CN115212306A - Noble metal-eggshell membrane photo-thermal material and preparation method and application thereof - Google Patents
Noble metal-eggshell membrane photo-thermal material and preparation method and application thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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Abstract
The invention provides a noble metal-eggshell membrane photothermal material and a preparation method and application thereof. According to the preparation method of the noble metal-eggshell membrane photothermal material, the noble metal nano particles are successfully assembled on the eggshell membrane by the in-situ generation and electrostatic self-assembly method, and then the carbon nano tubes are successfully assembled on a sample by the ultrasonic dispersion method. The noble metal-eggshell membrane photothermal material prepared by the invention has excellent photothermal conversion performance, and the temperature is basically stabilized at about 115-116 ℃ after 5min of illumination. The noble metal nano particles have a local surface plasmon resonance effect, can enhance the photothermal conversion efficiency of the composite eggshell membrane in a visible light region, and can quickly and efficiently convert light energy into heat energy under the synergistic action of the noble metal nano particles and the carbon nano tubes. The noble metal-eggshell membrane photothermal material has excellent photothermal conversion performance and has great application potential in the aspects of photothermal treatment of diseases and drug release.
Description
Technical Field
The invention relates to the technical field of photo-thermal materials, in particular to a noble metal-eggshell membrane photo-thermal material and a preparation method and application thereof.
Background
The solar photo-thermal conversion material is a material which can absorb sunlight and convert the sunlight into heat energy for accelerating water evaporation, and can be used in the fields of seawater desalination, wastewater treatment and the like. However, the conversion temperature of the current solar photo-thermal conversion materials is below 100 ℃, and in order to seek wider temperature variation, the improvement is necessary.
Carbon nanotubes are one type of plasmonic material, but it has a distinct LSPR effect from noble metal nanoparticles, causing a mechanism of converting radiation-absorbing light into thermal energy. The photo-thermal conversion mechanism of the carbon nanotube material is the same as that of the organic material, and the photo-thermal conversion effect is mainly caused by the electron transition in molecules. Carbon nanotubes have the characteristics of light weight, small size with high aspect ratio, good tensile strength, good electrical conductivity, chemical stability and the like, so that they are applied to the fields of aviation, communication, electronic components, medicine and the like. The carbon nano tube also has outstanding advantages in the aspect of thermal performance, ultrahigh thermal conductivity and stable thermal performance, and is beneficial to solving the problems of thermal management and heat dissipation. The light absorption range of the black substance is wide, and the color of the carbon nano tube is black, so that the carbon nano tube provides support for strong light absorption in a visible-near infrared region and can quickly convert light energy into heat energy.
However, the carbon nanotubes are not used to prepare the photothermal conversion material at present, so the photothermal conversion material can be prepared by using the carbon nanotubes to improve the temperature variation range.
Disclosure of Invention
In view of the above, the present invention provides a noble metal-eggshell membrane photothermal material, and a preparation method and an application thereof, so as to solve or partially solve the technical problems in the prior art.
In a first aspect, the invention provides a preparation method of a precious metal-eggshell membrane photothermal material, which comprises the following steps:
adding the eggshell membrane into the noble metal solution, using aldehyde group on the eggshell membrane as a reducing agent, heating in a water bath for reaction to reduce the noble metal, and drying to obtain the eggshell membrane loaded with the noble metal;
adding the eggshell membrane loaded with noble metal into the carbon nano tube solution, ultrasonically oscillating, dispersing and drying to obtain a noble metal-eggshell membrane photothermal material;
or, comprising the steps of:
adding the eggshell membrane into the carbon nano tube solution, performing ultrasonic oscillation dispersion, and drying to obtain the eggshell membrane loaded with the carbon nano tubes;
adding the eggshell membrane loaded with the carbon nano tube into the noble metal solution, using aldehyde group on the eggshell membrane as a reducing agent, heating in a water bath for reaction to reduce the noble metal, and drying to obtain the noble metal-eggshell membrane photothermal material.
Preferably, in the preparation method of the noble metal-eggshell membrane photothermal material, the noble metal solution comprises at least one of chloroauric acid solution and silver nitrate solution.
Preferably, the preparation method of the noble metal-eggshell membrane photothermal material comprises the following steps: adding the carbon nano tube into an alcohol solvent, and dispersing to obtain a carbon nano tube solution.
Preferably, in the preparation method of the noble metal-eggshell membrane photothermal material, the alcohol solvent comprises at least one of methanol, ethanol and glycerol.
Preferably, in the preparation method of the noble metal-eggshell membrane photothermal material, the water bath heating reaction temperature is 40-95 ℃, and the reaction time is 2-12 h.
Preferably, the preparation method of the noble metal-eggshell membrane photothermal material comprises the step of mixing eggshellsAdding the film into a noble metal solution, and in the step of reducing the noble metal by heating reaction in a water bath, the concentration of the noble metal solution is 1 multiplied by 10 -4 ～1.5×10 -4 mol/L, the mass volume ratio of the eggshell membrane to the noble metal solution is (0.1-0.3) g, (50-200) mL.
Preferably, in the preparation method of the noble metal-eggshell membrane photothermal material, the eggshell membrane loaded with the carbon nano tube is added into the noble metal solution, and in the step of reducing the noble metal by heating reaction in water bath, the concentration of the noble metal solution is 1 x 10 -4 ～1.5×10 -4 mol/L, the mass volume ratio of the eggshell membrane to the noble metal solution is (0.1-0.3) g, (50-200) mL.
Preferably, in the preparation method of the noble metal-eggshell membrane photothermal material, the concentration of the carbon nanotube solution is 1-3 g/L.
In a second aspect, the invention also provides a noble metal-eggshell membrane photothermal material prepared by the preparation method.
