CN115212306B - 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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Classifications
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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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Environmental & Geological Engineering (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a noble metal-eggshell membrane photo-thermal material, and a preparation method and application thereof. According to the preparation method of the noble metal-eggshell membrane photo-thermal material, the noble metal nano particles are successfully assembled on the eggshell membrane by in-situ generation and electrostatic self-assembly, and then the carbon nano tubes are successfully assembled on the sample by using an ultrasonic dispersion method. The noble metal-eggshell membrane photo-thermal material prepared by the invention has excellent photo-thermal 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 photo-thermal conversion efficiency of the composite eggshell membrane in a visible light region, and can be used for converting light energy into heat energy rapidly and efficiently by synergistic effect with the carbon nano tubes. The noble metal-eggshell membrane photo-thermal material has excellent photo-thermal conversion performance and has great application potential in the aspects of photo-thermal 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 capable of absorbing sunlight and converting the sunlight into heat energy for accelerating water evaporation, and can be used in various fields such as sea water desalination, wastewater treatment and the like. However, the conversion temperature of the solar photo-thermal conversion materials is below 100 ℃ at present, and in order to seek wider temperature variation, the materials must be improved.
Carbon nanotubes are one type of plasmonic material, but they have a special LSPR effect with noble metal nanoparticles to cause a different mechanism for converting radiation-absorbing light into thermal energy. The material of carbon nano tube is the same as the photo-thermal conversion mechanism of organic material, mainly through electron transition in molecule, thereby causing the effect of photo-thermal conversion. Carbon nanotubes have characteristics of light weight, small size with high aspect ratio, good tensile strength, good conductive properties, chemical stability, and the like, so that they are applied in aviation, communication, electronic components, medicine, and the like. The carbon nano tube also has outstanding advantages in thermal performance, ultrahigh thermal conductivity and stable thermal performance, and is helpful for solving the problems of thermal management and heat dissipation. The black material has a wide light absorption range, and the carbon nano tube has black color, so that the support is provided for the strong light absorption in the visible-near infrared region, and the light energy can be quickly converted into heat energy.
However, no photo-thermal conversion material is prepared by using carbon nanotubes, so the photo-thermal conversion material can be prepared by using carbon nanotubes to increase the temperature variation range.
Disclosure of Invention
In view of the above, the invention provides a noble metal-eggshell membrane photo-thermal material, and a preparation method and application thereof, so as to solve or partially solve the technical problems existing in the prior art.
In a first aspect, the invention provides a preparation method of a noble metal-eggshell membrane photo-thermal material, comprising the following steps:
adding eggshell membrane into noble metal solution, using aldehyde group on eggshell membrane as reducer, heating in water bath to react to reduce noble metal, and drying to obtain eggshell membrane loaded with noble metal;
adding the noble metal-loaded eggshell membrane into the carbon nanotube solution, performing ultrasonic oscillation dispersion, and drying to obtain a noble metal-eggshell membrane photo-thermal material;
or, the method comprises the following steps:
adding the eggshell membrane into the carbon nanotube solution, performing ultrasonic oscillation dispersion, and drying to obtain the eggshell membrane loaded with the carbon nanotubes;
adding the eggshell membrane loaded with the carbon nano tube into a noble metal solution, using aldehyde groups on the eggshell membrane as a reducing agent, carrying out water bath heating reaction to reduce noble metal, and drying to obtain the noble metal-eggshell membrane photo-thermal material.
Preferably, the noble metal-eggshell membrane photo-thermal material is prepared by a method that 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 photo-thermal material, the preparation method of the carbon nanotube solution is as follows: adding the carbon nano tube into an alcohol solvent, and dispersing to obtain the carbon nano tube solution.
Preferably, the preparation method of the noble metal-eggshell membrane photo-thermal material comprises the step of preparing the noble metal-eggshell membrane photo-thermal material, wherein the alcohol solvent comprises at least one of methanol, ethanol and glycerol.
Preferably, the preparation method of the noble metal-eggshell membrane photo-thermal material has the water bath heating reaction temperature of 40-95 ℃ and the reaction time of 2-12 h.
