CN115165933B - Graphene-porous membrane-graphene sandwich liquid pool structure and preparation method and application thereof - Google Patents
Graphene-porous membrane-graphene sandwich liquid pool structure and preparation method and application thereof Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/04—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and forming images of the material
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- C01B32/00—Carbon; Compounds thereof
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
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- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
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Abstract
The invention discloses a graphene-porous membrane-graphene sandwich liquid pool structure and a preparation method and application thereof, and belongs to the field of materials. The preparation method comprises the steps of attaching a porous membrane with controllable thickness and size to graphene to obtain a graphene-porous membrane composite structure, and transferring the graphene-porous membrane composite structure to a metal micro-grid to obtain the metal micro-grid-graphene-porous membrane composite structure; and transferring a self-supporting graphene film on the metal micro-grid-graphene-porous film composite structure to form a graphene-porous film-graphene sandwich liquid pool structure, wherein liquid is encapsulated in cylindrical holes of the porous film, and the upper surface and the lower surface are respectively encapsulated by graphene. The graphene-porous membrane-graphene sandwich liquid pool structure can be used for liquid-phase electron microscopy imaging or frozen electron microscopy imaging.
Description
Technical Field
The invention relates to the field of materials, in particular to a graphene-porous membrane-graphene sandwich liquid pool structure and a preparation method and application thereof.
Background
In recent years, transmission electron microscope technology has been rapidly developed, imaging resolution has been continuously improved, and the microstructure of a substance can be revealed on an atomic scale, and at the same time, imaging dimensions are advanced from initial two-dimensional imaging to multi-dimensional imaging. Three-dimensional structures of single-particle sample atomic resolution can be analyzed by a three-dimensional reconstruction technology of a refrigeration electron microscope, an atomic tomography technology and the like; the in-situ liquid-phase electron microscope technology realizes real-time high-resolution characterization of particles in a liquid phase, can realize time resolution and space resolution four-dimensional imaging of the particles, and is beneficial to revealing the structure-activity relationship and the internal mechanism in the chemical reaction process. The technology mainly realizes in-situ characterization of particles in a liquid phase by constructing a liquid pool structure, and the basic principle is as same as that of cells of organisms, and the solution is encapsulated by a cell membrane so as to obtain real-time motion information of the particles in the solution. The liquid pool structure not only prevents the sample from being damaged by high vacuum and strong electron beam irradiation, but also provides free motion environment for microscopic particles. Through the regulation and control of the liquid pool structure, the use of a high-sensitivity electronic detector and advanced 3D reconstruction software, researchers can observe the processes of nucleation, growth, movement and the like of nanoparticles, reconstruct the information of a high-resolution three-dimensional structure and the like of a sample, and are very suitable for in-situ high-resolution characterization of the samples such as metal nanoparticle catalysts, biological proteins and the like. Based on the advantages, the in-situ liquid-phase TEM characterization technology has wide application prospect in the fields of nano science, life science and the like.
With the continuous development of in-situ liquid phase TEM technology, sample preparation is becoming one of the primary obstacles limiting further resolution improvement. At present, materials for forming the liquid pool mainly comprise silicon nitride and graphene, the thickness of a traditional silicon nitride film is generally 50-500 nm, the thickness of packaging liquid is also larger than 1 mu m, and the imaging resolution of TEM is seriously reduced. And the graphene has excellent electrical, mechanical and optical properties, and is an ideal transmission electron microscope screen material. The regularly arranged carbon monoatomic layer greatly reduces imaging background noise and provides extremely high contrast for monoatoms, small organic molecules and the like. The good electric conductivity and heat conduction of graphene can reduce radiation damage of electrons to a sample, and high mechanical strength ensures that the sample is effectively loaded. And the pi-pi interaction between graphene layers is strong, so that good encapsulation of liquid can be realized. In recent years, a graphene liquid pool structure gradually becomes a research hotspot in the field of in-situ liquid-phase TEM, and is widely applied to research of nano science, energy science and life science.
