下述实施例中的相关说明，再次不做赘述。
在本公开的实施例中，建立空间直角坐标系以对各个结构的位置及方向进行说明。示例性的，如图1A所示，在该空间直角坐标系中，X轴与多孔膜的跨膜方向平行，Y(未示出)轴和Z轴与入液面101和出液面102平行。
例如，在本公开至少一个实施例提供的多孔膜中，直通道的延伸方向与沿入液面至出液面的跨膜方向的夹角小于90°。示例性的，如图1B所示，多孔膜100a中的直通道110a的延伸方向(图中的箭头“→”)与跨膜方向(X轴)的夹角为锐角，在该情况下，有利于物质(例如离子)主要在同一个直通道110a内移动。例如，该锐角越小，物质移动的距离越小，多孔膜100a的渗透性越高。
例如，在本公开至少一个实施例提供的多孔膜中，直通道的延伸方向与跨膜方向平行。示例性的，如图1A所示，多孔膜100中的直通道110的延伸方向(图中的箭头“→”)与跨膜方向(X轴)平行，在该情况下，从入液面101a至出液面102a，物质(例如离子)基本会在同一个直通道110内移动，物质移动的距离与多孔膜100沿跨膜方向的尺寸相等，在尺寸固定的情况下，多孔膜100的渗透性会更高。
例如，本公开至少一个实施例提供的多孔膜中还包括导流结构，导流结构设置为限定出直通道的边界。示例性的，如图1A和图1B，导流结构120、120a用于限定出直通道110、110a，从而限定出物质(例如离子)移动的边界。
在本公开的实施例中，对导流结构的具体形状不做限制，可以根据需要进行设计。例如，在一些实施例中，导流结构可以设置为包括多个管状结构，通过管状限定物质的流动边界，从而限定出直通道。例如，在本公开另一些实施例中，导流结构可以设置为包括多个片层结构，通过片层隔离物质的流动边界，从而限定出直通道。下面，针对导流结构分别包括管状结构和片层结构的情况，对多孔膜的结构进行说明。
例如，在本公开至少一个实施例提供的多孔膜中，导流结构包括多个片层结构，相邻的片层结构之间的间隔空间构成直通道。示例性的，如图1A所示，导流结构120由多个片层结构构成，直通道110位于相邻的片层结构之间。
例如，在本公开至少一个实施例提供的多孔膜中，至少两个片层结构依次相连，以使得其中的管道连接为一个直通道。示例性的，如图1A所示，沿X轴方向，多个片层结构排布在一条线上，如此，沿Z轴方向相邻的片层结构限定的间隔空间可以构成直通道110。
需要说明的是，如果片层结构的尺寸足够大，或者多孔膜足够薄(沿着跨膜方向)，一个片层结构即可以从入液面延伸至出液面，从而不需要将多个片层结构依次相连。
例如，在本公开至少一个实施例提供的多孔膜中，片层结构的材料包括墨烯、氧化石墨烯、二硫化钼、黑磷、氮化硼、硅烯和锗烯中的一种或组合，也可以为其它适用的材料，本公开的实施例对此不做限制。
例如，在本公开至少一个实施例提供的多孔膜中，片层结构的长、宽尺寸为10nm～1mm，例如进一步为100nm、1μm、10μm、100μm等，层间距为0.1nm～10μm，例如进一步为1nm、10nm、100nm、1μm等。
例如，在本公开至少一个实施例提供的多孔膜中，导流结构包括多个管状结构，管状结构的内部的管道和相邻的管状结构之间的间隔空间构成直通道。示例性的，如图1C所示，多孔膜100b中的导流结构120b由多个管状结构构成，相邻的管状结构之间的间隔空间构成直通道100b，管状结构的内部的管道构成直通道100c。
