CN111013503B - Liquid metal aerogel, preparation method and application thereof - Google Patents
Liquid metal aerogel, preparation method and application thereof Download PDFInfo
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- CN111013503B CN111013503B CN201911293760.5A CN201911293760A CN111013503B CN 111013503 B CN111013503 B CN 111013503B CN 201911293760 A CN201911293760 A CN 201911293760A CN 111013503 B CN111013503 B CN 111013503B
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- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
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- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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Abstract
The invention discloses a liquid metal aerogel, a preparation method and application thereof. The liquid metal aerogel has a continuous three-dimensional porous network structure, the continuous three-dimensional porous network structure is formed by mutually overlapping liquid metal nanoparticles and graphene sheets, and at least part of the liquid metal nanoparticles are wrapped by the graphene sheets. The preparation method comprises the following steps: dispersing liquid metal in a polysaccharide aqueous solution to form liquid metal nanoparticles, and wrapping the liquid metal nanoparticles with polysaccharide to obtain stable dispersion liquid; and then uniformly mixing the metal hydroxide colloid and the gluconic acid lactone, adding the metal hydroxide colloid and the gluconic acid lactone to carry out ionic crosslinking, standing to obtain liquid metal hydrogel, and then carrying out reduction, solvent replacement treatment and drying treatment to obtain the liquid metal aerogel. The liquid metal aerogel disclosed by the invention is high in specific surface area, low in density, high in heat conductivity, hydrophilic and chemically stable, simple in preparation process, mild and controllable in reaction conditions and wide in application prospect.
Description
Technical Field
The invention relates to a liquid metal aerogel, in particular to a liquid metal aerogel, a preparation method and application thereof, and belongs to the technical field of nano materials.
Background
Liquid metal is a metal that can be in a liquid state at room temperature, and has been drawing attention in recent years because of its metal characteristics and liquid fluidity. Because the liquid metal has excellent properties such as low melting point, high electrical conductivity, high thermal conductivity and the like, the liquid metal has wide application prospects in the fields of 3D printing, flexible electronic devices, molecular machines, thermal management, medicine carriers and the like. To date, the direct application of liquid metals faces two significant challenges: on the one hand, liquid metals generally have a large surface tension, are difficult to disperse and serve as a filler material. Although researchers have used electric field, ultrasound, pneumatic dispersion, microfluidics, and other methods to disperse liquid metals into micro-droplets to facilitate further manipulation, the stabilization of droplets remains a significant challenge. Meanwhile, high surface tension causes serious interface problems when liquid metal is compounded with other materials, and leakage is easy to occur. On the other hand, liquid metals lack precursors and are difficult to chemically synthesize into self-supporting macroscopic bulk materials. The Liu lacing group of the university of qinghua proposes to mix other metal nanoparticles and a certain amount of acid in liquid metal, and to form a liquid metal porous material (mater. horiz.,2018,5, 222-229) by pore-forming through forming a galvanic cell to generate gas, but the obtained porous liquid metal is re-melted at a higher temperature, and the pore structure disappears and is unstable. Although liquid metals have been studied more recently, the above two drawbacks still limit their application.
In view of the need for a liquid metal macroscopic body material that is self-supporting and stable in properties, the advantages of liquid metals are fully exerted, and the defects of the liquid metals are urgently needed to be overcome. The aerogel is used as a highly porous nano material and is assembled by specific nano units, so that the aerogel can show the characteristics of the nano structural units, the high specific surface area and the high porosity of the aerogel, and has wide application prospects in the fields of energy storage and conversion, catalysis, sensing and the like. Based on this, the liquid metal and the aerogel structure are organically combined, and the application of the aerogel structure assembled by the liquid metal nano structure can be greatly expanded, so that the liquid metal aerogel material with uniform and stable structure and the preparation method thereof are urgently needed to achieve the purposes of simple process, short period and low cost.
Disclosure of Invention
The invention mainly aims to provide a liquid metal aerogel and a preparation method thereof, so as to overcome the defects in the prior art.
It is also an object of the present invention to provide the use of the liquid metallic aerogel.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a liquid metal aerogel, which has a continuous three-dimensional porous network structure, wherein the continuous three-dimensional porous network structure is formed by mutually overlapping liquid metal nanoparticles and graphene sheets, and at least part of the liquid metal nanoparticles are wrapped by the graphene sheets.
The embodiment of the invention also provides a preparation method of the liquid metal aerogel, which comprises the following steps:
(1) dispersing liquid metal in a polysaccharide aqueous solution to form liquid metal nanoparticles, and wrapping the liquid metal nanoparticles with polysaccharide to obtain a stable dispersion liquid;
(2) uniformly mixing the dispersion liquid of the liquid metal nanoparticles obtained in the step (1) with graphene oxide, sequentially adding metal hydroxide colloid and gluconolactone for ionic crosslinking, and standing to obtain liquid metal hydrogel;
(3) reducing graphene oxide in the liquid metal hydrogel by using a reducing agent;
(4) and (4) carrying out solvent replacement and drying treatment on the liquid metal hydrogel obtained in the step (3) to obtain the liquid metal aerogel.
The embodiment of the invention also provides the liquid metal aerogel prepared by the method.
The embodiment of the invention also provides application of the liquid metal aerogel in the fields of heat preservation and insulation, catalysis, batteries, supercapacitors, adsorption and sensing or light-hot water evaporation and the like.