In a third aspect, the invention also provides the noble metal-eggshell membrane photothermal material prepared by the preparation method or the application of the noble metal-eggshell membrane photothermal material in seawater evaporation, photothermal therapy and drug release.
Compared with the prior art, the noble metal-eggshell membrane photothermal material and the preparation method thereof have the following beneficial effects:
according to the preparation method of the noble metal-eggshell membrane photothermal material, the noble metal nano particles are successfully assembled on the eggshell membrane by the in-situ generation and electrostatic self-assembly method, and then the carbon nano tubes are successfully assembled on a sample by the ultrasonic dispersion method. The eggshell membrane not only plays a role of a supporting material, but also plays a role of a reducing agent and a stabilizing agent in the process of generating the noble metal nano particles in situ. The noble metal-eggshell membrane photothermal material prepared by the invention has excellent photothermal conversion performance, and the temperature is basically stabilized at about 115-116 ℃ after 5min of illumination. The noble metal nanoparticles (such as gold nanoparticles and silver nanoparticles) have a Localized Surface Plasmon Resonance (LSPR), can enhance the photothermal conversion efficiency of the composite eggshell membrane in a visible light region, and can quickly and efficiently convert light energy into heat energy under the synergistic action of the noble metal nanoparticles and the carbon nanotubes. The eggshell membrane serving as a green biological membrane has good biocompatibility, shows excellent photothermal conversion performance under the composite of two photothermal conversion materials of the carbon nano tube and the noble metal nano particle and the synergistic effect of the two photothermal conversion materials, and has great application potential in the aspects of photothermal treatment and drug release of diseases.
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 of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is optical images of the noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3 of the present invention, comparative examples 1 to 2, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane in example 1;
FIG. 2 is a surface topography of a noble metal-eggshell membrane photothermal material prepared in examples 1-3, comparative example 1, an eggshell membrane photothermal material prepared in comparative example 3, and an eggshell membrane, and a scanning electron microscope image of the noble metal-eggshell membrane photothermal material in example 2 of the present invention;
fig. 3 is uv-vis diffuse reflection absorption spectra of the noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3, comparative examples 1 to 2 of the present invention, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane in example 1;
FIG. 4 is an X-ray photoelectron spectrum of the noble metal-eggshell membrane photothermal material prepared in examples 1-3 of the present invention and the eggshell membrane surface in example 1;
FIG. 5 is a thermogravimetric plot of the noble metal-eggshell membrane photothermal material prepared in examples 1-3, comparative examples 1-2 of the present invention, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane prepared in example 1;
FIG. 6 is a Raman scattering spectrum of the noble metal-eggshell membrane photothermal material of examples 2 to 3 of the present invention;
FIG. 7 is a graph showing infrared thermography of the noble metal-eggshell membrane photothermal materials prepared in examples 1-3, comparative examples 1-2, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane in example 1 according to the present invention;
FIG. 8 is a graph showing the temperature change of the noble metal-eggshell membrane photothermal material prepared in examples 1 to 3, comparative examples 1 to 2, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane in example 1 under xenon lamp irradiation according to the present invention;
fig. 9 is a view showing the heating and cooling cycles of the noble metal-eggshell membrane photothermal material in examples 2-3 of the present invention.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a preparation method of a noble metal-eggshell membrane photothermal material, which comprises the following steps:
s1, adding an eggshell membrane into a noble metal solution, using aldehyde groups on the eggshell membrane as a reducing agent, heating in a water bath for reaction to reduce noble metals, and drying to obtain the eggshell membrane loaded with noble metals;
s2, adding the eggshell membrane loaded with the noble metal into the carbon nanotube solution, and performing ultrasonic oscillation dispersion and drying to obtain the noble metal-eggshell membrane photothermal material;
or, comprising the steps of:
s1, adding an eggshell membrane into a carbon nano tube solution, performing ultrasonic oscillation dispersion, and drying to obtain an eggshell membrane loaded with carbon nano tubes;
s2, adding the eggshell membrane loaded with the carbon nano tubes into the noble metal solution, using aldehyde groups on the eggshell membrane as a reducing agent, carrying out a water bath heating reaction to reduce the noble metals, and drying to obtain the noble metal-eggshell membrane photothermal material.
In the present embodiment, the eggshell membrane refers to: after the egg is broken, the white translucent material attached to the eggshell is called eggshell membrane; the preparation method mainly comprises two technical schemes, namely: adding the eggshell membrane into the noble metal solution, using aldehyde group on the eggshell membrane as a reducing agent, carrying out water bath heating reaction to reduce noble metals, drying to obtain a noble metal-loaded eggshell membrane, adding the noble metal-loaded eggshell membrane into the carbon nanotube solution, carrying out ultrasonic oscillation dispersion, and drying to obtain a noble metal-eggshell membrane photothermal material; and the second method comprises the following steps: adding the eggshell membrane into the carbon nano tube solution, performing ultrasonic oscillation dispersion, and drying to obtain the eggshell membrane loaded with the carbon nano tubes; adding the eggshell membrane loaded with the carbon nano tube into the noble metal solution, using aldehyde group on the eggshell membrane as a reducing agent, heating in a water bath for reaction to reduce the noble metal, and drying to obtain the noble metal-eggshell membrane photothermal material; the noble metal-eggshell membrane photothermal material prepared by the two schemes has excellent photothermal conversion efficiency, and the conversion performance of the bifunctional composite membrane is further improved under the synergistic action of the noble metal nanoparticles and the carbon nanotubes, so that the method is provided for more efficiently utilizing solar clean energy, and the noble metal-eggshell membrane photothermal material has application prospects in the aspects of seawater evaporation, photothermal treatment and the like.