例如，在本公开至少一个实施例提供的多孔膜中，至少两个管状结构依次相连，以使得其中的管道连接为一个直通道。示例性的，如图1C所示，管状结构的长度小于入液面101b至出液面102b的间距，多个管状结构排布在一条线上且前后相连，如此，该多个管状结构的内部管道也会彼此相连以形成直通道100c。
需要说明的是，如果管状结构的长度足够大，或者多孔膜足够薄(沿着跨膜方向)，一个管状结构即可以从入液面延伸至出液面，从而不需要将多个管状结构依次相连。
例如，在本公开至少一个实施例提供的多孔膜中，管状结构的材料包括碳纳米管、氮化硼管和碳纤维中的一种或组合，也可以为其它适用的材料。
例如，在本公开至少一个实施例提供的多孔膜中，管状结构的直径为0.1nm～10μm，例如进一步为1nm、10nm、100nm、1μm等，长度为1nm～10mm，例如进一步为10nm、100nm、1μm、10μm、100μm、1mm等，相邻管状结构之间的间隔距离不大于2nm。
例如，在本公开至少一个实施例提供的多孔膜中，入液面和出液面的间距为5nm～10mm，例如进一步为10nm、100nm、1μm、10μm、100μm、1mm等。
在本公开至少一个实施例中，多孔膜还包括基质膜，导流结构嵌入在该基质膜中。基质膜可以作为多孔膜的支撑材料，并可以将导流结构结合以固定在一起。示例性的，如图1A所示，多孔膜100包括基质膜130，导流结构120(例如片层结构)嵌入在该基质膜130的内部。该基质膜的材料可以为环氧树脂等。
图1D和图2示出了两种多孔膜的工作原理示意图，其中，图1D使用本公开的图1A所示实施例中的多孔膜，图2示出的多孔膜未完全使用本公开的技术方案进行设计，该两个多孔膜的导流结构都有片层结构(图中的带电荷片层)构成。在实际工艺中，不同层的片层结构之间的间隔(直通道的内径)可以进行设计，而同层的相邻片层之间的间隔距离难以调控。由图1D可以看出，带电荷片层之间形成直通道，而且该直通道用于使得物质(离子)流过，因此，通过工艺设置，很容易设计直通道的直径，使得直径小于直通道的内径的离子或者颗粒才能够进入直通道，在配合片层的电荷的情况下，可以使得所有直径小于直通道的内径且电性与片层的电荷相反的离子进入直通道，因此多孔膜的选择性非常高。由图2可以看出，离子需要通过同层的带电荷片层之间的间隙进入多孔膜，而该间隙的尺寸难以确定，如此，难以对适合尺寸的离子进行筛选，相比图1D所示的多孔膜，其选择性低。此外，与图1D所示的离子可以在多孔膜的直通道内单向移动相比，图2中的离子需要在多个片层的多个间隙之 间移动才能够贯穿多孔膜，无法做到单向移动且路径过长，图1D所示的多孔膜的渗透性会远高于图2所示的多孔膜的渗透性。
需要说明的是，在本公开上述示例中的附图示出的多孔膜为示意图，其真实结构可以参照图3所示的扫描电子显微镜(Scanning electron microscope，简称“SEM”)的照片可以如图3所示。在图3中，多孔膜的导流结构有片层结构构成。
本公开至少一个实施例提供一种根据多孔膜的制备方法，该多孔膜包括多个直通道，该多个直通道设置为具有同一延伸方向。多孔膜包括用于待透过物质进入和透出的两个相对的两端，直通道沿与两端之一至另一的方向垂直的方向并列排布。例如，在该多孔膜中，直通道贯穿多孔膜的两端。该两个相对的两端之一为入液面，另一为出液面，直通道沿与从入液面至出液面的方向垂直的方向并列排布，直通道贯穿多孔膜以使得入液面和出液面连通。多孔膜的结构可以参见前述实施例中的相关说明，再次不做赘述。如图4所示，该制备方法包括：形成堆叠的薄膜；提供封装物质以对单个或者多个薄膜阵列进行封装和固化处理；切割并研磨封装材料以暴露薄膜的两个相对的表面；以及从两个相对的表面对薄膜执行减薄工艺，以获得多孔膜；其中，两个相对的表面对应于入液面和出液面。在通过上述制备方法获得的多孔膜中，直通道贯穿多孔膜的两端，提供了极低的跨膜流阻，在物质(例如离子)透过多孔膜的过程中，会呈现短路径和低摩擦，从而使得多孔膜在具有较高的选择性的同时，还可以有较高的渗透性(通量)。