Preferably, in the preparation method of the noble metal-eggshell membrane photo-thermal material, eggshell membrane is added into noble metal solution, and in the step of reducing noble metal by water bath heating reaction, the concentration of noble metal solution is 1 multiplied by 10 -4 ～1.5×10 -4 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 photo-thermal material, the eggshell membrane loaded with the carbon nano tube is added into a noble metal solution, and in the step of reducing the noble metal through water bath heating reaction, the concentration of the noble metal solution is 1 multiplied by 10 -4 ～1.5×10 -4 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 photo-thermal 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 photo-thermal material prepared by the preparation method.
In a third aspect, the invention also provides a noble metal-eggshell membrane photo-thermal material prepared by the preparation method or application of the noble metal-eggshell membrane photo-thermal material in seawater evaporation, photo-thermal treatment and drug release.
The noble metal-eggshell membrane photo-thermal material and the preparation method thereof have the following beneficial effects compared with the prior art:
according to the preparation method of the noble metal-eggshell membrane photo-thermal material, the noble metal nano particles are successfully assembled on the eggshell membrane by in-situ generation and electrostatic self-assembly, and then the carbon nano tubes are successfully assembled on the sample by using an ultrasonic dispersion method. In the process of generating noble metal nano particles in situ, 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. The noble metal-eggshell membrane photo-thermal material prepared by the invention has excellent photo-thermal conversion performance, and the temperature is basically stabilized at about 115-116 ℃ after 5min of illumination. Noble metal nano particles (such as gold nano particles and silver nano particles) have a Localized Surface Plasmon Resonance (LSPR) effect, so that the photo-thermal conversion efficiency of the composite eggshell membrane in a visible light region can be enhanced, and the composite eggshell membrane can be cooperated with a carbon nano tube to quickly and efficiently convert light energy into heat energy. The eggshell membrane is used as a green biological membrane, has better biocompatibility, and has great application potential in the aspects of photo-thermal treatment and drug release of diseases under the synergistic effect of the eggshell membrane and two photo-thermal conversion materials of carbon nano tubes and noble metal nano particles.
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 evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is an optical image of the noble metal-eggshell membrane photothermal material prepared in examples 1 to 3, comparative examples 1 to 2, eggshell membrane photothermal material prepared in comparative example 3, and eggshell membrane of example 1 according to the present invention;
FIG. 2 is a graph showing the surface morphology of the noble metal-eggshell membrane photo-thermal material prepared in examples 1 to 3, comparative example 1, comparative example 3, and the scanning electron microscope image of the noble metal-eggshell membrane photo-thermal material in example 2;
FIG. 3 is an ultraviolet-visible diffuse reflection absorption spectrum of the noble metal-eggshell membrane photothermal material prepared in examples 1 to 3, comparative examples 1 to 2, eggshell membrane photothermal material prepared in comparative example 3, and eggshell membrane in example 1 according to the present invention;
FIG. 4 is an X-ray photoelectron spectrum of the noble metal-eggshell membrane photothermal material prepared in examples 1 to 3 of the present invention, and the eggshell membrane surface in example 1;
FIG. 5 is a graph showing the thermogravimetric profile of the noble metal-eggshell membrane photo-thermal material prepared in examples 1 to 3, comparative examples 1 to 2, eggshell membrane photo-thermal material prepared in comparative example 3, and eggshell membrane of example 1 according to the present invention;
FIG. 6 is a Raman scattering spectrum of the noble metal-eggshell membrane photothermal material in examples 2 to 3 of the present invention;
FIG. 7 is an infrared thermal imaging diagram of the noble metal-eggshell membrane photothermal material prepared in examples 1 to 3, comparative examples 1 to 2, eggshell membrane photothermal material prepared in comparative example 3, and eggshell membrane of example 1 according to the present invention;
FIG. 8 is a graph showing the trend of temperature change under irradiation of a xenon lamp in examples 1 to 3, the noble metal-eggshell membrane photo-thermal material prepared in comparative examples 1 to 2, the eggshell membrane photo-thermal material prepared in comparative example 3, and the eggshell membrane prepared in example 1 according to the present invention;
FIG. 9 is a graph showing the heating and cooling cycle of the noble metal-eggshell membrane photothermal material according to examples 2 to 3 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the embodiments of the present invention, but it should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The embodiment of the application provides a preparation method of a noble metal-eggshell membrane photo-thermal material, which comprises the following steps:
s1, adding eggshell membranes into a noble metal solution, using aldehyde groups on the eggshell membranes as a reducing agent, carrying out a water bath heating reaction to reduce noble metals, and drying to obtain the eggshell membranes loaded with the noble metals;
s2, adding the noble metal-loaded eggshell membrane into the carbon nanotube solution, performing ultrasonic oscillation dispersion, and drying to obtain a noble metal-eggshell membrane photo-thermal material;
or, the method comprises the following steps:
s1, adding eggshell membranes into a carbon nanotube solution, performing ultrasonic oscillation dispersion, and drying to obtain eggshell membranes loaded with carbon nanotubes;
s2, adding the eggshell membrane loaded with the carbon nano tube into a noble metal solution, using aldehyde groups on the eggshell membrane as a reducing agent, carrying out a water bath heating reaction to reduce noble metal, and drying to obtain the noble metal-eggshell membrane photo-thermal material.