In some embodiments, the noble metal solution comprises at least one of a chloroauric acid solution and a silver nitrate solution, both of which are aqueous solutions, and the chloroauric acid solution or the silver nitrate solution is prepared by: adding chloroauric acid or silver nitrate into water respectively to obtain chloroauric acid solution or silver nitrate solution.
Specifically, for the first technical scheme, aldehyde groups on the eggshell membrane are used as reducing agents, chloroauric acid solution is reduced, gold nanoparticles are further formed and loaded on the eggshell membrane, or silver nanoparticles are loaded on the eggshell membrane by using an electrostatic self-assembly principle, then the eggshell membrane loaded with the gold nanoparticles and the silver nanoparticles is placed in carbon nanotube solution, ultrasonic oscillation dispersion is carried out, the carbon nanotubes are coated on the surface of the eggshell membrane fibers through van der waals force, and the silver nanoparticles and the carbon nanotubes can be better coated on the eggshell membrane fibers; however, after assembling gold nanoparticles, the carbon nanotubes are difficult to coat due to the formation of steric hindrance effect, and in order to solve the problem, a second technical scheme can be adopted, namely: the preparation method comprises the steps of adding an eggshell membrane into a carbon nano tube solution, performing ultrasonic oscillation dispersion, drying to enable the carbon nano tubes to be coated on the surfaces of eggshell membrane fibers through Van der Waals force, adding the eggshell membrane fibers coated with the carbon nano tubes into a chloroauric acid solution, using aldehyde groups on the eggshell membrane as a reducing agent, performing water bath heating reaction to reduce gold, drying, loading gold nanoparticles on the eggshell membrane coated with the carbon nano tubes, and finally preparing the noble metal-eggshell membrane photothermal material.
In some embodiments, the reducing agent comprises at least one of trisodium citrate, sodium borohydride.
In some embodiments, the carbon nanotube solution is prepared by: adding the carbon nano tube into an alcohol solvent, and dispersing to obtain a carbon nano tube solution.
Specifically, the alcohol solvent used comprises at least one of methanol, ethanol and glycerol, and preferably ethanol is used.
In some embodiments, the water bath heating reaction temperature is 40-95 ℃ and the reaction time is 2-12 h.
In some embodiments, the eggshell membrane is added into the noble metal solution, and the noble metal is reduced by heating in water bath by using aldehyde group on the eggshell membrane as a reducing agent, wherein the concentration of the noble metal solution is 1 × 10 -4 ～1.5×10 -4 mol/L, the mass volume ratio of the reducing agent to the noble metal solution is (0.1-0.3) g (50-200) mL.
In some embodiments, the carbon nanotube-loaded eggshell membrane is added into the noble metal solution, and the aldehyde group on the eggshell membrane is used as a reducing agent, and in the step of reducing the noble metal by heating reaction in water bath, the concentration of the noble metal solution is 1 for a long time10 -4 ～1.5×10 -4 mol/L, the mass volume ratio of the reducing agent to the noble metal solution is (0.1-0.3) g (50-200) mL.
In some embodiments, the concentration of the carbon nanotube solution is 1 to 3g/L.
In some embodiments, the ultrasonic oscillation dispersion time is 20 to 40min.
Based on the same inventive concept, the embodiment of the application also provides a noble metal-eggshell membrane photothermal material prepared by the preparation method.
Based on the same inventive concept, the embodiment of the application also provides application of the precious metal-eggshell membrane photothermal material prepared by the preparation method in seawater evaporation, photothermal therapy and drug release.
The method for preparing the noble metal-eggshell membrane photothermal material of the present application is further illustrated by the following specific examples. This section further illustrates the present invention with reference to specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
The following examples and comparative examples of multi-walled carbon nanotubes (CNTs > 90.0%, inner diameter of about 5-10nm, outer diameter of about 20-40nm, length of about 10-30 μm) were purchased from Aladdin (Shanghai, china).
The following examples and comparative eggshell membranes (denoted as Pristine ESM) were prepared: removing eggshell from fresh egg with tweezers to obtain eggshell membrane fiber, and repeatedly washing with deionized water. Clean eggshell membrane was cut into small pieces (2.0 cm. Times.1.5 cm) and dried at room temperature for further experiments.
Example 1
The embodiment of the application provides a preparation method of a noble metal-eggshell membrane photothermal material, which comprises the following steps:
s1, adding the eggshell membrane to 150mL of the eggshell membrane with the concentration of 1.5 multiplied by 10 -4 Reacting the gold chloride acid solution of mol/L at the temperature of 95 ℃ for 2h, and drying at room temperature to obtain the negative goldEgg shell membrane carrying gold nanoparticles;
s2, adding the multi-wall carbon nano tube into ethanol to obtain a carbon nano tube solution with the concentration of 2 g/L;
and S3, adding the eggshell membrane loaded with the gold nanoparticles in the step S1 into 150mL of 2g/L carbon nanotube solution, ultrasonically oscillating and dispersing for 30min, and drying at room temperature to obtain the precious metal-eggshell membrane photothermal material (recorded as Au/CNT/ESM).
Example 2
The embodiment of the application provides a preparation method of a noble metal-eggshell membrane photothermal material, which comprises the following steps:
s1, adding a multi-walled carbon nanotube into ethanol to obtain a carbon nanotube solution with the concentration of 2 g/L;
s2, adding the eggshell membrane into 150mL of 2g/L carbon nanotube solution, ultrasonically oscillating and dispersing for 30min, and drying at room temperature to obtain the eggshell membrane loaded with the carbon nanotubes;
s3, adding the eggshell membrane loaded with the carbon nanotubes in the step S2 to 150mL, wherein the concentration of the eggshell membrane is 1.5 multiplied by 10 -4 And (3) reacting the chloroauric acid solution of mol/L at the temperature of 95 ℃ for 2 hours, and drying at room temperature to obtain the noble metal-eggshell membrane photothermal material (marked as CNT/Au/ESM).