The traditional graphene liquid pool utilizes pi-pi interaction between graphene layers to paste two graphene pairs together, the liquid pool is simple in structure preparation and good in liquid pool tightness, the liquid pool is formed randomly, the thickness and the volume of the liquid pool are nonuniform, a large amount of screening is needed during imaging, a liquid pool with a proper size is searched for characterization, and data acquisition efficiency is low. In addition, the construction of the traditional graphene liquid pool generally needs to assist in transferring graphene by using a polymer (such as PMMA), and the photoresist removing process can damage a system on one hand and can cause the problem of residual photoresist pollution on the other hand.
Disclosure of Invention
Aiming at the problems, the invention provides a graphene-porous membrane-graphene sandwich liquid pool structure, a preparation method and application thereof, and the graphene-porous membrane-graphene sandwich liquid pool structure is used for multi-dimensional electron microscope imaging, can accurately control the thickness and the volume of a liquid pool, and is beneficial to high-efficiency data acquisition due to the arrayed structure; meanwhile, the liquid pool structure is frozen to obtain the ice layer with uniform thickness, and the ice layer has important application prospect in the field of high-resolution frozen electron microscope imaging.
The invention firstly provides a preparation method of a metal micro-grid-graphene-porous membrane composite structure, which comprises the following steps:
(1) Preparing a porous membrane floating on the water surface;
(2) Immersing the graphene on the metal substrate in water with the front side facing upwards, and fishing out the porous membrane from bottom to top to obtain a porous membrane-graphene-metal substrate composite structure;
(3) Wet etching the metal substrate in the porous membrane-graphene-metal substrate composite structure to obtain a self-supporting porous membrane-graphene composite membrane on the liquid surface;
(4) Immersing a substrate fixed with a batch of metal micro-grids in liquid where the porous membrane-graphene composite membrane is located, and fishing out the porous membrane-graphene composite membrane from bottom to top to obtain the metal micro-grid-graphene-porous membrane composite structure;
Or placing the substrate fixed with the batched metal micro-grids under the porous membrane-graphene composite membrane, and slowly pumping out water to enable the porous membrane-graphene composite membrane to be slowly deposited on the metal micro-grids, so as to obtain the metal micro-grid-graphene-porous membrane composite structure.
In the preparation method, the thickness of the porous film is 10-100 nm; in particular 50nm or 80nm;
the porous film is a gold film or a carbon film;
The metal substrate is copper foil, a copper wafer or copper-nickel alloy;
The porous membrane floating on the water surface is prepared by a method described in patent number ZL202110333466.3 (the name of the invention is that a porous transmission electron microscope support membrane and an ultra-flat graphene electron microscope carrier net and a preparation method thereof are adopted).
The specific method comprises the following steps: and sequentially plating a water-soluble sacrificial layer and a porous electron microscope supporting film layer on the array template by using vacuum coating, and separating the porous electron microscope supporting film layer from the array template in water to obtain the porous film floating on the water surface.
The number of layers of the graphene is a single layer or a plurality of layers (2-5 layers);
in the step (2), hydrophilizing treatment is performed on the graphene on the metal substrate.
The hydrophilization treatment specifically adopts plasma etching or ultraviolet-ozone hydrophilization;
Specifically, the plasma etching is oxygen plasma etching, and the flow rate of oxygen gas is 1-5 sccm; the power is 10-100W; the time is 6-60 s; more specifically, the oxygen gas flow rate was 1sccm, the power was 30W, and the time was 18s.
In the step (3), the etching liquid of the wet etching is ammonium persulfate, sodium polysulfide or ferric chloride;
the concentration of the etching liquid is 0.1 mol/L-1 mol/L; specifically, the concentration of the catalyst can be 0.5mol/L;
The etching temperature is room temperature.
The preparation method of the graphene on the metal substrate is a method commonly used in the field, and specifically can be prepared by adopting a chemical vapor deposition method.
In the preparation method, the metal micro-grid is made of gold, copper, nickel, molybdenum or nonmetallic material silicon nitride;
The metal micro-grid is 200-400 meshes; specifically 300 mesh.