例如，在本公开至少一个实施例提供的多孔膜的制备方法中，形成堆叠的薄膜包括：提供底膜并将其平铺到润湿的流动相过滤器的珐琅滤芯上并夹紧；注入分散液以进行抽真空过滤；以及将抽滤形成的膜放入50℃烘箱内使其进一步脱水，分散液脱水后形成薄膜。示例性的，通过真空抽滤法制备由水平堆叠的氧化石墨烯(Graphene Oxide，简称“GO”)片层构成的薄膜：将底膜(例如，混合纤维素酯膜或聚碳酸酯膜等)平铺到润湿的流动相过滤器的珐琅滤芯上，然后盖好上层配套装置并用夹子(或其其它固定装置)夹紧。再注入合适量的GO分散液进行抽真空过滤，并将抽滤形成的膜放入50℃烘箱内使其进一步脱水，形成排列致密的材料。例如，在本公开的实施例中，GO分散液中的GO含量可以为0.01mg/ml-50mg/ml，例如进一步为0.1mg/ml、1mg/ml、10mg/ml、20mg/ml、30mg/ml、40mg/ml等。
例如，在本公开至少一个实施例提供的多孔膜的制备方法中，分散液包括氧化石墨烯或其它合适的材料。
例如，在本公开至少一个实施例提供的多孔膜的制备方法中，封装材料包括环氧树脂或其它合适的材料。示例性的，在利用环氧树脂封装处理中，将制备好的材料裁剪成合适宽度(1mm到4mm)的长条状，借助亚克力板使裁剪好的片层垂直竖立在环氧树脂胶中，在紫外线灯下照射5min便可固化。例如，该封装材料用于形成多孔膜的基质膜(可参见图1A中的基质膜130)。
示例性的，在切割与研磨处理中，切割材料的多余部分，用砂纸湿法打磨 这个封装体，并使其两端暴露到空气中。这时便制备成GO片层垂直排列的高通量氧化石墨烯膜。
例如，在本公开至少一个实施例提供的多孔膜的制备方法中，减薄工艺可以包括机械研磨、离子减薄或其它合适的减薄方法。使用离子减薄仪进一步削减薄膜(多孔膜)的厚度，可以增大其通量。
需要说明的是，在本公开的实施例中，通过上述制备方法获得的高通量多孔膜的孔隙率可达20％～90％，例如进一步为。需要说明的是，在本公开的实施例中，可以在保持多孔膜的高通量的同时降低了对孔隙率的要求。在本公开的实施例中，物质主要在多孔膜的直通道内移动，从理想状态而言，物质可以不需要在不同的直通道之间移动，因此即便多孔膜的孔隙度不高，与当前的多孔膜相比，也会呈现更高通量的性能。
本公开至少一个实施例提供一种多孔膜的使用方法，该多孔膜包括多个直通道，该多个直通道设置为具有同一延伸方向。多孔膜包括用于待透过物质进入和透出的两个相对的两端，直通道沿与两端之一至另一的方向垂直的方向并列排布。例如，在该多孔膜中，直通道贯穿多孔膜的两端。该两个相对的两端之一为入液面，另一为出液面，直通道沿与从入液面至出液面的方向垂直的方向并列排布，直通道贯穿多孔膜以使得入液面和出液面连通。多孔膜的结构可以参见前述实施例中的相关说明，再次不做赘述。如图5所示，该使用方法包括：将多孔膜置于包括正电荷和负电荷的离子的溶液槽中，在溶液的作用下，多孔膜发生电离，以使得直通道的表面带有电荷；多孔膜将溶液槽中的与直通道的电荷电性相同且尺寸小于直通道的内径的离子从入液面导入直通道，并使得进入直通道的离子从出液面离开；多孔膜阻挡溶液槽中的与直通道的电荷电性相异且尺寸大于或等于直通道的内径的离子进入直通道。在该多孔膜的使用方法中，因为直通道贯穿多孔膜的两端，提供了极低的跨膜流阻，在物质(例如离子)透过多孔膜的过程中，会呈现短路径和低摩擦，从而使得多孔膜在具有较高的选择性的同时，还可以有较高的渗透性(通量)。