Example 3
The embodiment of the application provides a preparation method of a noble metal-eggshell membrane photothermal material, which comprises the following steps:
s1, preparing the concentration of 1 multiplied by 10 in advance -4 The silver nitrate solution of mol/L is added with 1ml of 1 multiplied by 10 concentration -1 1mL of an aqueous solution of trisodium citrate (8X 10) in mol/L is slowly added with vigorous stirring -3 Obtaining yellow silver seed solution by using mol/L sodium borohydride aqueous solution, and then placing the yellow silver seed solution under a sodium lamp (NAV-T70, purchased from Oselta Lighting Co., ltd., china) to irradiate for 12 hours to obtain blue silver seed solution by induction; then putting the eggshell membrane into blue silver seed solution, reacting for 12h at the temperature of 40 ℃, and drying at room temperature to obtain the eggshell membrane loaded with silver nanoparticles;
s2, adding the multi-wall carbon nano tube into ethanol to obtain a carbon nano tube solution with the concentration of 2 g/L;
and S3, adding the eggshell membrane loaded with the silver nanoparticles in the step S1 into 150mL of 2g/L carbon nanotube solution, ultrasonically oscillating and dispersing for 30min, and drying at room temperature to obtain the precious metal-eggshell membrane photothermal material (marked as Ag/CNT/ESM).
Comparative example 1
The comparative example provides a preparation method of a noble metal-eggshell membrane photothermal material, which comprises the following steps:
s1, adding the eggshell membrane into 150mL of chloroauric acid solution with the concentration of 3mol/L, reacting for 2h at the temperature of 95 ℃, and drying at room temperature to obtain the eggshell membrane loaded with the gold nanoparticles, namely the precious metal-eggshell membrane photothermal material (marked as Au/ESM).
Comparative example 2
The comparative example provides a preparation method of a noble metal-eggshell membrane photothermal material, which comprises the following steps:
s1, preparing the concentration of 1 multiplied by 10 in advance -4 Adding 1ml of silver nitrate solution with the concentration of 1 × 10 -1 Adding 1mL of trisodium citrate solution with concentration of 8X 10 slowly under vigorous stirring -3 Obtaining yellow silver seed solution by using mol/L sodium borohydride aqueous solution, and then placing the yellow silver seed solution under a sodium lamp (NAV-T70, purchased from Oselta Lighting Co., ltd., china) to irradiate for 12 hours to obtain blue silver seed solution by induction; and then putting the eggshell membrane into blue silver seed solution, reacting for 12h at the temperature of 40 ℃, and drying at room temperature to obtain the eggshell membrane loaded with the silver nanoparticles, namely the precious metal-eggshell membrane photothermal material (marked as Ag/ESM).
Comparative example 3
The comparative example provides a preparation method of an eggshell membrane photothermal material, which comprises the following steps:
s1, adding a multi-wall carbon nano tube into ethanol to obtain a carbon nano tube solution with the concentration of 2 g/L;
and S3, adding the eggshell membrane into 150mL of 2g/L carbon nanotube solution, performing ultrasonic oscillation dispersion for 30min, and drying at room temperature to obtain the eggshell membrane photothermal material (marked as CNT/ESM).
Performance testing
Optical images of the noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3 and comparative examples 1 to 2, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane in example 1 are shown in fig. 1.
The untreated native eggshell membrane in FIG. 1 is white (Prinstine ESM in FIG. 1). And the eggshell membrane photothermal material CNT/ESM prepared in the comparative example 3 is black, because the carbon nano tube is black. In addition, the carbon nano tube shows better adhesiveness, and the carbon nano tube can be still well fixed on the surface of the eggshell membrane after being washed by water. In the comparative example 2, the surface of the eggshell membrane Ag/ESM which is generated by electrostatic self-assembly and loaded with the silver nanoparticles is blue; in example 3, the Ag/ESM is obtained by loading the carbon nanotubes on the Ag/ESM, and the color is changed from blue to black, which indicates that the carbon nanotubes are successfully assembled on the surface of the eggshell membrane fiber. In comparative example 1, the eggshell membrane Au/ESM loaded with the gold nanoparticles is generated in situ, the surface is brownish red, and the color distribution is uniform; in the bifunctional composite membrane Au/CNT/ESM obtained by reducing gold nanoparticles in situ and assembling carbon nanotubes in the embodiment 1, the carbon nanotubes cannot be uniformly loaded on the surface of the membrane, and the color of the membrane is close to that of an eggshell membrane Au/ESM only loaded with the gold nanoparticles, which means that only a small amount of carbon nanotubes are loaded on the surface of the eggshell membrane, and the assembly effect is poor. In example 2, the carbon nanotubes are assembled first, and then the gold nanoparticles are reduced in situ by using the aldehyde group reduction performance of the eggshell membrane to obtain the uniformly-loaded bifunctional composite membrane, wherein the carbon nanotubes and the gold nanoparticles are uniformly distributed on the eggshell membrane, as shown in fig. 1 by the CNT/Au/ESM.
The noble metal-eggshell membrane photothermal material prepared in examples 1-3 and comparative example 1, the eggshell membrane photothermal material prepared in comparative example 3 and the surface morphology of the eggshell membrane are characterized by a thermal field scanning electron microscope (FESEM, JEOL JSM-7800F); the EDS energy spectrum element distribution of the noble metal-eggshell membrane photothermal material in the example 2 is analyzed, and the result is shown in figure 2.