In the preparation method, in the step (3), the porous membrane-graphene composite membrane is washed after the metal substrate is etched;
Specifically, the washing mode is to drag up and transfer the porous membrane-graphene composite membrane to the deionized water surface for floating washing by using a glass slide or a stainless steel net;
the washing step is carried out for 2 to 3 times of transfer, and the time of each washing is 10 to 20 minutes.
In the step (4), a step of drying the metal micro-grid-graphene-porous membrane composite structure is further carried out;
Specifically, the drying time is 0.5-5 days, and specifically can be 1 day; the drying temperature is 20-80 ℃; specifically, the room temperature is available.
The invention also provides a metal micro-grid-graphene-porous membrane composite structure prepared by the preparation method.
The application of the metal micro-grid-graphene-porous membrane composite structure in the preparation of a transmission electron microscope carrier net or a low-temperature freezing electron microscope carrier net also belongs to the protection scope of the invention.
The invention further provides a preparation method of the graphene-porous membrane-graphene sandwich liquid pool structure, which comprises the following steps:
a) Preparing a self-supporting graphene film on a gas-liquid interface:
b) Hydrophilizing the metal micro-grid-graphene-porous membrane composite structure, and dripping a solution containing a target sample on the surface of the metal micro-grid-graphene-porous membrane composite structure to form a uniform liquid film;
c) And transferring the self-supported graphene film on the gas-liquid interface to the surface of the porous film in the step b) to obtain the graphene-porous film-graphene sandwich liquid pool structure.
In the preparation method, in the step a), the number of layers of the graphene film is a single layer or multiple layers (2-5 layers);
The self-supporting graphene film on the gas-liquid interface is prepared by a method described in application number 202210107288.7 (the name of the invention is a controllable preparation and transfer method of a self-supporting two-dimensional material).
The method specifically comprises the following steps: 1) Growing a graphene film on a metal substrate, retaining the graphene film on one surface of the metal substrate, and uniformly dripping a surfactant solution on the graphene film until the graphene film is completely infiltrated:
2) After the solvent volatilizes, the surfactant molecules form a self-assembled structure on the surface of the graphene film, and then a metal substrate with the graphene film on the surface floats on etching liquid to remove the metal substrate: and after the metal substrate is completely etched, obtaining the self-supporting graphene film on the gas-liquid interface.
In the step b), the hydrophilization treatment is plasma etching or ultraviolet ozone oxidation; specifically, oxygen plasma etching can be adopted, and the flow rate of oxygen gas is 1-5 sccm; the power is 10-100W; the time is 6-60 s; more specifically, the oxygen gas flow rate was 1sccm, the power was 30W, and the time was 18s.
In the step c), the transfer method of the self-supporting graphene film on the gas-liquid interface is a direct fishing method or a liquid film transfer method.
In the preparation method, the direct fishing method is to insert the metal micro-grid-graphene-porous membrane composite structure with solution into the liquid where the self-supporting graphene is located at a certain inclination angle, and drag the graphene to the surface of the porous membrane from bottom to top;
specifically, the certain inclination angle can be 30-60 degrees; specifically, the angle of the light beam can be 45 degrees;
The liquid film transfer method is to drag out the self-supporting graphene film on the gas-liquid interface by using a circular ring, and then drop the self-supporting graphene film on the surface of the porous film with the metal micro-grid-graphene-porous film composite structure of the solution from top to bottom.
The diameter of the circular ring is 4-50 mm, and the material is iron, copper, stainless steel or rubber.
In the step c), the self-supporting graphene film on the gas-liquid interface is transferred to the surface of the porous film in the step b), and then the steps of drying and washing are carried out;
specifically, the washing step sequentially adopts isopropanol and water for washing;
The washing time of the isopropanol is 15-100 s; specifically, 30s;
the water washing time is 15-100 s; specifically, 30s;
and the drying is natural airing.
The invention also provides a graphene-porous membrane-graphene sandwich liquid pool structure prepared by the preparation method.
The graphene-porous membrane-graphene sandwich liquid pool structure is characterized in that liquid is encapsulated in cylindrical holes of a porous membrane, and the upper surface and the lower surface are respectively encapsulated by graphene.