Compared with the prior art, the invention has the advantages that:
1) the liquid metal aerogel provided by the invention mainly comprises liquid metal nano particles and graphene nanosheets, the assembly of a liquid metal nano structure unit is realized for the first time, and the liquid metal aerogel is uniform in structure, has the characteristics of aerogel and liquid metal, and has low density, high specific surface area, high thermal conductivity, good hydrophilicity and chemical stability;
2) in the preparation process, the liquid metal is firstly subjected to ultrasonic dispersion by using the polysaccharide, and the polysaccharide can be used as a surfactant to be beneficial to stable dispersion of liquid metal nanoparticles in a solution. The polysaccharide contains more hydroxyl groups and can form hydrogen bond action with the graphene oxide lamella, so that the liquid metal nano-particles coated by the polysaccharide can be well combined with the graphene oxide lamella; in the presence of gluconolactone, the metal hydroxide releases metal ions to rapidly crosslink the graphene oxide sheet layer, so that a gel structure with a uniform structure is formed;
3) the liquid metal aerogel provided by the invention has the advantages of simple preparation process, mild and controllable reaction conditions, low energy consumption, greenness, no pollution, suitability for large-scale production and wide application prospect;
4) the liquid metal aerogel provided by the invention has high specific surface area and good conductivity, and can be applied to the fields of catalysis, batteries, supercapacitors, sensing and the like. Meanwhile, the characteristics of high specific surface area, porosity and the like can be used in the field of adsorption. In addition, the graphene sheet layer has strong sunlight absorption characteristics and excellent photo-thermal conversion performance, and the aerogel structure has a heat preservation effect and can effectively reduce the heat energy from diffusing to the outside. The liquid metal aerogel has certain hydrophilicity because of the existence of polysaccharide, can pump water through the pore structure, and can transfer heat to water locally because the liquid metal nanoparticles have higher thermal conductivity, so that higher light hot water evaporation rate is brought, and the liquid metal aerogel has wide application prospect in the field of light hot water evaporation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1a and 1b are TEM images and SEM images of gallium aerogel of gallium nanoparticles obtained in example 1 of the present invention.
FIG. 2 is a graph showing the distribution of the particle size of indium nanoparticles in the gallium aerogel obtained in example 2 of the present invention.
Fig. 3 is an SEM image of rubidium aerogel obtained in example 3 of the present invention.
FIG. 4 is an SEM image of the gallium-indium alloy aerogel obtained in example 4 of the present invention.
Fig. 5a and 5b are STEM images and SEM images of cesium aerogel of cesium nanoparticles obtained in example 5 of the present invention.
FIG. 6 is a DSC of gallium aerogel obtained in example 6 of the present invention.
FIG. 7 is a photograph showing the contact angle of the surface of the gallium aerogel obtained in example 7 of the present invention with water.
FIG. 8 is a light absorption spectrum of a gallium aerogel obtained in example 8 of the present invention.
FIG. 9 is a photo-thermal infrared photograph of a gallium aerogel obtained in example 9 of the present invention.
FIG. 10 is a photo-thermal infrared photograph of a gallium aerogel obtained in example 10 of the present invention.
FIG. 11 is a photograph showing the contact angle of the surface of the gallium aerogel obtained in comparative example 1 of the present invention with water.
FIG. 12 is a transmission electron micrograph of a gallium aerogel obtained in comparative example 2 of the present invention.
FIG. 13 is a photograph showing the contact angle of the surface of the gallium aerogel obtained in comparative example 3 of the present invention with water.
Detailed Description
In view of the defects in the prior art, the inventors of the present invention have made extensive studies and practice to provide a technical solution of the present invention, which prepares a self-supporting liquid metal aerogel through a strategy of self-assembly of a liquid metal nanostructure unit and a graphene nanosheet layer. The technical solution, its implementation and principles, etc. will be further explained as follows.
An aspect of an embodiment of the present invention provides a liquid metal aerogel, which has a continuous three-dimensional porous network structure, and the continuous three-dimensional porous network structure is formed by overlapping liquid metal nanoparticles and graphene sheets, wherein at least a portion of the liquid metal nanoparticles are wrapped by the graphene sheets. The liquid metal nanoparticles are wrapped by graphene nanosheets and are closely lapped together.
Further, the liquid metal nanoparticles are wrapped by polysaccharide molecules and can be tightly combined with graphene sheet layers through hydrogen bonding, so that a continuous three-dimensional porous network structure is formed.
Further, the liquid metal nanoparticles are tightly combined with the graphene sheet layer through the polysaccharide coated on the surface of the liquid metal nanoparticles.
In some embodiments, the material of the liquid metal nanoparticles includes any one or a combination of two or more of gallium, indium, rubidium, cesium, and the like, but is not limited thereto.
In some embodiments, the liquid metal nanoparticles have a particle size of 0.01 μm to 2 μm, preferably 0.05 μm to 1 μm, and more preferably 0.075 μm to 0.75 μm.
Further, the liquid metal aerogel comprises micropores, mesopores and macropores, wherein the pore diameter of the micropores is 0.5-2 nm, the pore diameter of the mesopores is 2-50 nm, and the pore diameter of the macropores is 50 nm-500 microns.
Further, the three-dimensional porous network structure is composed of micropores with the aperture of 0.5-2 nm, mesopores with the aperture of 2-50 nm and macro pores with the aperture of 50 nm-500 mu m.