In fig. 2, (a) is the surface morphology of the untreated eggshell membrane Pristine ESM, (B) is the surface morphology of the eggshell membrane photothermal material CNT/ESM in comparative example 3, (C) is the surface morphology of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, (D) is the surface morphology of the noble metal-eggshell membrane photothermal material Au/ESM in comparative example 1, (E) is the surface morphology of the noble metal-eggshell membrane photothermal material Au/CNT/ESM in example 1, (F) is the surface morphology of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2, and (G) is the EDS energy spectrum element distribution diagram of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2.
From fig. 2 it can be seen that the eggshell membrane is a three-dimensional network structure with fiber-to-fiber bonds and a porous structure, similar to a non-woven fabric. From FIG. 2 (A), it can be observed that the surface of the natural eggshell membrane Pristine ESM fibers is relatively clean. As shown in FIG. 2 (B), in the eggshell membrane photothermal material CNT/ESM of comparative example 3, the carbon nanotubes are also uniformly coated on the surface of the eggshell membrane fibers, and only a small part of the carbon nanotubes are aggregated. As shown in fig. 2 (C), in example 3, the noble metal-eggshell membrane photothermal material Ag/CNT/ESM carbon nanotubes are distributed on the surface of the eggshell membrane fiber relatively uniformly, which indicates that the carbon nanotubes are successfully coated on the surface of the eggshell membrane fiber, and the silver nanoparticles are also coated therein. As shown in FIG. 2 (D), in comparative example 1, the noble metal-eggshell membrane photothermal material Au/ESM, a large number of gold nanoparticles were uniformly coated on the eggshell membrane surface. As shown in fig. 2 (E), in the noble metal-eggshell membrane photothermal material Au/CNT/ESM of example 1, the carbon nanotubes are difficult to coat on the eggshell membrane fibers, only a small amount of carbon nanotubes are present, and the carbon nanotubes are not uniformly distributed, and easily aggregate, and the photo-photo color thereof is similar to the Au/ESM composite membrane. Because the eggshell membrane contains a large amount of amino acids and saccharides, which all contain a large amount of aldehyde groups (R-CHO), the aldehyde groups can be used as reducing agents to reduce a large amount of gold ions into gold nanoparticles and are generated on the surface of the eggshell membrane fibers. Due to the formation of the gold nanoparticles, a steric hindrance effect is formed on the surface of the eggshell membrane fiber, so that the carbon nanotubes cannot effectively contact hydrophobic groups on the surface of the eggshell membrane, and the surface of the eggshell membrane fiber is less coated. As shown in fig. 2 (F), in the noble metal-eggshell membrane photothermal material CNT/Au/ESM of example 2, a large amount of carbon nanotubes are uniformly coated on the eggshell membrane surface, and then the carbon nanotubes do not fall off after gold nanoparticles are generated in situ. Part of the gold nanoparticles are uniformly dispersed on the surface of the eggshell membrane which is not covered by the carbon nano tubes, and the other part of the gold nanoparticles are agglomerated into a sphere and are uniformly distributed on the surface of the eggshell membrane.
As seen from fig. 2 (G), C, N and Au element are uniformly distributed on the surface in EDS of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2, further confirming the successful assembly of gold nanoparticles on the eggshell membrane fiber.
Spectra of the noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3, comparative examples 1 to 2, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane in example 1 were measured using an ultraviolet-visible-near infrared spectrometer (Solidspec-3700, shimadzu, japan) to characterize optical properties of different composite eggshell membrane samples, and the results are shown in fig. 3.
Specifically, in fig. 3, a represents the untreated eggshell membrane Pristine ESM in example 1, b represents the noble metal-eggshell membrane photothermal material Ag/ESM in comparative example 2, c represents the noble metal-eggshell membrane photothermal material Au/ESM in comparative example 1, d represents the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2, e represents the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, f represents the eggshell membrane photothermal material CNT/ESM in comparative example 3, and g represents the noble metal-eggshell membrane photothermal material Au/CNT/ESM in example 1.
As can be seen from FIG. 3, the untreated eggshell membrane Pristine ESM in example 1 has a strong absorption only in the UV band, since its main component is protein, corresponding to the absorption band of protein. The absorption range of the eggshell membrane photothermal material CNT/ESM in comparative example 3, the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, and the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2 was 200-800nm, which covered almost the entire visible region due to the coverage of the sample surface with carbon nanotubes. The carbon nano tube is black, absorbs the spectral bandwidth, and therefore has high light absorption efficiency. The property is beneficial to the sample to absorb light energy and carry out photothermal conversion. In example 1, the precious metal-eggshell membrane photothermal material Au/CNT/ESM has a lower content of carbon nanotubes covered on the surface and a relatively higher content of gold nanoparticles, so that more ultraviolet absorption characteristics of the gold nanoparticles are shown, and the characteristic absorption band of the gold nanoparticles can be observed at 510 nm. Compared with the obvious characteristic absorption band of the noble metal-eggshell membrane photothermal material Au/ESM at 540nm in the comparative example 1, the gold nanoparticle absorption band of the noble metal-eggshell membrane photothermal material Au/CNT/ESM in the example 1 is blue-shifted, which shows that the carbon nanotube can regulate and control the LSPR effect of the gold nanoparticle, so that the gold nanoparticle can show the light absorption effect at different wave bands.
The noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3 and the chemical element composition of the eggshell membrane surface in example 1 were obtained by measurement using an X-ray photoelectron spectroscopy (XPS, thermo ESCALAB 250 XL) system, and the results are shown in fig. 4.