It should be noted that, in the embodiment of the present application, the eggshell membrane refers to: after breaking the eggs, the white semitransparent substances attached to the eggshells are called eggshell membranes; the preparation method mainly comprises two technical schemes, namely, the first scheme: adding eggshell membrane into noble metal solution, using aldehyde group on eggshell membrane as reducer, heating in water bath to react to reduce noble metal, drying to obtain noble metal-loaded eggshell membrane, adding noble metal-loaded eggshell membrane into carbon nanotube solution, ultrasonic oscillating for dispersion, and drying to obtain noble metal-eggshell membrane photo-thermal material; second kind: adding the eggshell membrane into the carbon nanotube solution, performing ultrasonic oscillation dispersion, and drying to obtain the eggshell membrane loaded with the carbon nanotubes; adding the eggshell membrane loaded with the carbon nano tube into a noble metal solution, using aldehyde groups on the eggshell membrane as a reducing agent, carrying out water bath heating reaction to reduce noble metal, and drying to obtain a noble metal-eggshell membrane photo-thermal material; the noble metal-eggshell membrane photo-thermal material prepared by the two schemes has excellent photo-thermal conversion efficiency, and the synergistic effect of the noble metal nano particles and the carbon nano tubes enables the conversion performance of the double-function composite membrane to be further improved, so that the method is provided in the aspect of more efficiently utilizing solar clean energy, and the method has application prospects in the aspects of sea water evaporation, photo-thermal treatment and the like.
In some embodiments, the noble metal solution comprises at least one of chloroauric acid solution and silver nitrate solution, the chloroauric acid solution and the silver nitrate solution are both aqueous solutions, and the preparation method of the chloroauric acid solution or the silver nitrate solution is as follows: and respectively adding chloroauric acid or silver nitrate into water to obtain chloroauric acid solution or silver nitrate solution.
Specifically, for the first technical scheme, aldehyde groups on eggshell membranes are used as reducing agents, chloroauric acid solution is reduced, gold nanoparticles are further formed and loaded on the eggshell membranes, or silver nanoparticles are loaded on the eggshell membranes by using an electrostatic self-assembly principle, then the eggshell membranes loaded with the gold nanoparticles and the silver nanoparticles are placed in carbon nanotube solution, ultrasonic oscillation is carried out for dispersion, carbon nanotubes are coated on the surfaces of eggshell membrane fibers by Van der Waals force, and both the silver nanoparticles and the carbon nanotubes can be well coated on the eggshell membrane fibers; however, after the gold nanoparticles are assembled, the carbon nanotubes are difficult to coat due to the steric hindrance effect, so that a second technical scheme can be adopted to solve the problem: firstly adding eggshell membrane into a carbon nano tube solution, carrying out ultrasonic oscillation dispersion and drying to enable the carbon nano tube to be coated on the surface of eggshell membrane fiber through Van der Waals force, then adding the eggshell membrane fiber coated with the carbon nano tube into chloroauric acid solution, utilizing aldehyde groups on the eggshell membrane as a reducing agent, carrying out water bath heating reaction to reduce gold, and drying, namely, loading gold nano particles on the eggshell membrane coated with the carbon nano tube, thereby finally obtaining the noble metal-eggshell membrane photo-thermal material.