Further, the specific surface area of the liquid metal aerogel is 10-1000 m2Preferably 100 to 500 m/g2/g。
Further, the density of the liquid metal aerogel is 25-200 mg/cm3Preferably 45 to 150mg/cm3。
Further, the thermal conductivity of the liquid metal aerogel is 0.10-0.80W/m-1 .k-1Preferably 0.20 to 0.60W/m-1 .k-1。
Further, the pore volume of the liquid metal aerogel is 0.2-3.2 cm3Preferably 0.5 to 2.5 cm/g3A more preferable range is 0.7 to 2.0 cm/g3/g。
Further, the liquid metal aerogel has a porosity of 1-99%.
Further, the static contact angle of the surface of the liquid metal aerogel and water is 30-130 degrees, and preferably 50-90 degrees.
In some embodiments, the liquid metal aerogel comprises 10 to 90wt% liquid metal nanoparticles and 90 to 10wt% graphene sheets.
Another aspect of the embodiments of the present invention also provides a method for preparing a liquid metal aerogel, including the following steps:
(1) dispersing liquid metal in a polysaccharide aqueous solution to form liquid metal nanoparticles, and wrapping the liquid metal nanoparticles with polysaccharide to obtain a stable dispersion liquid;
(2) uniformly mixing the dispersion liquid of the liquid metal nanoparticles obtained in the step (1) with graphene oxide, sequentially adding metal hydroxide colloid and gluconolactone for ionic crosslinking, and standing to obtain liquid metal hydrogel;
(3) reducing graphene oxide in the liquid metal hydrogel by using a reducing agent;
(4) and (4) carrying out solvent replacement and drying treatment on the liquid metal hydrogel obtained in the step (3) to obtain the liquid metal aerogel.
In some more specific embodiments, the preparation method specifically comprises:
(1) ultrasonically dispersing liquid metal into a natural polysaccharide aqueous solution, dispersing liquid metal nano particles under the action of ultrasonic, and coating the outer layer with polysaccharide to avoid agglomeration and precipitation to form liquid metal nano particles which can be stably dispersed in the solution;
(2) mixing the liquid metal nanoparticles with a graphene oxide solution, stably dispersing the liquid metal nanoparticles in the graphene oxide solution, sequentially adding a metal hydroxide colloid and gluconolactone for ionic crosslinking, and standing to obtain a liquid metal hydrogel;
(3) dipping the liquid metal hydrogel into a reducing agent aqueous solution to reduce graphene oxide in the liquid metal hydrogel;
(4) and (3) carrying out solvent replacement treatment on the liquid metal hydrogel by using an organic solvent such as water or ethanol, and then carrying out drying treatment to obtain the liquid metal aerogel.
In some embodiments, in step (1), a polysaccharide aqueous solution with a certain concentration is prepared, the liquid metal is dispersed into liquid metal nanoparticles under the action of ultrasonic waves with a certain power, and polysaccharide molecules wrap the outer layer of the liquid metal nanoparticles to maintain the stability of the liquid metal nanoparticles.
Further, the liquid metal includes any one or a combination of two or more of gallium, indium, rubidium, cesium, and the like, but is not limited thereto.
Further, the polysaccharide includes any one or a combination of two or more of polysaccharides such as sodium alginate, chitin, chitosan, glycosaminoglycan polysaccharides, cellulose polysaccharides, pectin polysaccharides, and the like, but is not limited thereto.
Further, the polysaccharide content in the polysaccharide aqueous solution is 0.01-1 wt%, preferably 0.05-0.3 wt%.
Further, the ultrasonic power is 200-800W, preferably 400-600W.
Further, the content of the liquid metal in the polysaccharide aqueous solution is 1-100 mg/mL, preferably 5-50 mg/mL.
Further, the thickness of the polysaccharide wrapped outside the liquid metal nanoparticles is 5-30 nm, and preferably 8-20 nm.
In some embodiments, the concentration of the graphene oxide aqueous solution in the step (2) is 2 to 20mg/mL, preferably 5 to 15 mg/mL.
Further, the metal hydroxide colloid includes any one or a combination of two or more of lanthanum hydroxide, iron hydroxide, aluminum hydroxide, magnesium hydroxide, chromium hydroxide, copper hydroxide, barium hydroxide, calcium hydroxide, and the like, but is not limited thereto.
Further, the molar ratio of the metal hydroxide colloid to the gluconolactone is 1:20 to 10:1, preferably 1:10 to 5: 1.
Further, the standing time is 8-48 h, preferably 12-36 h, and further preferably 18-24 h.
In some embodiments, step (3)) The reducing agent is selected from HI, ascorbic acid, sodium ascorbate, hydrazine hydrate, ethylenediamine, Fe-containing2+Any one or a combination of two or more of the compounds and dopamine, etc., but not limited thereto.
Further, the mass ratio of the reducing agent to the graphene oxide is 3: 1-50: 1, and preferably 5: 1-15: 1.
Further, the temperature of the reduction treatment is room temperature to 180 ℃, preferably 40 to 120 ℃, and the time of the reduction treatment is 2 to 72 hours, preferably 12 to 48 hours.
In some embodiments, in the step (4), the volume of the water and the organic solvent used for solvent replacement is 5 to 100 times, preferably 20 to 60 times that of the liquid metal hydrogel.
Furthermore, the number of times of the solvent replacement treatment is 3-10, and the time of each replacement is 3-24 h, preferably 5-18 h.
Further, the organic solvent includes any one or a combination of two or more of t-butyl alcohol, ethanol, n-hexane, acetone, and the like, but is not limited thereto.
In some embodiments, the drying process comprises supercritical fluid CO2Any one or a combination of two or more of drying, drying under atmospheric pressure, freeze-drying and the like, but the present invention is not limited thereto.