Fig. 4 shows the XPS spectra of the noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3 (where a is the XPS spectrum of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, B is the XPS spectrum of the noble metal-eggshell membrane photothermal material Au/CNT/ESM in example 1, C is the XPS spectrum of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2), (B) is the C1s spectrum of the untreated eggshell membrane Pristine ESM in example 1, (C) is the C1s spectrum of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, (D) is the C1s spectrum of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2, and (E) is the Ag3D spectrum of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, and (F) is the XPS spectrum of the noble metal-eggshell membrane photothermal material Au/ESM in example 1/ESM 4.
As can be seen from FIG. 4, the main elements on the surface of the noble metal-eggshell membrane photothermal materials (Ag/CNT/ESM, au/CNT/ESM and CNT/Au/ESM) prepared in examples 1-3 are C, N, O elements, and their binding energies are 285.08eV, 400.08eV and 532.08eV, respectively, and C, N, O are the basic constituent elements of proteins. In addition, the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3 has two characteristic peaks at 368.18eV and 573.61eV, which correspond to the binding energy Ag3d and Ag3p, respectively, which indicates that the existence of the silver nanoparticles can be detected on the surface of the composite membrane fiber, and indicates that the existence of the silver nanoparticles on the surface of the eggshell membrane fiber is not affected after the carbon nanotubes are coated. Shown in FIG. 4 (E)Is the 3d bimodal splitting of Ag in the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, and represents Ag3d in 368.08eV and 374.08eV respectively 5/2 And Ag3d 3/2 The binding energy further indicates the existence of silver element. The noble metal-eggshell membrane photothermal material Au/CNT/ESM in example 1 and the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2 have two characteristic peaks at 84.18eV and 335.18eV, which correspond to Au4f and Au4d, respectively, and the existence of a large number of gold nanoparticles on the surface of the composite membrane is proved. The Au4F peak is composed of two characteristic peaks at 84.18eV and 87.4eV, which correspond to Au4F7 and Au4F5 (shown in FIG. 4 (F)), respectively. The C1s bands of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3 and the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2 can be fitted with five peaks 284.28eV, 284.98eV, 285.88eV, 287.08eV and 288.78eV, corresponding to C = C, C-C, C-O, C = O, O-C = O, respectively. Wherein the peak of the C-C bond corresponds to the defect in the conjugated ring of the carbon nano tube and the aromatic hydrocarbon.
Thermogravimetric curves of the noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3, comparative examples 1 to 2, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane in example 1 were tested, and the results are shown in fig. 5. The specific test method comprises the following steps: obtained by thermogravimetric analysis (TAG, perkin Elmer's Diamond TG/DTA system) with a heating rate of 10 ℃ for min under argon atmosphere -1 。
Specifically, in fig. 5, a represents the untreated eggshell membrane Pristine ESM in example 1, b represents the noble metal-eggshell membrane photothermal material Ag/ESM in comparative example 2, c represents the eggshell membrane photothermal material CNT/ESM in comparative example 3, d represents the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, e represents the noble metal-eggshell membrane photothermal material Au/ESM in comparative example 1, f represents the noble metal-eggshell membrane photothermal material Au/CNT/ESM in example 1, and g represents the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2.
The weight loss of the eggshell membrane sample below 105 ℃ was due to evaporation of water bound to the eggshell membrane sample. After reaching 233 ℃ all material weight loss started to accelerate, probably due to the starting thermal degradation of collagen. In example 1, the untreated eggshell membrane Pristine ESM is decomposed to reach a stable state at about 500 ℃, and then the temperature is raised to 800 ℃ to leave a residual mass percentage of about 26.19%. The eggshell membrane only coated with carbon nanotubes on the eggshell membrane fibers has a residual mass percentage of 28.86 percent after the temperature reaches 800 ℃. Since the carbon nanotubes can withstand high temperatures, tested under an argon atmosphere, and can hardly be pyrolyzed in this temperature range, the above amount of CNT/ESM can be found to be about 2.67% by comparing the mass percentage of the residue of the untreated eggshell membrane Pristine ESM and the eggshell membrane photothermal material CNT/ESM prepared in comparative example 3. In the noble metal-eggshell membrane photothermal material Au/ESM in the comparative example 1, after the temperature reaches 800 ℃, the residual mass percentage is about 40.90%, and the gold nanoparticles cannot be pyrolyzed at high temperature, which shows that the gold nanoparticles are loaded on the eggshell membrane and the content is about 12.04%. This is not very different from the content tested in an air atmosphere. After the temperature reaches 800 ℃, the mass percent of the residue of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2 is 47.42%, and compared with the mass percent of the residue of the Au/ESM composite membrane, the content of the carbon nanotube on the CNT/Au/ESM dual-function composite membrane can be calculated to be about 6.52%. The final mass percentage of the precious metal-eggshell membrane photothermal material Au/CNT/ESM in example 1 was 41.79%, and the amount of the above carbon nanotubes was calculated by the same method to be about 0.89%, which shows that the content of the carbon nanotubes in the Au/CNT/ESM composite membrane is very small, as the previous analysis result. The residual mass percentage of the noble metal-eggshell membrane photothermal material Ag/ESM in the comparative example 2 was about 27.27%, and the silver nanoparticles loaded on the eggshell membrane fibers were calculated to be about 1.08% by comparison with the residual mass percentage of the untreated eggshell membrane Pristine ESM. The mass percentage of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM residue in example 3 is about 35.10%, and the mass percentage of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM residue is about 7.83% by calculation.
The raman scattering spectra of the noble metal-eggshell membrane photothermal material CNT/Au/ESM (shown in fig. 6 (B)) in example 2 and the noble metal-eggshell membrane photothermal material Ag/CNT/ESM (shown in fig. 6 (a)) in example 3 were tested, and the results are shown in fig. 6. Specifically, the Raman spectrum (Raman) was measured by using an INVIA-type confocal micro Raman spectrometer from Renishaw corporation, and the excitation light source was a He-Ne laser with a wavelength of 633nm, a power of 0.5%, and an integration time of 10s.