Finally, the application of the graphene-porous membrane-graphene sandwich liquid pool structure in-situ liquid-phase electron microscopy imaging or low-temperature freezing electron microscopy imaging also belongs to the protection scope of the invention.
In the present invention, the room temperature is well known to those skilled in the art, and is generally 15 to 35 ℃.
According to the method, a graphene-porous membrane composite structure is obtained after a porous membrane with controllable thickness and size is attached to graphene, and then the graphene-porous membrane composite structure is transferred to a metal micro-grid to obtain a graphene carrier net with a sandwich structure of the porous membrane-graphene-metal micro-grid; and transferring a self-supporting suspended graphene on the graphene carrying net to form a sandwich liquid pool structure of 'graphene-porous membrane-graphene', wherein liquid-phase electron microscopy imaging or freezing electron microscopy imaging can be performed.
The invention has the following advantages:
(1) The array porous membrane constructed by the invention has controllable aperture, thickness and material quality, and is suitable for loading different samples;
(2) The invention utilizes the small molecular self-assembly structure to assist in preparing large-area self-supporting suspended graphene (patent application number 202210107288.7) on a gas-liquid interface, the graphene is kept complete, the washing process is simple and rapid, and the problems of residual glue pollution, damage and the like caused by the traditional high molecular assisted method are avoided;
(3) According to the graphene-porous membrane-graphene sandwich liquid pool structure constructed by the invention, the volume and the thickness of a liquid pool can be controlled in-situ liquid phase electron microscope imaging, so that the high-efficiency automatic acquisition of data is facilitated; in the imaging of the freezing electron microscope, the ice layer with uniform and controllable thickness can be prepared, the damage of electron beam irradiation to a sample is reduced, and the method has important application prospect in the field of high-resolution imaging of the freezing electron microscope;
(4) The graphene-porous membrane-graphene sandwich liquid pool structure constructed by the invention can effectively load samples such as metal nano particles, biological macromolecules and the like.
Drawings
FIG. 1 is a schematic cross-sectional view of a preparation flow process of a graphene-porous membrane-graphene sandwich liquid pool structure of the invention;
fig. 2 is a schematic diagram of two methods for constructing a graphene-porous membrane-graphene sandwich liquid pool structure, wherein a in fig. 2 is a direct fishing method, and B is a liquid film transfer method;
FIG. 3 is a graph showing morphology characterization and pore depth statistics of a metal micro-grid-graphene-porous gold film composite structure; a, B in fig. 3 is a scanning electron microscope image of a gold micro-grid-graphene-porous gold film composite structure of a 50nm thick porous gold film; atomic force microscope images and pore depth statistics of a gold micro-grid-graphene-porous gold film composite structure of which the thickness is 50nm are carried out on C; D. e is a scanning electron microscope image of a gold micro-grid-graphene-porous gold film composite structure of a porous gold film with the thickness of 80 nm; f is an atomic force microscope image and pore depth statistics of a gold micro grid-graphene-porous gold film composite structure of a porous gold film with the thickness of 80 nm;
FIG. 4 is a scanning electron microscope image (A-B) of a graphene-porous membrane-graphene sandwich cell structure constructed using an 80nm thick porous gold membrane and cell surface typical morphology and cell thickness statistics (C-D) measured using an atomic force microscope;
FIG. 5 is a transmission electron microscope characterization result of a graphene-porous membrane-graphene sandwich liquid pool structure; A-C in FIG. 5 is an electron microscope image of the encapsulated pure water; D-F in FIG. 5 is an electron microscope image of encapsulated Au@Ce 2 nanoparticles;
Fig. 6 is an imaging result of encapsulating an aqueous solution for frozen transmission electron microscopy using a graphene-porous membrane-graphene sandwich liquid pool structure.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
The experimental methods in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Fig. 1 is a schematic process section of a preparation flow of a graphene-porous membrane-graphene sandwich liquid pool structure, and specifically includes steps of evaporation of a sacrificial layer and a porous membrane, membrane bleaching, graphene membrane scooping, etching, gold micro-grid membrane scooping, graphene transferring, drying/washing and the like.