Further, the temperature of the freeze drying sample chamber is 0-50 ℃.
Further, the drying time is 6-48 h, preferably 12-24 h.
Further, the liquid metal aerogel substituted with water or t-butanol is subjected to a freeze-drying method, and the liquid metal aerogel substituted with a solvent using any one or a combination of two or more of ethanol, n-hexane, and acetone is subjected to a supercritical drying method.
Another aspect of an embodiment of the present invention also provides a liquid metal aerogel prepared by the aforementioned method.
In another aspect, the embodiment of the present invention further provides an application of any one of the aforementioned liquid metal aerogels in the fields of thermal insulation, catalysis, batteries, supercapacitors, adsorption, sensing, or photo-thermal water evaporation.
Further, the application of the liquid metal aerogel in the field of photo-thermal water evaporation: the graphene sheet layer in the liquid metal aerogel has strong sunlight absorption characteristics and excellent photo-thermal conversion performance, can be converted into heat by absorbing solar energy, and meanwhile, the aerogel structure has a heat preservation effect and can effectively reduce the diffusion of heat energy to the outside.
Furthermore, the liquid metal aerogel has certain hydrophilicity because of the existence of polysaccharide, can pump water through the pore structure, and because the liquid metal nanoparticles have higher thermal conductivity, the liquid metal with high thermal conductivity can locally transfer heat to a small amount of water, carry out intensive local heating, generate steam, and the hydrophilicity is favorable for the water to be pumped to the pore structure in time.
By the technical scheme, the liquid metal aerogel provided by the invention mainly comprises liquid metal nano particles and graphene nanosheets, the assembly of the liquid metal nano structure unit is realized for the first time, and the liquid metal aerogel is uniform in structure, has the characteristics of aerogel and liquid metal, and has low density, high specific surface area, high thermal conductivity, good hydrophilicity and chemical stability.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustration and are not to be construed as limiting the scope of the invention, which may be varied in practice by those skilled in the art.
Example 1
(1) Preparing liquid metal nanoparticles: preparing 0.01 wt% sodium alginate aqueous solution, adding 40mg of liquid metal gallium into 40mL of the sodium alginate aqueous solution, and performing ultrasonic treatment with 400W power to obtain gallium nanoparticle dispersion liquid, wherein the thickness of the sodium alginate coated on the surface of the liquid metal gallium is 5 nm.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.1mol of lanthanum hydroxide colloidal solution, then adding 2mol of gluconolactone, stirring for 30s, and standing for 12h to obtain the liquid metal gallium hydrogel.
(3) And (3) soaking the liquid metal hydrogel into 1.5mol/L ascorbic acid aqueous solution at room temperature for 48h to reduce the graphene oxide.
(4) Replacing the liquid metal gallium hydrogel with ethanol, wherein the volume ratio of ethanol to liquid metal gallium hydrogel is 5:1, the replacement time is 3h each time, and supercritical fluid CO is performed after 4 times of replacement2Drying for 12h to obtain the liquid metal gallium aerogel.
The structural and performance characterization data of the liquid metal gallium aerogel obtained in this example are as follows: the specific surface area of the liquid metallic gallium aerogel tested by BET test is about 305m2In terms of/g, the mean pore diameter is approximately 22.4 nm. Please refer to fig. 1a and 1b, wherein the data is an average value of a plurality of batches of samples after a plurality of tests.
Example 2
(1) Preparing liquid metal nanoparticles: preparing a chitin solution with the mass percentage of 1 wt%, taking 40mL, adding 40mg of liquid metal indium, and performing ultrasonic treatment by adopting 400W power to obtain an indium nanoparticle dispersion liquid, wherein the thickness of sodium alginate coated on the surface of the liquid metal indium is 8 nm.
(2) And (3) mixing 4mL of the indium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 1mol of ferric hydroxide colloidal solution, then adding 0.1mol of gluconolactone, stirring for 30s, and standing for 12h to obtain the liquid metal indium hydrogel.
(3) And (3) soaking the liquid metal indium hydrogel into 3mol/L ascorbic acid aqueous solution at 40 ℃ for 40h to reduce the graphene oxide.
(4) Replacing the liquid indium hydrogel with ethanol at a volume ratio of 8:1, and standing each timeThe time for replacement is 5h, and supercritical fluid CO is performed after 5 times of replacement2And drying for 18h to obtain the liquid metallic indium aerogel.
The structural and performance characterization data of the indium aerogel obtained in this example are as follows: the specific surface area of the indium aerogel measured by BET test is about 366m2The particle size distribution of indium nanoparticles in gallium aerogel with a mean pore diameter of about 15.9nm is shown in fig. 2, and it should be noted that these test data are the average values of multiple batches of samples tested.
Example 3
(1) Preparing liquid metal nanoparticles: preparing 0.05 wt% cellulose aqueous solution, taking 40mL, adding 40mg of liquid metal rubidium, and performing ultrasonic treatment by adopting 400W power to obtain rubidium nanoparticle dispersion liquid, wherein the thickness of sodium alginate wrapping the surface of the liquid metal rubidium is 10 nm.
(2) And (3) mixing 8mL of the rubidium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.1mol of aluminum hydroxide colloidal solution, then adding 1mol of gluconolactone, stirring for 30s, and standing for 36h to obtain the liquid metal rubidium hydrogel.
(3) And (3) soaking the liquid metal rubidium hydrogel into 0.5mol/L hydrazine hydrate aqueous solution for 72 hours at 50 ℃ to reduce the graphene oxide.