Carbon-based materials typically have significant raman activity and therefore raman spectroscopy is used to characterize composite films with silver (gold) nanoparticles and carbon nanotubes bi-functionalized. Under the excitation light source of 633nm, the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3 can be observed to be 1320cm -1 A characteristic peak appears, which is considered as a D band of the carbon nano tube and corresponds to a structural defect in the carbon nano tube; 1568cm -1 The characteristic peak corresponds to the G band and is sp of the carbon nano tube 3 Characteristic peaks of the structure. Relative intensities of D and G bands R = (ID/IG) and structural defects and sp in carbon nanotube samples 3 The number of hybridized carbon atoms is related and can provide direct information on the degree of sidewall functionalization. The R value of the treated sample was about 0.84 and was substantially unchanged from the original carbon nanotubes, indicating that the original structure of the carbon nanotubes was maintained after the carbon nanotubes were combined with the functional groups on the surface of the eggshell membrane. Raman spectra of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2 also showed similar spectra, at 1328cm -1 The characteristic peak is shown to belong to a D band on the carbon nano tube and is caused by the defect on the carbon nano tube, the D band is related to a hybridization vibration mode related to the edge of a graphite layer, and the characteristic peak shows that the carbon nano tube has some disorder, and the band is also called a disorder band or a defect band. At 1579cm -1 The characteristic peaks shown there represent the G bands of the carbon nanotubes, also caused by defects.
The noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3 and comparative examples 1 to 2, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane photothermal conversion performance in example 1 were tested. Specifically, the photothermal conversion performance of the eggshell membrane photothermal material is completed in the environment of simulating sunlight. The eggshell membrane photothermal material is placed on a quartz plate, is placed below a xenon lamp (the xenon lamp (lambda =350-780 nm) is used as a simulated solar light source), and is 30cm away from the xenon lamp. And (3) recording the temperature change of the eggshell membrane sample by using a small thermal imaging camera, recording the data of the temperature change once every 5min, and recording the temperature change condition within 30 min.
Fig. 7 shows the infrared thermal imaging graphs of different eggshell membrane photothermal materials under xenon lamp irradiation for 0min, 2 min and 30min before and after illumination. After the eggshell membrane is illuminated, the temperature is raised to some extent, and the sample compounded with the carbon nano tube can be seen by observing the heat distribution area, the temperature is raised obviously, and the heat is concentrated on the sample. This is because the carbon nanotube has a thermal conversion capability that is highly efficient for near infrared light, and can generate a local high temperature as a photothermal conversion material.
Fig. 8 shows the temperature change tendency of the noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3, comparative examples 1 to 2, the eggshell membrane photothermal material prepared in comparative example 3, and the eggshell membrane in example 1 under the irradiation of a xenon lamp.
Specifically, in FIG. 8, a represents the untreated eggshell membrane Prsistine ESM of example 1, b represents the noble metal-eggshell membrane photothermal material Ag/ESM of comparative example 2, c represents the noble metal-eggshell membrane photothermal material Au/ESM of comparative example 1, d represents the eggshell membrane photothermal material CNT/ESM of comparative example 3, e represents the noble metal-eggshell membrane photothermal material Au/CNT/ESM of example 1, f represents the noble metal-eggshell membrane photothermal material CNT/Au/ESM of example 2, and g represents the noble metal-eggshell membrane photothermal material Ag/CNT/ESM of example 3.
As can be seen in FIG. 8, the temperature of the untreated eggshell membrane Pristine ESM of example 1 rose from 30.5 ℃ to 46.2 ℃ after 30min of illumination, and only rose by 15.7 ℃. Under the same illumination conditions, the temperature of the noble metal-eggshell membrane photothermal material Au/ESM in the comparative example 1 is increased to 75.1 ℃, the temperature of the eggshell membrane photothermal material CNT/ESM in the comparative example 3 is increased to 108.9 ℃, the temperature of the noble metal-eggshell membrane photothermal material Ag/ESM in the comparative example 2 is increased to 73.9 ℃, and the temperature of the noble metal-eggshell membrane photothermal material Au/CNT/ESM in the example 1 is increased to 107.2 ℃, wherein the temperature of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM in the example 3 and the temperature of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in the example 2 are increased to 116.8 ℃ and 116.3 ℃ respectively. The LSPR bands of the silver nanoparticles are located at 603nm, the LSPR bands of the gold nanoparticles are located at 528nm, light absorption in a visible light region is facilitated, the carbon nanotubes have a strong light absorption effect in a near infrared region, and the photo-thermal conversion efficiency of the film is enhanced by the synergistic effect of the nanoparticles.
The heating and cooling cycle profiles of the noble metal-eggshell membrane photothermal material Ag/CNT/ESM of example 3 and the noble metal-eggshell membrane photothermal material CNT/Au/ESM of example 2 were tested, as shown in FIG. 9.