例如，在本公开至少一个实施例提供的多孔膜的使用方法中，使得直通道的表面带有电荷的方法包括利用表面化学基团在溶液中电离产生电荷、通过化学修饰形成电荷或者通过辐照处理之后形成电荷。
本公开至少一个实施例提供一种高通量的多孔膜设计方法，该方法的具体步骤可以如下：
由管状结构或片层结构组成多孔膜结构，管状结构或片层结构沿跨膜方向定向排布，构成贯穿多孔膜两端的直通道，直通道提供流体跨膜输运路径和跨膜流阻，同时管状结构或片层结构原子级别的平整界面(多孔膜为纳米多孔膜，直通道使得流体有序移动而呈现高的平滑性能)和高孔隙率(20％～90％)为流体输运提供高流阻；直通道可采用最短(参考前述实施例中的相关说明，例如为入液面至出液面的距离)的流体跨膜输运路径；流体在孔道内(例如管状结构的管道)或层间传输(相邻管状结构或者相邻片层结构的间隙)的方向与跨膜方向一致，直通道的延伸方向与跨膜的方向小于90°，单个直通道可以不需 要完全穿透多孔膜的两端，可由多个直通道前后相连形成跨膜的输运通道。片层结构采用二维片层结构，管状结构采用一维管状结构，一维管状结构组成多孔膜，流体在管道内部或管道之间传输，流体在空间的三个维度上，是一个二维受限空间内的一维传输，由二维片层结构组成多孔膜，流体在片层(片层结构)与片层之间输运或流动，流体在一维受限空间内传输；贯穿多孔膜两端的直通道由一维管状结构或二维片层结构组成，构成贯穿多孔膜两端的直通道。
例如，一维管状结构的直径为0.1nm～10μm，长度为1nm～10mm；二维片层结构的片径为10nm～1mm，层间距为0.1nm～10μm。贯穿多孔膜两端的直通道的厚度为5nm～10mm。一维管状结构包括但不限于碳纳米管、氮化硼管、碳纤维等；二维片层结构包括但不限于石墨烯、氧化石墨烯、二硫化钼、黑磷、氮化硼、硅烯和锗烯等。
例如，在本公开的实施例中，一维管状结构和二维片层结构的制备方法包括但不限于物理剥离、静电自组装、片层堆叠、化学自组装、界面与多相自组装、旋涂法、真空抽滤、喷墨与喷雾法、溶胶-凝胶法、气相-溶液-固相法、声波降解法、溶剂热法、模板法、化学气相沉积法等中的一种。跨膜的内壁带电直通道结构的离子选择方式，包括阴离子选择性和阳离子选择性，选择性包括对离子、分子、颗粒等多种成分。
将多孔膜置于溶液槽中，在水溶液的作用下，多孔膜发生电离，使孔道表面带有电荷。发生电离后的纳米通道对携带同种电荷的离子产生排斥作用，从而阻碍离子进入孔道；极窄(例如不大于2nm)的层间距对大于层间距尺寸的水合离子(以溶液的溶剂是水为例)产生空间尺寸上的限制作用，从而限制其通过，水溶液中的溶剂分子、离子和微粒在驱动力(例如异性电荷之间的引力、电场影响下的作用力或其它)的作用下，沿贯穿的直通道从多孔膜的一侧(例如入液面)到达另一侧(例如出液面)时，通过有限空间上的距离完成流体的输运。纳米通道(例如直通道)内表面携带的电荷，可以是材料表面自身携带的电荷，也可以是通过化学修饰或辐照处理之后形成的电荷，所携带的电荷可为正电荷也可以为负电荷。
高通量多孔膜的孔隙率可为20％～90％。