(4) Replacing the liquid metal rubidium hydrogel with ethanol, wherein the volume ratio of ethanol to liquid metal rubidium hydrogel is 10:1, the replacement time is 18h, and supercritical fluid CO is performed after 6 times of replacement2And drying for 24h to obtain the liquid metal rubidium aerogel.
The structure and performance characterization data of the rubidium aerogel obtained in the example are as follows: the specific surface area of the rubidium aerogel tested by BET test is about 114m2The microstructure of the sample with a pore diameter of about 14 nm/g is shown in FIG. 3, and it should be noted that the test data is the average value of a plurality of batches of samples after a plurality of tests.
Example 4
(1) Preparing liquid metal nanoparticles: preparing 0.1 wt% of pectin aqueous solution, taking 40mL of the pectin aqueous solution, adding 40mg of gallium-indium alloy, and performing ultrasonic treatment with 400W of power to obtain a gallium-indium alloy nanoparticle dispersion solution, wherein the thickness of sodium alginate coated on the surface of liquid metal gallium-indium is 15 nm.
(2) And (3) mixing 4mL of the gallium-indium alloy nanoparticle dispersion liquid with 2mL of 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 1.5mol of magnesium hydroxide colloidal solution, then adding 0.3mol of gluconolactone, stirring for 30s, and standing for 48h to obtain the liquid metal gallium-indium hydrogel.
(3) And (3) soaking the liquid metal gallium indium hydrogel into 1mol/L ethylenediamine aqueous solution at 120 ℃ for 12h to reduce the graphene oxide.
(4) The liquid metal gallium indium hydrogel is replaced by n-hexane, the volume ratio of the n-hexane to the liquid metal gallium indium hydrogel is 20:1, the replacement time is 24 hours each time, and supercritical fluid CO is performed after 10 times of replacement2Drying for 6h to obtain the gallium indium alloy aerogel.
The structural and performance characterization data of the gallium-indium aerogel obtained in this example are as follows: the specific surface area of the gallium indium alloy aerogel tested by BET is about 325m2The microstructure of the sample is shown in FIG. 4, and it should be noted that these test data are the average values of a plurality of batches of samples after a plurality of tests.
Example 5
(1) Preparing liquid metal nanoparticles: preparing 0.05 wt% of glycosaminoglycan aqueous solution, taking 40mL of glycosaminoglycan aqueous solution, adding 100mg of liquid cesium metal, and performing ultrasonic treatment with 600W power to obtain cesium nanoparticle dispersion, wherein the thickness of sodium alginate coated on the surface of the liquid cesium metal is 20 nm.
(2) And (3) mixing 4mL of the cesium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.3mol of copper hydroxide colloidal solution, then adding 0.6mol of gluconolactone, stirring for 30s, and standing for 8h to obtain the liquid cesium metal hydrogel.
(3) And (3) soaking the liquid cesium metal hydrogel into 2mol/L sodium ascorbate aqueous solution at 100 ℃ for 60 hours to reduce the graphene oxide.
(4) Replacing the liquid metal cesium hydrogel with acetone, wherein the volume ratio of the acetone to the liquid metal cesium hydrogel is 100:1, the replacement time is 24 hours each time, and supercritical fluid CO is performed after 8 times of replacement2And drying for 48 hours to obtain the liquid cesium metal aerogel.
The structural and performance characterization data of the cesium aerogel obtained in this example are as follows: the specific surface area of the cesium aerogel, measured by BET, was about 428m2(g), the average pore diameter is about 16.8nm, the scanning transmission electron microscope image of the cesium nanoparticles and the scanning electron microscope image of the cesium aerogel are shown in fig. 5a and 5b, and it should be noted that these test data are the average values of a plurality of batches of samples after a plurality of tests.
Example 6
(1) Preparing liquid metal nanoparticles: preparing 0.1 wt% chitosan aqueous solution, taking 40mL, adding 4000mg of liquid metal gallium, and performing ultrasonic treatment with 300W power to obtain gallium nanoparticle dispersion liquid, wherein the thickness of sodium alginate coated on the surface of the liquid metal gallium is 25 nm.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.3mol of chromium hydroxide colloidal solution, then adding 0.6mol of gluconolactone, stirring for 30s, and standing for 24h to obtain the liquid metal gallium hydrogel.
(3) And (3) soaking the liquid metal gallium hydrogel into 1.5mol/L dopamine aqueous solution at 180 ℃ for 2h to reduce the graphene oxide.
(4) Replacing the liquid metal gallium hydrogel with ethanol, wherein the volume ratio of the ethanol to the liquid metal gallium hydrogel is 60:1, the replacement time is 15h each time, and supercritical fluid CO is performed after 6 times of replacement2Drying for 40h to obtain the liquid metal gallium aerogel.
The structural and performance characterization data of the gallium aerogel obtained in this example are as follows: the specific surface area of the gallium aerogel measured by BET was about 344m2The DSC curve is shown in FIG. 6, and it should be noted that these test data are the average values of a plurality of batches of samples after a plurality of tests.
Example 7
(1) Preparing liquid metal nanoparticles: preparing 0.05 wt% sodium alginate aqueous solution, adding 3000mg liquid metal gallium into 40mL of the sodium alginate aqueous solution, and performing ultrasonic treatment with 400W power to obtain gallium nanoparticle dispersion liquid, wherein the thickness of the sodium alginate coated on the surface of the liquid metal gallium is 30 nm.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.3mol of barium hydroxide colloidal solution, then adding 0.6mol of gluconolactone, stirring for 30s, and standing for 20h to obtain the liquid metal gallium hydrogel.