As can be seen from fig. 9, in example 2, the temperature of the noble metal-eggshell membrane photothermal material CNT/Au/ESM can reach 117.4 ℃ after being irradiated for 30s, the temperature is basically kept stable with the increase of the irradiation time, the temperature reduction rate is fast, after the irradiation is stopped for 5s, the temperature is rapidly reduced to 39.2 ℃, and then the temperature reduction rate is slowed down, and the state of room temperature is basically reached within 30 s. The noble metal-eggshell membrane photothermal material Ag/CNT/ESM in the embodiment 3 also shows the property, the temperature rising and the temperature lowering are faster, after the light irradiation is carried out for 15s, the temperature can reach 117.1 ℃, the light irradiation is continued, the temperature rising is slower, the temperature changes about 1 ℃, the temperature basically keeps stable, after the light source is turned off, the temperature has a tendency of suddenly dropping, the temperature is reduced to 39 ℃ within 5s, and the temperature slowly stabilizes within the range of the room temperature along with the increase of time. And after multiple cycle experiments, the sample is basically unchanged, the photo-thermal conversion capability is also kept constant, and the method has the characteristic of repeated use. After the carbon nano tube is added, the photo-thermal response of the CNT/Au/ESM and Ag/CNT/ESM dual-functional composite film sample is very fast, the temperature can be raised to be more than 100 ℃ within a few tens of seconds, and the cooling speed is also very fast, which can be attributed to the high thermal conductivity of the carbon nano tube and the strong visible-near infrared light absorption capability, thereby causing the fast illumination conversion response. The composite material has the characteristics of rapid temperature rise and reduction and obvious photo-thermal effect, and has certain potential in the aspects of seawater desalination, drug release and the like.
In summary, the gold nanoparticles and the silver nanoparticles are successfully assembled on the eggshell membrane by the in-situ generation and electrostatic self-assembly method, and then the carbon nanotubes are successfully assembled on the sample by the ultrasonic dispersion method. The eggshell membrane not only plays a role of a supporting material, but also plays a role of a reducing agent and a stabilizing agent in the process of generating the gold nanoparticles in situ. When the eggshell membrane is bi-functionalized, gold nanoparticles are generated in situ, and then the carbon nanotubes are coated, so that the carbon nanotubes are difficult to attach to the eggshell membrane; the generation of gold nanoparticles cannot be influenced by the existence of the carbon nano tubes, and the bifunctional CNT/Au/ESM prepared by changing the treatment sequence has high loading capacity of the gold nanoparticles and the carbon nanoparticles and uniform surface coating. Therefore, the CNT/Au/ESM shows excellent photo-thermal conversion performance, and the temperature is basically stabilized to be about 116 ℃ after 5min of illumination. The Ag/CNT/ESM sample also shows good photo-thermal conversion performance, the temperature is rapidly increased after illumination, and the temperature is stabilized at about 115 ℃ after 5 min. The gold nanoparticles and the silver nanoparticles have Localized Surface Plasmon Resonance (LSPR), can enhance the photothermal conversion efficiency of the composite eggshell membrane in a visible light region, and can quickly and efficiently convert light energy into heat energy under the synergistic action of the gold nanoparticles and the silver nanoparticles and the carbon nanotubes. The eggshell membrane serving as a green biological membrane has good biocompatibility, shows excellent photothermal conversion performance under the composite of two photothermal conversion materials of a carbon nano tube and a gold nano particle or a silver nano particle and the synergistic effect of the two photothermal conversion materials, and has great application potential in the aspects of photothermal treatment and drug release of diseases.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the noble metal-eggshell membrane photothermal material is characterized by comprising the following steps:
adding the eggshell membrane into the noble metal solution, using aldehyde group on the eggshell membrane as a reducing agent, heating in a water bath for reaction to reduce the noble metal, and drying to obtain the eggshell membrane loaded with the noble metal;
adding the eggshell membrane loaded with noble metal into the carbon nano tube solution, ultrasonically oscillating, dispersing and drying to obtain a noble metal-eggshell membrane photothermal material;
or, comprising the steps of:
adding the eggshell membrane into the carbon nano tube solution, performing ultrasonic oscillation dispersion, and drying to obtain the eggshell membrane loaded with the carbon nano tubes;
adding the eggshell membrane loaded with the carbon nano tube into the noble metal solution, using aldehyde group on the eggshell membrane as a reducing agent, heating in a water bath for reaction to reduce the noble metal, and drying to obtain the noble metal-eggshell membrane photothermal material.
2. The method for preparing a noble metal-eggshell membrane photothermal material as claimed in claim 1, wherein the noble metal solution comprises at least one of chloroauric acid solution and silver nitrate solution.
3. The method for preparing the noble metal-eggshell membrane photothermal material as claimed in claim 1, wherein the method for preparing the carbon nanotube solution comprises the following steps: adding the carbon nano tube into an alcohol solvent, and dispersing to obtain a carbon nano tube solution.
4. The method for preparing a noble metal-eggshell membrane photothermal material as claimed in claim 3, wherein the alcohol solvent comprises at least one of methanol, ethanol and glycerol.
5. The method for preparing a noble metal-eggshell membrane photothermal material as claimed in claim 1, wherein the reaction temperature of the water bath heating is 40-95 ℃ and the reaction time is 2-12 h.
6. The method for preparing noble metal-eggshell membrane photothermal material as claimed in claim 1, wherein the eggshell membrane is added to the noble metal solution, and the noble metal solution is reduced by heating in water bath, wherein the noble metal solution has a concentration of 1 x 10 -4 ～1.5×10 -4 mol/L, the mass volume ratio of the eggshell membrane to the noble metal solution is (0.1-0.3) g, (50-200) mL.
7. Noble metal-egg according to claim 1The preparation method of the shell membrane photo-thermal material is characterized in that the egg shell membrane loaded with the carbon nano tubes is added into a noble metal solution, and in the step of reducing the noble metal by heating reaction in water bath, the concentration of the noble metal solution is 1 multiplied by 10 -4 ～1.5×10 -4 mol/L, the mass volume ratio of the eggshell membrane to the noble metal solution is (0.1-0.3) g, (50-200) mL.
8. The method of claim 1, wherein the concentration of the carbon nanotube solution is 1-3 g/L.
9. A noble metal-eggshell membrane photothermal material, which is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the noble metal-eggshell membrane photothermal material prepared by the preparation method according to any one of claims 1 to 8 or the noble metal-eggshell membrane photothermal material according to claim 9 in seawater evaporation, photothermal therapy and drug release.
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