In some embodiments, the reducing agent includes at least one of trisodium citrate, sodium borohydride.
In some embodiments, the method of preparing the carbon nanotube solution is: adding the carbon nano tube into an alcohol solvent, and dispersing to obtain the carbon nano tube solution.
Specifically, the alcohol solvent used includes 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 hours.
In some embodiments, the eggshell membrane is added to a noble metal solution, and the aldehyde groups on the eggshell membrane are used as reducing agents, and in the step of reducing the noble metal by water bath heating reaction, the concentration of the noble metal solution is 1 multiplied by 10 -4 ～1.5×10 -4 The mass volume ratio of the reducer to the noble metal solution is (0.1-0.3) g (50-200) mL.
In some embodiments, the eggshell membrane loaded with carbon nanotubes is added into a noble metal solution, and the aldehyde groups on the eggshell membrane are used as a reducing agent, and in the step of reducing the noble metal by water bath heating reaction, the concentration of the noble metal solution is 1×10 -4 ～1.5×10 -4 The mass volume ratio of the reducer 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 1-3 g/L.
In some embodiments, the sonication dispersion time is from 20 to 40 minutes.
Based on the same inventive concept, the embodiment of the application also provides a noble metal-eggshell membrane photo-thermal material, which is prepared by adopting the preparation method.
Based on the same inventive concept, the embodiment of the application also provides application of the noble metal-eggshell membrane photo-thermal material prepared by the preparation method in seawater evaporation, photo-thermal treatment and drug release.
The preparation method of the noble metal-eggshell membrane photo-thermal material is further described in the following specific examples. This section further illustrates the summary of the invention in connection with specific embodiments, but 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 specifically stated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
The multiwall carbon nanotubes (CNTs. Gtoreq.90.0%, inner diameter about 5-10nm, outer diameter about 20-40nm, length about 10-30 μm) in the following examples and comparative examples were purchased from Allatin (Shanghai, china).
The following examples and comparative eggshell membranes (noted Pristine ESM) were prepared as follows: and (3) peeling off eggshells of fresh eggs by using tweezers to obtain eggshell membrane fibers, 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 photo-thermal material, which comprises the following steps:
s1, adding eggshell membrane into 150mL with concentration of 1.5X10 -4 Reacting the chloroauric acid solution with mol/L at 95 ℃ for 2 hours, and drying at room temperature to obtain an eggshell membrane loaded with 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;
s3, adding the eggshell membrane loaded with the gold nanoparticles in the step S1 into 150mL of 2g/L carbon nanotube solution, performing ultrasonic oscillation dispersion for 30min, and drying at room temperature to obtain the noble 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 photo-thermal 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;
s2, 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 loaded with the carbon nanotubes;
s3, adding the eggshell membrane loaded with the carbon nano tubes in the step S2 to 150mL with the concentration of 1.5X10 -4 And (3) reacting the chloroauric acid solution with mol/L at 95 ℃ for 2 hours, and drying at room temperature to obtain the noble metal-eggshell membrane photo-thermal material (marked as CNT/Au/ESM).
Example 3
The embodiment of the application provides a preparation method of a noble metal-eggshell membrane photo-thermal material, which comprises the following steps:
s1, firstly, preparing the concentration of 1 multiplied by 10 -4 mol/L silver nitrate solution is then added with 1ml of 1X 10 concentration -1 1mL of trisodium citrate aqueous solution having a concentration of 8X 10 was slowly added with vigorous stirring -3 The yellow silver seed solution is obtained by mol/L sodium borohydride aqueous solution, and then is placed in a sodium lamp (NAV-T70, purchased in China)The company of oslan illumination limited) for 12 hours, inducing a blue silver seed solution; then placing the eggshell membrane into a blue silver seed solution, reacting for 12 hours at the temperature of 40 ℃, and drying at room temperature to obtain the eggshell membrane loaded with silver nano particles;
s2, adding the multi-wall carbon nano tube into ethanol to obtain a carbon nano tube solution with the concentration of 2 g/L;
s3, adding the eggshell membrane loaded with the silver nano particles in the step S1 into 150mL of 2g/L carbon nano tube solution, performing ultrasonic oscillation dispersion for 30min, and drying at room temperature to obtain the noble metal-eggshell membrane photo-thermal material (marked as Ag/CNT/ESM).