(3) And (3) soaking the liquid metal gallium hydrogel into a 20% diluted hydriodic acid aqueous solution at room temperature for 72 hours to reduce the graphene oxide.
(4) Replacing the liquid metal gallium hydrogel with ethanol, wherein the volume ratio of the ethanol to the liquid metal gallium hydrogel is 40:1, the replacement time is 16h each time, and supercritical fluid CO is performed after 7 times of replacement2Drying for 48h to obtain the liquid metal gallium aerogel.
The structural and performance characterization data of the gallium aerogel obtained in this example are as follows: the specific surface area of the gallium aerogel tested by BET was about 224m2G, average pore diameter of about 13nm, contact angle with water as measured in FIG. 7, and an average contact angle of 64.6. It should be noted that these test data are the average values of a plurality of batches of samples after a plurality of tests.
Example 8
(1) Preparing liquid metal nanoparticles: preparing 0.1 wt% sodium alginate aqueous solution, adding 2000mg liquid metal gallium into 40mL of the sodium alginate aqueous solution, and performing ultrasonic treatment with 200W power to obtain gallium nanoparticle dispersion liquid, wherein the thickness of the sodium alginate coated on the surface of the liquid metal gallium is 15 nm.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.3mol of calcium hydroxide colloidal solution, then adding 1.2mol of gluconolactone, stirring for 30s, and standing for 24h to obtain the liquid metal gallium hydrogel.
(3) And (3) soaking the liquid metal gallium hydrogel into 1.5mol/L ascorbic acid aqueous solution at 80 ℃ for 48 hours to reduce the graphene oxide.
(4) Replacing the liquid metal gallium hydrogel with ethanol, wherein the volume ratio of ethanol to liquid metal gallium hydrogel is 50:1, the replacement time is 10h each time, and supercritical fluid CO is performed after 4 times of replacement2Drying for 12h to obtain the liquid metal gallium aerogel.
The structural and performance characterization data of the gallium aerogel obtained in this example are as follows: the absorption spectrum is shown in fig. 8, and it should be noted that the test data is the average value of a plurality of batches of samples after a plurality of tests.
Example 9
(1) Preparing liquid metal nanoparticles: preparing 0.1 wt% sodium alginate aqueous solution, adding 400mg liquid metal gallium into 40mL of the sodium alginate aqueous solution, and performing ultrasonic treatment with 800W power to obtain gallium nanoparticle dispersion liquid, wherein the thickness of the sodium alginate coated on the surface of the liquid metal gallium is 10 nm.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.3mol of lanthanum hydroxide colloidal solution, then adding 0.6mol of gluconolactone, stirring for 30s, and standing for 20h to obtain the liquid metal gallium hydrogel.
(3) And (3) soaking the liquid metal gallium hydrogel into 1.5mol/L ascorbic acid aqueous solution at 150 ℃ for 48h to reduce the graphene oxide.
(4) And (2) replacing the liquid metal gallium hydrogel by using tert-butyl alcohol, wherein the volume ratio of the tert-butyl alcohol to the liquid metal gallium hydrogel is 5:1, the replacement time is 3h each time, and after 4 times of replacement, freeze drying is carried out at the temperature of 0 ℃, and drying is carried out for 24h, so as to obtain the liquid metal gallium aerogel.
An infrared photograph of the film under sunlight intensity is shown in fig. 9, and the film is heated by light to a temperature of 68.1 ℃. It should be noted that these test data are the average values of a plurality of batches of samples after a plurality of tests.
Example 10
(1) Preparing liquid metal nanoparticles: preparing 0.3 wt% chitosan aqueous solution, adding 200mg of liquid metal gallium into 40mL of the chitosan aqueous solution, and performing ultrasonic treatment with 500W power to obtain gallium nanoparticle dispersion liquid, wherein the thickness of sodium alginate coated on the surface of the liquid metal gallium is 5 nm.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.3mol of lanthanum hydroxide colloidal solution, then adding 0.6mol of gluconolactone, stirring for 30s, and standing for 18h to obtain the liquid metal gallium hydrogel.
(3) And (3) soaking the liquid metal gallium hydrogel into 1.5mol/L ascorbic acid aqueous solution at 120 ℃ for 48 hours to reduce the graphene oxide.
(4) And (3) replacing the liquid metal gallium hydrogel with deionized water, wherein the time of each replacement is 3h, and after 4 times of replacement, carrying out freeze drying at 50 ℃ for 48h to obtain the liquid metal gallium aerogel.
The photo-thermal conversion under the irradiation of sunlight generates heat, and the infrared photograph is shown in fig. 10, and it should be noted that the test data is the average value of a plurality of batches of samples after being tested for a plurality of times.
The embodiment proves that the liquid metal aerogel disclosed by the invention is excellent in performance, the required preparation equipment is simple to operate, continuous automatic production can be realized, the preparation period and the cost are greatly shortened, and the liquid metal aerogel has a huge application prospect.
Comparative example 1
(1) Preparing liquid metal nanoparticles: preparing 0.1 wt% sodium dodecyl benzene sulfonate solution, taking 40mL, adding 40mg of liquid metal gallium, and performing ultrasonic treatment by adopting 400W power to obtain gallium nanoparticle dispersion liquid.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.3mol of lanthanum hydroxide colloidal solution, then adding 1.2mol of gluconolactone, stirring for 30s, and standing for 12h to obtain the liquid metal gallium hydrogel.
(3) And (3) soaking the liquid metal hydrogel into 1.5mol/L ascorbic acid aqueous solution for 48 hours to reduce the graphene oxide.