本公开的实施例中的高通量多孔膜都具有高离子选择性。将多孔膜置于特定溶液槽(根据具体的实施例决定溶液槽的类型)中，在水溶液的作用下，多孔膜会发生电离使孔道(孔隙，包括直通道)的表面带有电荷。根据库伦效应可知，发生电离后的纳米通道(直通道)会对携带同种电荷的离子产生排斥作用从而阻碍离子进入孔道；极窄(例如不大于2nm)的层间距能对大于层间距尺寸的水合离子产生空间尺寸上的限制作用，从而限制其通过。溶液中的溶剂分子、离子和微粒在驱动力(例如异性电荷之间的引力、电场影响下的作用力或其它)的作用下，沿贯穿的直通道从膜的一侧(例如入液面)到达另一侧(例如出液面)时，仅需通过有限空间上的距离就可完成，大大提高了流体的输运速度。参见图1D和图2，示出了二维片层沿跨膜方向定向排布的纳米多孔膜，图2示出了二维片层与跨膜方向垂直排布的纳米多孔膜，可以看出图1D的结 构更有利于流体的输运。
本发明利用二维材料片层或者一维管道，制备二维片层或者一维管道沿跨膜方向定向排布的纳米多孔膜。这样的纳米结构具有均一的层间距以及丰富的表面电荷(大于0.1mC m -2)提供了高离子选择性，同时二维片层原子级别的平整界面、贯穿的直孔道和高孔隙率为流体输运提供了极低的流阻，有望突破现有材料中渗透性-选择性的限制，其选择性来源于孔径或者层间距的空间位阻和物理尺寸效应、表面电荷效应、化学相互作用(包括氢键、形成新的化学配位键等)等。
本发明提供了一种高通量的多孔膜结构，该多孔膜由管状结构或片层结构组成，构成贯穿膜两端的直通道，提供了极低的跨膜流阻；这些直通道具有非常窄的孔径或层间距分布，提供了多孔膜的高选择性；该多孔膜还具有非常高的孔隙率提供了高通量。该高通量的多孔膜结构可广泛应用于正渗透过程、反渗透过程、渗透汽化过程、电渗析过程，还可以用于气体、液体、固体的过滤、分离、检测、盐差能转化、电池隔膜、质子交换膜、电渗析、膜吸收、膜萃取、膜蒸馏、膜反应器等体系中；其所具有的高通量性质在上述领域中有着在重要意义。
本公开至少一个实施例提供一种装置，该装置包括上述实施例中的多孔膜。本公开的实施例对该装置的具体应用不做限制，可以根据需要进行设计，下面，在几个示例中，对装置的几种类型进行说明。
例如，在本公开的一个示例中，装置可以为盐差能-电能转化装置。
例如，该盐差能-电能转化装置中的多孔膜为二硫化钼高通量选择性膜，其材料可以为二硫化钼。二硫化钼高通量选择性膜的制备可以包括：利用超声细胞粉碎机制备片径均匀的二硫化钼分散液，采用真空抽滤二硫化钼分散液的方法，在纤维素膜或者核孔膜上形成所需的二维层状薄膜。由于二硫化钼片层所带的负电荷，在沉积过程中，二硫化钼片层在静电斥力的作用下自组装成层间距介于0.8～1.1nm的多孔膜材料。经过进一步的高温热处理，制得核孔膜-二硫化钼复合材料。之后将样品用环氧树脂进行包埋，通过切片的方法将包埋过的单个二硫化钼纳米多孔材料加工成合适的尺寸，并组装成大面积的样品，最后通过对膜表面的研磨和减薄制得需要面积和厚度的样品(多孔膜)。
如图6所示，将二硫化钼高通量膜封装到溶液槽，在左侧溶液槽加入500mM NaCl溶液，在右侧溶液槽加入10mM NaCl溶液；在离子浓度梯度的驱动下，离子形成跨膜的净扩散导致净电流和电动势，并能够向外电路输出电能。需要说明的是，左、右两侧的溶液槽中的溶液不限于NaCl溶液，而且该两个溶液槽中的溶液的类型也可以不同，本公开的实施例对此不做限制。
根据公式P out＝I 2.R，可计算出该系统(装置)的输出功率。其中P out为该系统的输出功率，I为系统中的电流，R为外电路中的负载电阻。