Comparative example 1
The comparative example provides a preparation method of a noble metal-eggshell membrane photo-thermal material, which comprises the following steps:
s1, adding the eggshell membrane into 150mL chloroauric acid solution with the concentration of 3mol/L, reacting for 2 hours at the temperature of 95 ℃, and drying at room temperature to obtain the eggshell membrane loaded with gold nanoparticles, namely the noble metal-eggshell membrane photo-thermal material (recorded as Au/ESM).
Comparative example 2
The comparative example provides a preparation method of a noble metal-eggshell membrane photo-thermal material, which comprises the following steps:
s1, firstly, preparing the concentration of 1 multiplied by 10 -4 1ml of 1X 10 concentration silver nitrate solution was added -1 1mL of trisodium citrate aqueous solution having a concentration of 8X 10 was slowly added with vigorous stirring -3 The sodium borohydride aqueous solution with mol/L is used for obtaining yellow silver seed solution, and then the silver seed solution is placed under a sodium lamp (NAV-T70, purchased from Eurana illumination Co., ltd., china) for irradiation for 12 hours, and is induced to obtain blue silver seed solution; then putting the eggshell membrane into blue silver seed solution, reacting for 12 hours at 40 ℃, and drying at room temperature to obtain the eggshell membrane loaded with silver nano particles, namely the noble metal-eggshell membrane photo-thermal material (marked as Ag/ESM).
Comparative example 3
The comparative example provides a preparation method of an eggshell membrane photo-thermal 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;
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 photo-thermal material (marked as CNT/ESM).
Performance testing
The optical images 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 are shown in fig. 1.
The natural eggshell membrane without treatment in fig. 1 is white (Pristine ESM in fig. 1). Whereas the eggshell membrane photo-thermal material CNT/ESM prepared in comparative example 3 was black, since the carbon nanotubes were black. In addition, the carbon nano tube shows good adhesiveness, and can be well fixed on the surface of the eggshell membrane after being washed by water. In comparative example 2, the surface of the eggshell membrane Ag/ESM which is formed by electrostatic self-assembly and loaded with silver nano particles is blue; in example 3, the Ag/CNT/ESM was obtained by re-loading the carbon nanotubes on the Ag/ESM, and the color was changed from blue to black, which indicates that the carbon nanotubes were successfully assembled on the surface of eggshell membrane fibers. In comparative example 1, eggshell membrane Au/ESM loaded with gold nanoparticles is generated in situ, the surface of the eggshell membrane Au/ESM is brownish red, and the color distribution is more uniform; in example 1, gold nanoparticles were reduced in situ, and then carbon nanotubes were assembled to obtain a bifunctional complex film Au/CNT/ESM, the carbon nanotubes could not be uniformly supported on the surface of the film, and the color was close to that of an eggshell film Au/ESM with gold nanoparticles supported only, which means that only a small amount of carbon nanotubes were supported on the surface of the eggshell film, and the assembly effect was poor. In example 2, the carbon nanotubes were assembled first, and then the gold nanoparticles were reduced in situ by using the reduction performance of aldehyde groups on eggshell membrane, so as to obtain a uniformly loaded bifunctional composite membrane, in which the carbon nanotubes and gold nanoparticles were uniformly distributed on the eggshell membrane, as shown in fig. 1 as CNT/Au/ESM.
The noble metal-eggshell membrane photo-thermal material prepared in examples 1 to 3, comparative example 1, eggshell membrane photo-thermal material prepared in comparative example 3, and the surface morphology of eggshell membrane were characterized by thermal field scanning electron microscopy (FESEM, JEOL JSM-7800F); the EDS spectrum element distribution of the noble metal-eggshell membrane photothermal material of example 2 was analyzed, and the result is shown in fig. 2.