(4) And (3) replacing the liquid metal gallium hydrogel by using ethanol, performing supercritical drying after 4 times of replacement, and drying for 12 hours to obtain the liquid metal gallium aerogel.
The contact angle photograph of the gallium aerogel obtained in this example is shown in fig. 11, the contact angle is 136.3 °, and it should be noted that these test data are the average values of multiple batches of samples after multiple tests.
Comparative example 2
(1) Preparing liquid metal nanoparticles: preparing 0.1 wt% sodium alginate solution, taking 40mL, adding 40mg of liquid metal gallium, and performing ultrasonic treatment with 400W power to obtain gallium nanoparticle dispersion liquid.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 1.5mol/L ascorbic acid solution, stirring for 30s, standing at room temperature for 48h, and reducing the graphene oxide.
(3) And (3) replacing the liquid metal gallium hydrogel by using ethanol, performing supercritical drying after 4 times of replacement, and drying for 12 hours to obtain the liquid metal gallium aerogel.
Fig. 12 shows a transmission electron micrograph of the gallium aerogel obtained in this example, and it should be noted that these test data are average values of multiple batches of samples after multiple tests.
Comparative example 3
(1) Preparing liquid metal nanoparticles: preparing 0.1 wt% chitosan aqueous solution, taking 40mL, adding 40mg of liquid metal gallium, and performing ultrasonic treatment by adopting 400W power to obtain gallium nanoparticle dispersion liquid.
(2) And (3) mixing 4mL of the gallium nanoparticle dispersion liquid with 2mL of a 4mg/mL graphene oxide aqueous solution, uniformly mixing, adding 0.3mol of lanthanum hydroxide colloidal solution, then adding 0.6mol of gluconolactone, stirring for 30s, and standing for 12h to obtain the liquid metal gallium hydrogel.
(3) And (3) replacing the liquid metal gallium hydrogel by using deionized water, freezing and drying for 24 hours after 4 times of replacement, and obtaining the liquid metal gallium aerogel.
The contact angle photograph of the gallium aerogel obtained in this example is shown in fig. 13, the contact angle is 45 °, and it should be noted that these test data are the average values of a plurality of batches of samples after a plurality of tests.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (49)
1. A method for preparing a liquid metal aerogel, characterized by comprising:
(1) dispersing liquid metal in a polysaccharide aqueous solution to form liquid metal nano particles, and wrapping the liquid metal nano particles with polysaccharide to obtain a stable dispersion liquid, wherein the liquid metal is selected from any one or a combination of more than two of gallium, indium, rubidium and cesium;
(2) uniformly mixing the dispersion liquid of the liquid metal nanoparticles obtained in the step (1) with graphene oxide, sequentially adding metal hydroxide colloid and gluconolactone for ionic crosslinking, and standing to obtain liquid metal hydrogel;
(3) reducing graphene oxide in the liquid metal hydrogel by using a reducing agent;
(4) and (4) carrying out solvent replacement and drying treatment on the liquid metal hydrogel obtained in the step (3) to obtain the liquid metal aerogel.
2. The method of claim 1, wherein: in the step (1), the polysaccharide comprises any one or a combination of more than two of sodium alginate, chitin, chitosan, glycosaminoglycan polysaccharides, cellulose polysaccharides and pectin polysaccharides.
3. The method of claim 1, wherein: the polysaccharide content in the polysaccharide aqueous solution is 0.01-1 wt%.
4. The production method according to claim 3, characterized in that: the polysaccharide content in the polysaccharide water solution is 0.05-0.3 wt%.
5. The method of claim 1, wherein: the content of the liquid metal in the polysaccharide aqueous solution is 1-100 mg/mL.
6. The method of claim 5, wherein: the content of the liquid metal in the polysaccharide aqueous solution is 5-50 mg/mL.
7. The method of claim 1, wherein: the thickness of the polysaccharide wrapped on the liquid metal nanoparticles is 5-30 nm.
8. The method of claim 7, wherein: the thickness of the polysaccharide wrapped on the liquid metal nanoparticles is 8-20 nm.
9. The method according to claim 1, wherein the step (1) comprises: ultrasonically dispersing liquid metal into a polysaccharide aqueous solution, wherein the ultrasonic dispersion power is 200-800W.
10. The method of claim 9, wherein: the power of ultrasonic dispersion is 400-600W.
11. The method of claim 1, wherein: in the step (2), the metal hydroxide colloid includes one or a combination of two or more of lanthanum hydroxide, iron hydroxide, aluminum hydroxide, magnesium hydroxide, chromium hydroxide, copper hydroxide, barium hydroxide, and calcium hydroxide.
12. The method of claim 1, wherein: the molar ratio of the metal hydroxide colloid to the gluconolactone is 1: 20-10: 1.
13. The method of manufacturing according to claim 12, wherein: the molar ratio of the metal hydroxide colloid to the gluconolactone is 1: 10-5: 1.
14. The method of claim 1, wherein: the standing time is 8-48 h.
15. The method of claim 14, wherein: the standing time is 12-36 h.
16. The method of claim 15, wherein: the standing time is 18-24 h.
17. The method according to claim 1, wherein in the step (3), the reducing agent comprises HI, ascorbic acid, sodium ascorbate, hydrazine hydrate, ethylenediamine, Fe-containing2+Any one or a combination of two or more of the compound and dopamine.