Example 1 graphene-porous Membrane-graphene Sandwich liquid pool Structure for in situ liquid-phase Electron microscopy imaging
1) Preparation of a porous gold film: a large-area round hole array silicon template (the aperture of a single round hole is 1.2 mu m, the depth of a round hole groove is 0.5-5 mu m) is sequentially coated with a 30nm thick water-soluble sacrificial layer sodium metaphosphate and a 50nm or 80nm thick porous gold film by using a thermal evaporation vacuum coating instrument, the vacuum degree is 5 multiplied by 10 -4 Pa, and the coating speed is 5 multiplied by 80nmThen, clamping one corner of the template, slowly immersing the template in water at an inclination angle of 45 degrees, quickly dissolving sodium metaphosphate after immersing in water, separating the porous gold membrane from the template at a separation speed of 0.1cm/s, and completely floating the porous membrane on the water surface after the template is completely immersed.
2) Preparation of a porous gold film-graphene composite structure: taking a single-layer graphene with the area similar to that of a gold film, and growing the single-layer graphene on a copper foil by a chemical vapor deposition method, firstly removing the graphene on one surface of the copper foil by using air plasma, wherein the gas flow is 10sccm, the power is 150W, and the time is 2min; and carrying out hydrophilization treatment on the graphene on the other surface of the copper foil by using oxygen plasma etching, wherein the gas flow is 1sccm, the power is 30W, and the time is 18s. And then, sticking the copper foil/graphene on a glass slide with the front side facing upwards, immersing the glass slide in water, fishing out the porous gold film from bottom to top, and naturally drying for 1 day to obtain the porous gold film-graphene-copper foil composite structure.
3) Preparing a porous gold film-graphene composite film on a gas-liquid interface: placing the porous gold film-graphene-copper foil composite structure obtained in the step 2) on the surface of (NH 4)2S2O8 solution with the concentration of 0.5M for etching, and obtaining the porous gold film-graphene composite film after the copper foil is completely etched; and transferring the porous gold film-graphene composite film from the surface of etching liquid to the surface of deionized water by using a stainless steel bailer net for cleaning, and transferring for 2 times, wherein each time is 10 minutes.
4) Preparation of a gold micro-grid-graphene-porous gold film composite structure: gold micro-grids with 300 meshes are selected, the gold micro-grids are fixed on a flat substrate in batches, the total area of the gold micro-grids is similar to that of a porous gold film-graphene composite film, the gold micro-grids are immersed in water, the porous gold film-graphene composite film is fished out from bottom to top, and then natural drying is carried out for 1 day, so that a gold micro-grid-graphene-porous gold film composite structure is obtained.
5) Preparation of self-supporting graphene on a gas-liquid interface: taking a small layer (3-5 layers) of graphene grown on a copper foil by a chemical vapor deposition method, firstly removing the graphene on one side of the copper foil by using air plasma, wherein the gas flow is 10sccm, the power is 150W, and the time is 2min; dripping stearic acid/isopropanol solution with mass concentration of two parts per million on the surface of the few-layer graphene on the other side of the copper foil, and completely covering the surface; and then etching the copper foil by using a solution (NH 4)2S2O8) with the concentration of 0.5M to obtain self-supporting graphene on a gas-liquid interface, and then transferring the graphene from etching solution to the surface of deionized water by using a stainless steel bailer to wash for 10min.
6) Preparation of a graphene-porous membrane-graphene sandwich liquid pool structure: performing hydrophilization treatment on the gold micro-grid-graphene-porous gold film composite structure by using oxygen plasma etching, wherein the gas flow is 1sccm, the power is 30W, the time is 18s, 2 mu L of water or Au@CeO 2 nano particle solution is dropwise added on the porous gold film, and filter paper is used for carefully absorbing redundant liquid to form a layer of uniform liquid film on the surface of the porous gold film; the self-supporting graphene is covered on the surface of the liquid film by adopting a direct fishing method or a liquid film transfer method as described below, and a sandwich liquid pool structure of graphene-porous film-graphene is constructed.