In fig. 2, (a) is the surface morphology of untreated eggshell membrane Pristine ESM, (B) is the surface morphology of eggshell membrane photo-thermal material CNT/ESM in comparative example 3, (C) is the surface morphology of noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM in example 3, (D) is the surface morphology of noble metal-eggshell membrane photo-thermal material Au/ESM in comparative example 1, (E) is the surface morphology of noble metal-eggshell membrane photo-thermal material Au/CNT/ESM in example 1, (F) is the surface morphology of noble metal-eggshell membrane photo-thermal material CNT/Au/ESM in example 2, and (G) is the EDS energy spectrum element profile of noble metal-eggshell membrane photo-thermal 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 staggered connections between fibers, and has a porous structure, similar to a nonwoven fabric. From fig. 2 (a), it can be observed that the surface of the natural eggshell membrane Pristine ESM fiber is relatively clean. As can be seen from fig. 2 (B), in comparative example 3, the eggshell membrane photo-thermal material CNT/ESM, the carbon nanotubes were uniformly coated on the surface of the eggshell membrane fiber, and only a small portion of the carbon nanotubes were aggregated. As shown in fig. 2 (C), the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM carbon nanotubes in example 3 were distributed uniformly on the surface of the eggshell membrane fiber, which indicates that the carbon nanotubes were successfully coated on the surface of the eggshell membrane fiber and the silver nanoparticles were also coated inside. As can be seen from 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 photo-thermal material Au/CNT/ESM in example 1, carbon nanotubes are difficult to coat on the eggshell membrane fiber, only a small amount of carbon nanotubes are unevenly distributed, aggregation is easy to occur, and the color of the optical photograph is similar to that of the Au/ESM composite membrane. Because eggshell membrane contains a large number of amino acids and saccharides, the eggshell membrane contains a large number of aldehyde groups (R-CHO), and the aldehyde groups can serve as reducing agents to reduce a large number of gold ions into gold nanoparticles and generate on the surfaces of eggshell membrane fibers. Due to the formation of 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, the carbon nanotubes were coated on the surface of the eggshell membrane in a large amount and uniformly, and the carbon nanotubes were not detached after the gold nanoparticles were generated in situ. Part of gold nano particles are uniformly dispersed on the surface of the eggshell membrane which is not covered by the carbon nano tube, and the other part of gold nano particles are agglomerated into spheres and are uniformly distributed on the surface of the eggshell membrane.
As can be seen from fig. 2 (G), in EDS of the noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2, C, N and Au elements are uniformly distributed on the surface, which further confirms that gold nanoparticles are successfully assembled on eggshell membrane fibers.
The optical properties of the different composite eggshell membrane samples were characterized using ultraviolet-visible-near infrared spectrometer (Solidspec-3700, shimadzu) to measure the spectra of the noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3, the eggshell membrane photothermal materials prepared in comparative example 3, and the eggshell membrane in example 1, and the results are shown in fig. 3.
Specifically, fig. 3 a shows untreated eggshell membrane Pristine ESM in example 1, b shows noble metal-eggshell membrane photo-thermal material Ag/ESM in comparative example 2, c shows noble metal-eggshell membrane photo-thermal material Au/ESM in comparative example 1, d shows noble metal-eggshell membrane photo-thermal material CNT/Au/ESM in example 2, e shows noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM in example 3, f shows eggshell membrane photo-thermal material CNT/ESM in comparative example 3, and g shows noble metal-eggshell membrane photo-thermal material Au/CNT/ESM in example 1.