18. The method of claim 1, wherein: the mass ratio of the reducing agent to the graphene oxide is 3: 1-50: 1.
19. The method of claim 18, wherein: the mass ratio of the reducing agent to the graphene oxide is 5: 1-15: 1.
20. The method of claim 1, wherein: the temperature of the reduction treatment is room temperature-180 ℃, and the time is 2-72 hours.
21. The method of claim 20, wherein: the temperature of the reduction treatment is 40-120 ℃, and the time is 12-48 h.
22. The method according to claim 1, wherein the step (4) comprises: and (2) carrying out solvent replacement treatment on the liquid metal hydrogel by adopting water or an organic solvent, wherein the organic solvent comprises any one or the combination of more than two of tert-butyl alcohol, ethanol, n-hexane and acetone.
23. The method of claim 22, wherein: the volume ratio of the water or the organic solvent to the liquid metal hydrogel is 5-100: 1.
24. The method of claim 23, wherein: the volume ratio of the water or the organic solvent to the liquid metal hydrogel is 20-60: 1.
25. The method of claim 1, wherein: the number of times of solvent replacement treatment is 3-10, and the time of replacement for each time is 3-24 h.
26. The method of claim 25, wherein: the time of each replacement is 5-18 h.
27. The method of claim 1, wherein: the drying process comprises supercritical fluid CO2Any one or combination of more than two of drying, normal pressure drying and freeze drying modes, wherein the freeze drying temperature is 0-50 ℃.
28. The method of claim 1, wherein: the drying time is 6-48 h.
29. The method of claim 28, wherein: the drying time is 12-24 h.
30. A liquid metal aerogel produced by the method of any of claims 1-29, having a continuous three-dimensional porous network structure comprised of liquid metal nanoparticles and graphene sheets that overlap, wherein at least a portion of the liquid metal nanoparticles are encapsulated by the graphene sheets, and wherein the liquid metal nanoparticles comprise any one or a combination of two or more of gallium, indium, rubidium, and cesium.
31. The liquid metallic aerogel of claim 30, wherein: the particle size of the liquid metal nanoparticles is 0.01-2 μm.
32. The liquid metallic aerogel of claim 31, wherein: the particle size of the liquid metal nanoparticles is 0.05-1 μm.
33. The liquid metallic aerogel of claim 32, wherein: the particle size of the liquid metal nano-particles is 0.075-0.75 μm.
34. The liquid metallic aerogel of claim 30, wherein: the liquid metal nanoparticles are tightly combined with the graphene lamella through the polysaccharide wrapped on the surface of the liquid metal nanoparticles.
35. The liquid metallic aerogel of claim 30, wherein: the liquid metal aerogel comprises 10-90 wt% of liquid metal nanoparticles and 90-10 wt% of graphene sheets.
36. The liquid metallic aerogel of claim 30, wherein: the three-dimensional porous network structure is composed of micropores with the aperture of 0.5-2 nm, mesopores with the aperture of 2-50 nm and macro pores with the aperture of 50 nm-500 mu m.
37. The liquid metallic aerogel of claim 30, wherein: the specific surface area of the liquid metal aerogel is 10-1000 m2/g。
38. The liquid metallic aerogel of claim 37, wherein: the specific surface area of the liquid metal aerogel is 100-500 m2/g。
39. The liquid metallic aerogel of claim 30, wherein: the density of the liquid metal aerogel is 25-200 mg/cm3。
40. The liquid metallic aerogel of claim 39, wherein: the density of the liquid metal aerogel is 45-150 mg/cm3。
41. The liquid metallic aerogel of claim 30, wherein: the thermal conductivity of the liquid metal aerogel is 0.10-0.80W/m-1.k-1。
42. The liquid metallic aerogel of claim 41, wherein: the thermal conductivity of the liquid metal aerogel is 0.20-0.60W/m-1.k-1。
43. The liquid metallic aerogel of claim 30, wherein: the pore volume of the liquid metal aerogel is 0.2-3.2 cm3/g。
44. The liquid metallic aerogel of claim 43, wherein: the pore volume of the liquid metal aerogel is 0.5-2.5 cm3/g。
45. The liquid metallic aerogel of claim 44, wherein: the pore volume of the liquid metal aerogel is 0.7-2.0 cm3/g。
46. The liquid metallic aerogel of claim 30, wherein: the liquid metal aerogel is 1-99% in porosity.
47. The liquid metallic aerogel of claim 30, wherein: the static contact angle between the surface of the liquid metal aerogel and water is 30-130o。
48. The liquid metallic aerogel of claim 47, wherein: the static contact angle of the surface of the liquid metal aerogel and water is 50-90 degrees.
49. Use of the liquid metal aerogel prepared by the method of any of claims 1-29 in the fields of thermal insulation, catalysis, batteries, supercapacitors, adsorption, sensing, or photo-thermal water evaporation.
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| CN114633468B (en) * | 2020-12-16 | 2024-02-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing stereoscopic aramid aerogel by suspension 3D printing and application |
| CN113150364B (en) * | 2021-03-29 | 2022-04-08 | 南京林业大学 | Photo-thermal response type bio-based aerogel and preparation method thereof |
| CN115462366A (en) * | 2021-06-11 | 2022-12-13 | 中国科学院理化技术研究所 | Liquid metal composite material and preparation method and application thereof |
| CN114988416B (en) * | 2022-07-15 | 2023-11-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Silica-based super-black aerogel, and preparation method and application thereof |
| CN115121192B (en) * | 2022-07-25 | 2023-05-26 | 中北大学 | Preparation method and application of PVA/HACC piezoelectric hydrogel of liquid metal/reduced graphene oxide |
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