The 'direct fishing method' in the step 6) is as follows: the gold micro grid-graphene-porous gold film loaded with liquid is clamped by self-locking tweezers, the graphene is obliquely inserted into the liquid where the self-supporting graphene is located at an inclination angle of 45 degrees, the graphene is fished up to the surface of the porous gold film from bottom to top, and naturally dried, and isopropanol and water are respectively washed for 30s, so that a gold micro grid-graphene-porous gold film-graphene composite structure, namely a graphene-porous film-graphene sandwich liquid pool structure is obtained.
The "liquid film transfer method" in step 6) is: transferring a gold micro-grid-graphene-porous gold film composite structure loaded with liquid to a PDMS surface with similar area, then fishing out the graphene on the liquid surface by using an iron ring with the diameter of 5mm, and forming a liquid film along the iron ring by the liquid under the action of self surface tension, wherein the graphene floats on the surface of the liquid film; enabling the graphene on the liquid film to pass through a gold micro grid-graphene-porous gold film from top to bottom, so that the graphene falls on the porous gold film, and obtaining a gold micro grid-graphene-porous gold film-graphene composite structure; and finally, taking the composite structure off the PDMS, naturally drying, and washing with isopropanol and water respectively for 30s to obtain the graphene-porous membrane-graphene sandwich liquid pool structure.
The schematic diagrams of the direct fishing method and the liquid film transfer method are shown in figure 2.
FIG. 3 shows the morphology characterization and pore depth statistics of the gold micro-grid-graphene-porous gold film composite structure prepared in the step 4), wherein A, B is a scanning electron microscope image of the gold micro-grid-graphene-porous gold film composite structure of a porous gold film with a thickness of 50nm in FIG. 3, and C is an atomic force microscope image and pore depth statistics of the gold micro-grid-graphene-porous gold film composite structure of a porous gold film with a thickness of 50 nm; d, E in fig. 3 is a scanning electron microscope image of a "gold micro gate-graphene-porous gold film" composite structure of an 80nm thick porous gold film, and F is an atomic force microscope image and pore depth statistics of a "gold micro gate-graphene-porous gold film" composite structure of an 80nm thick porous gold film;
As can be seen from FIG. 3, the composite structure of the gold micro-grid-graphene-porous gold film has high integrity, smoother surface and more uniform structure depth and is equivalent to the thickness of the metal porous film, which indicates that the yield of the composite structure of the gold micro-grid-graphene-porous gold film prepared by the method is high.
FIG. 4 is a scanning electron microscope image of a "gold micro-grid-graphene-porous membrane-graphene" sandwich pool liquid structure (encapsulated liquid is water) constructed using an 80nm thick porous gold membrane and pool surface typical morphology and pool thickness statistics measured using an atomic force microscope; as can be seen from fig. 4, the upper graphene layer completely covers the surface of the carrier mesh, the liquid pool is uniformly distributed in most porous structures, and the thickness of the liquid pool is mostly 40-60nm.
FIG. 5 is a transmission electron microscope characterization result of a graphene-porous membrane-graphene sandwich liquid pool structure; a, B and C in fig. 5 are electron microscopic images of encapsulated pure water, and it can be seen that bubbles generated due to electron beam irradiation are remarkable; d, E, F in fig. 5 is an electron microscope image of encapsulated au@ceo 2 nanoparticles.
Example 2 graphene-porous Membrane-graphene Sandwich liquid pool Structure for frozen Transmission Electron microscopy imaging
The sandwich liquid pool structure (packed pure water) of "graphene-porous membrane-graphene" prepared by the same method as in example 1 was rapidly inserted into liquid nitrogen for rapid freezing, and frozen samples were stored in liquid nitrogen, followed by characterization by a cryoelectron microscope.
FIG. 6 shows imaging results and ice layer thickness measurement using a graphene-porous membrane-graphene sandwich pool structure with porous gold film thicknesses of 50nm and 80nm, respectively, for a cryoelectron microscope. A-C in FIG. 6 is a frozen transmission electron microscope characterization result of the encapsulated amorphous ice, and D in FIG. 6 is a selected area electron diffraction characterization result of the upper and lower layers of graphene.