As can be seen from fig. 3, the untreated eggshell membrane Pristine ESM of example 1 has 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 photo-thermal material CNT/ESM in comparative example 3, the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM in example 3, and the noble metal-eggshell membrane photo-thermal material CNT/Au/ESM in example 2 was 200 to 800nm, which covers almost the entire visible region, due to the coverage of the sample surface with carbon nanotubes. The carbon nanotubes are black and have a broad absorption spectrum, so that the absorption efficiency of light is high. This property is favorable for the sample to absorb light energy and perform photo-thermal conversion. In example 1, the noble metal-eggshell membrane photothermal material Au/CNT/ESM has a relatively high gold nanoparticle content because of a small content of surface-coated carbon nanotubes, so that the noble metal-eggshell membrane photothermal material is more characterized by ultraviolet absorption of gold nanoparticles, and a 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 photo-thermal material Au/ESM at 540nm in comparative example 1, the gold nanoparticle absorption band of the noble metal-eggshell membrane photo-thermal material Au/CNT/ESM in example 1 has blue shift, which indicates that the carbon nanotube can regulate and control the LSPR effect of the gold nanoparticle, so that the gold nanoparticle exhibits light absorption effect in 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 esclab 250 XL) system, and the results are shown in fig. 4.
In fig. 4, (a) is XPS full spectrum of the noble metal-eggshell membrane photo-thermal material prepared in examples 1 to 3 (where a is XPS full spectrum of the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM in example 3, B is XPS full spectrum of the noble metal-eggshell membrane photo-thermal material Au/CNT/ESM in example 1, C is XPS full spectrum of the noble metal-eggshell membrane photo-thermal material CNT/Au/ESM in example 2), (B) is C1s spectrum of the untreated eggshell membrane Pristine ESM in example 1, (C) is C1s spectrum of the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM in example 3, (D) is C1s spectrum of the noble metal-eggshell membrane photo-thermal material CNT/Au/ESM in example 2, (E) is Ag3D of the noble metal-eggshell membrane photo-thermal material CNT/ESM in example 3, and (F) is a C1s spectrum of the noble metal-eggshell membrane photo-thermal material Au/ESM in example 1.
As can be seen from FIG. 4, the noble metal-eggshell membrane photothermal materials (Ag/CNT/ESM, au/CNT/ESM and CNT/Au/ESM) prepared in examples 1 to 3 have a surface main element C, N, O, their binding energies are 285.08eV, 400.08eV and 532.08eV, respectively, and C, N, O are the basic composition of proteinsAn element. In addition, in example 3, there were two characteristic peaks at about 368.18eV and 573.61eV of the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM, corresponding to binding energies Ag3d and Ag3p, respectively, which indicates that the presence of silver nanoparticles can be detected on the surface of the composite membrane fiber, indicating that the presence of silver nanoparticles on the surface of the eggshell membrane fiber is not affected after coating the carbon nanotubes. FIG. 4 (E) shows the 3d bimodal splitting of Ag in the noble metal-eggshell membrane photothermal material Ag/CNT/ESM of example 3, representing Ag3d at 368.08eV and 374.08eV, respectively 5/2 And Ag3d 3/2 Binding energy further indicates the presence of elemental silver. 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 both present two characteristic peaks at about 84.18eV and 335.18eV, which correspond to Au4f and Au4d, respectively, demonstrating the presence of a large number of gold nanoparticles on the surface of the composite membrane. Wherein the Au4F peak is composed of two characteristic peaks at 84.18eV and 87.4eV, corresponding to Au4F7 and Au4F5, respectively (shown in (F) of fig. 4). The C1s bands of the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM in example 3 and the noble metal-eggshell membrane photo-thermal material CNT/Au/ESM in example 2 can fit five peaks of 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 peaks of the C-C bonds correspond to defects and aromatic hydrocarbons in the conjugated rings of the carbon nanotubes.
The noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3, comparative examples 1 to 2, eggshell membrane photothermal material prepared in comparative example 3, and eggshell membrane thermogravimetric curves of example 1 were tested, and the results are shown in fig. 5. The specific test method comprises the following steps: obtained by characterization of thermogravimetric analysis (TAG, perkin Elmer's Diamond TG/DTA system) under argon atmosphere at a heating rate of 10℃for min -1 。
Specifically, fig. 5 a shows untreated eggshell membrane Pristine ESM in example 1, b shows noble metal-eggshell membrane photothermal material Ag/ESM in comparative example 2, c shows eggshell membrane photothermal material CNT/ESM in comparative example 3, d shows noble metal-eggshell membrane photothermal material Ag/CNT/ESM in example 3, e shows noble metal-eggshell membrane photothermal material Au/ESM in comparative example 1, f shows noble metal-eggshell membrane photothermal material Au/CNT/ESM in example 1, and g shows noble metal-eggshell membrane photothermal material CNT/Au/ESM in example 2.