在保证溶液槽两端浓度不变的时候，通过调节外电路中负载电阻大小的方式可获得该系统中的最大输出功率，结果如图7所示。图6中，所用二硫化钼混合膜的厚度(沿垂直于纸面的方向)为250μm，有效膜面积(沿平行于纸面 的截面的面积)为1mm*6μm。示例性的，在图7中，通过调节外部电阻，输出功率最高可达6.03W m -2。
例如，在本公开的一个示例中，装置可以为海水淡化装置。
例如，该海水淡化装置中的多孔膜为氧化石墨烯高通量选择性膜。氧化石墨烯高通量选择性膜的制备可以包括：用旋涂法将氧化石墨烯的悬浊液均匀地涂抹在纤维素膜上，经过热处理后得到氧化石墨烯的多孔膜结构。制备好的氧化石墨烯膜的横截面透射电镜照片如图3所示。之后将样品用有机玻璃进行包埋，通过切片的方法将包埋好的单个纳米多孔材料加工成合适的尺寸，并组装成大面积的样品，最后通过对表面的研磨和减薄制得需要面积和厚度的样品；减薄后氧化石墨烯高通量膜的暴露端呈现出图3中的片层结构。
如图8所示，将氧化石墨烯多孔膜封装到抽滤槽中，在槽的入口室中添加不同盐度的NaCl溶液(盐溶液)，并在抽滤端口处进行抽真空(如图中所示，通过抽气改变气压条件)。在外界大气压的作用下，水分子通过氧化石墨烯膜到达膜的另一侧，形成例如图8中所示的液态水，而Na +和Cl -等水合离子由于氧化石墨烯层间距的空间限制作用，被阻隔在多孔膜外。该测试过程中，氧化石墨烯膜的有效面积为4cm 2。当NaCl的浓度分别为0.8wt％、3.5wt％、4wt％和10wt％时，其所对应的截留率分别为99.3％、98％、97.5％和96％。
例如，在本公开的一个示例中，装置可以为分子筛装置，具有对不同离子的筛分作用。
例如，该分子筛装置中的多孔膜为高通量氧化石墨烯膜。如图9所示，将高通量氧化石墨烯膜置于两个溶液槽之间，氧化石墨烯膜的横截面透射电镜照片如图3所示。在左侧(进料端)的溶液槽装入30mM的NaCl和MgCl 2混合液，在右侧(筛分端)的溶液槽装上纯水。氧化石墨烯膜的有效面积为1mm 2。通过电压源对氧化石墨烯膜施加在0.01V的跨膜电压，同时在膜两端施加1个大气压的压强差(压力施加的位置可如图9所示)。2小时后，右侧溶液槽里能够测得Mg 2+的浓度为1mM，而Na +的浓度为0.01mM，说明氧化石墨烯膜在电场辅助下可以实现对不同离子的筛分。
以上所述仅为本公开的较佳实施例而已，并不用以限制本公开，凡在本公开的精神和原则之内，所作的任何修改、等同替换等，均应包含在本公开的保护范围之内。

Claims (23)

  1. 一种多孔膜，包括：
    多个直通道，设置为具有同一延伸方向；
    其中，所述多孔膜包括用于待透过物质进入和透出的两个相对的两端，所述直通道沿与所述两端之一至另一的方向垂直的方向并列排布。
  2. 根据权利要求1所述的多孔膜，其中，
    所述直通道贯穿所述多孔膜的两端。
  3. 根据权利要求1或2所述的多孔膜，其中，
    所述直通道的内径尺寸设置为小于待阻隔物质的尺寸且大于或等于所述待透过物质的尺寸。
  4. 根据权利要求1-3中任一项所述的多孔膜，其中，
    所述直通道的延伸方向与从所述两端之一至另一的跨膜方向的夹角小于90°。
  5. 根据权利要求4所述的多孔膜，其中，
    所述直通道的延伸方向与所述跨膜方向平行。
  6. 根据权利要求1-5中任一项所述的多孔膜，还包括导流结构，其中，所述导流结构设置为限定出所述直通道的边界。
  7. 根据权利要求6所述的多孔膜，还包括基质膜，其中，
    所述导流结构嵌入在所述基质膜中。
  8. 根据权利要求5或6所述的多孔膜，其中，