Claims (9)
1. A preparation method of a graphene-porous membrane-graphene sandwich liquid pool structure comprises the following steps:
a) Preparing a self-supporting graphene film on a gas-liquid interface:
b) Hydrophilizing a metal micro-grid-graphene-porous membrane composite structure, and dripping a solution containing a target sample on the surface of the metal micro-grid-graphene-porous membrane composite structure to form a uniform liquid film;
c) Transferring the self-supported graphene film on the gas-liquid interface to the surface of the porous film in the step b) to obtain the graphene-porous film-graphene sandwich liquid pool structure;
The preparation method of the metal micro-grid-graphene-porous membrane composite structure comprises the following steps:
(1) Preparing a porous membrane floating on the water surface;
(2) Immersing the graphene on the metal substrate in water with the front side facing upwards, and fishing out the porous membrane from bottom to top to obtain a porous membrane-graphene-metal substrate composite structure;
(3) Wet etching the metal substrate in the porous membrane-graphene-metal substrate composite structure to obtain a self-supporting porous membrane-graphene composite membrane on the liquid surface;
(4) Immersing a substrate fixed with a batch of metal micro-grids in liquid where the porous membrane-graphene composite membrane is located, and fishing out the porous membrane-graphene composite membrane from bottom to top to obtain the metal micro-grid-graphene-porous membrane composite structure;
Or placing the substrate fixed with the batched metal micro-grids under the porous membrane-graphene composite membrane, and slowly pumping out water to enable the porous membrane-graphene composite membrane to be slowly deposited on the metal micro-grids, so as to obtain the metal micro-grid-graphene-porous membrane composite structure.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the thickness of the porous film is 10-100 nm;
the porous film is a gold film or a carbon film;
In the step (2), the metal substrate is copper foil, a copper wafer or copper-nickel alloy;
The number of layers of the graphene is a single layer or a plurality of layers;
in the step (2), hydrophilizing treatment is performed on the graphene on the metal substrate.
3. The preparation method according to claim 1 or 2, characterized in that: in the step (4), the metal micro-grid is made of gold, copper, nickel, molybdenum or nonmetallic material silicon nitride;
the metal micro-grid is 200-400 meshes.
4. The preparation method according to claim 1 or 2, characterized in that: in the step (3), washing the porous membrane-graphene composite membrane after etching the metal substrate;
the washing mode is that the porous membrane-graphene composite membrane is fished up and transferred to a deionized water surface for floating washing by a glass slide or a stainless steel net;
And transferring for 2-3 times in the washing step, wherein the washing time is 10-20 minutes each time.
5. The method of manufacturing according to claim 1, characterized in that: in the step a), the number of layers of the graphene film is a single layer or multiple layers;
in the step b), the hydrophilization treatment is plasma etching or ultraviolet ozone oxidation;
In the step c), the self-supporting graphene film transfer method on the gas-liquid interface is a direct fishing method or a liquid film transfer method.
6. The method of manufacturing according to claim 5, wherein: the direct fishing method is to insert the metal micro-grid-graphene-porous membrane composite structure with solution into the liquid where the self-supporting graphene is located at a certain inclination angle, and drag the graphene to the surface of the porous membrane from bottom to top;
The liquid film transfer method is to drag out the self-supporting graphene film on the gas-liquid interface by using a circular ring, and then drop the self-supporting graphene film on the surface of the porous film with the metal micro-grid-graphene-porous film composite structure of the solution from top to bottom.
7. The method of manufacturing according to claim 6, wherein: the certain inclination angle is 30-60 degrees.
8. The graphene-porous membrane-graphene sandwich liquid pool structure prepared by the preparation method of any one of claims 1-7.
9. The application of the graphene-porous membrane-graphene sandwich liquid pool structure in-situ liquid-phase electron microscopy imaging or low-temperature cryoelectron microscopy imaging as claimed in claim 8.
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