    所述导流结构包括多个管状结构，所述管状结构的内部的管道和相邻的所述管状结构之间的间隔空间用于构成所述直通道。
  9. 根据权利要求8所述的多孔膜，其中，
    至少两个所述管状结构依次相连，以使得其中的管道连接为一个所述直通道。
  10. 根据权利要求8或9所述的多孔膜，其中，
    所述管状结构的材料包括碳纳米管、氮化硼管和碳纤维中的一种或组合。
  11. 根据权利要求8-10中任一项所述的多孔膜，其中，
    所述管状结构的直径为0.1nm～10μm，长度为1nm～10mm，以及相邻所述管状结构之间的间隔距离不大于2nm。
  12. 根据权利要求5或6所述的多孔膜，其中，
    所述导流结构包括多个片层结构，相邻的所述片层结构之间的间隔空间构成所述直通道。
  13. 根据权利要求12所述的多孔膜，其中，
    至少两个所述片层结构依次相连，以使得其中的管道连接为一个所述直通道。
  14. 根据权利要求12或13所述的多孔膜，其中，
    所述片层结构的材料包括墨烯、氧化石墨烯、二硫化钼、黑磷、氮化硼、 硅烯和锗烯中的一种或组合。
  15. 根据权利要12-14中任一项所述的多孔膜，其中，
    所述片层结构的长、宽尺寸为10nm～1mm，层间距为0.1nm～10μm。
  16. 根据权利要求15所述的多孔膜，其中，
    所述两端的间距为5nm～10mm。
  17. 一种根据权利要求1-16中任一项所述的多孔膜的制备方法，包括：
    形成堆叠的薄膜；
    提供封装材料以对所述薄膜进行封装和固化处理；
    切割并研磨所述封装材料以暴露所述薄膜的两个相对的表面；以及
    从所述两个相对的表面对所述薄膜执行减薄工艺，以获得所述多孔膜；
    其中，所述两个相对的表面分别对应于所述相对的两端。
  18. 根据权利要求17所述的制备方法，其中，所述形成堆叠的薄膜包括：
    提供底膜并将其平铺到润湿的流动相过滤器的珐琅滤芯上并夹紧；
    注入分散液以进行抽真空过滤；以及
    将抽滤形成的膜放入50℃烘箱内使其进一步脱水，所述分散液脱水后形成所述薄膜。
  19. 根据权利要求18所述的制备方法，其中，
    所述分散液包括氧化石墨烯。
  20. 根据权利要求17-19中任一项所述的制备方法，其中，
    所述封装材料包括环氧树脂。
  21. 根据权利要求17-20中任一项所述的制备方法，其中，
    所述减薄工艺为机械研磨和离子减薄的一种或组合。
  22. 一种根据权利要求1-16中任一项所述的多孔膜的使用方法，包括：
    将所述多孔膜置于包括正电荷和负电荷的离子的溶液槽中，在溶液的作用下，所述多孔膜发生电离，以使得所述直通道的表面带有电荷；
    所述多孔膜将所述溶液槽中的与所述直通道的电荷电性相同且尺寸小于所述直通道的内径的所述离子从所述两端之一导入所述直通道，并使得进入所述直通道的所述离子从所述两端之另一离开；以及
    所述多孔膜阻挡所述溶液槽中的与所述直通道的电荷电性相异且尺寸大于或等于所述直通道的内径的所述离子进入所述直通道。
  23. 根据权利要求21所述的使用方法，其中，
    所述使得所述直通道的表面带有电荷的方法包括利用表面化学基团在溶液中电离产生电荷、通过化学修饰形成电荷或者通过辐照处理之后形成电荷。
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