The weight loss of the eggshell membrane sample below 105 ℃ is due to evaporation of the moisture bound to the eggshell membrane sample. After the temperature reached 233 ℃, all material weight loss began to accelerate, probably due to the onset of thermal degradation of collagen. The untreated eggshell membrane Pristine ESM of example 1 was decomposed to a steady state at approximately 500℃and then warmed to 800℃with a residual mass of approximately 26.19%. Only the eggshell membrane of the carbon nano tube is coated on the eggshell membrane fiber, and the residual mass percentage is 28.86% after the temperature reaches 800 ℃. Since carbon nanotubes can withstand high temperatures, and can hardly be pyrolyzed in this temperature range, the amount of CNT/ESM on top can be found to be about 2.67% by comparing the mass percentage of CNT/ESM residues of the eggshell membrane photo-thermal material prepared in comparative example 3 with untreated eggshell membrane Pristine ESM. In comparative example 1, the noble metal-eggshell membrane photo-thermal material Au/ESM, after the temperature reaches 800 ℃, the residual mass percentage is about 40.90%, and the gold nanoparticles cannot be pyrolyzed at high temperature, which indicates 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 under an air atmosphere. After the temperature reached 800 ℃, the mass percentage of the residual CNT/Au/ESM of the noble metal-eggshell membrane photo-thermal material in example 2 was about 47.42%, and the content of the carbon nanotubes on the CNT/Au/ESM dual-function composite membrane was calculated to be about 6.52% by comparison with the mass percentage of the residual Au/ESM composite membrane. The final residual mass percentage of the noble metal-eggshell membrane photothermal material Au/CNT/ESM in example 1 was about 41.79%, and the amount of the above carbon nanotubes was about 0.89% calculated by the same method, and this data shows that the content of carbon nanotubes on the Au/CNT/ESM composite film was very small, as in the previous analysis results. The residual mass percentage of the noble metal-eggshell membrane photo-thermal material Ag/ESM in 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 untreated eggshell membrane Pristine ESM. The mass percent of the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM residue in example 3 was about 35.10%, and the above residue was calculated to be about 7.83%.
Raman scattering spectra of noble metal-eggshell membrane photothermal material CNT/Au/ESM (shown in (B) of fig. 6) in example 2 and noble metal-eggshell membrane photothermal material Ag/CNT/ESM (shown in (a) of fig. 6) in example 3 were tested, and the results are shown in fig. 6. Specifically, raman spectrum (Raman) was measured by using an INVIA confocal microscopic Raman spectrometer from Renishaw company, the excitation light source was a He-Ne laser, the wavelength was 633nm, the power was 0.5%, and the integration time was 10s.
Carbon-based materials generally have significant raman activity, so raman spectroscopy is used to characterize dual-functionalized composite films of silver (gold) nanoparticles and carbon nanotubes. Under 633nm excitation light, it was observed that the noble metal-eggshell membrane photothermal material Ag/CNT/ESM of example 3 was at 1320cm -1 Characteristic peaks appear at the positions, which are regarded as D bands of the carbon nanotubes and correspond to structural defects in the carbon nanotubes; 1568cm -1 The characteristic peak corresponds to the G band and is sp of the carbon nano tube 3 Characteristic peaks of the structure. The relative intensities of the D and G bands, r= (ID/IG), and the structural defects and sp in the carbon nanotube sample 3 The number of hybridized carbon atoms can provide direct information about the degree of sidewall functionalization. The R value of the treated sample was about 0.84, which was substantially unchanged from the original carbon nanotubes, indicating that the original structure of the carbon nanotubes was maintained after the functional groups on the surfaces of the carbon nanotubes and eggshell membrane were combined. The Raman spectrum of the noble metal-eggshell membrane photothermal material CNT/Au/ESM of example 2 also shows a similar spectrum at 1328cm -1 The characteristic peak is shown as a D band on the carbon nanotubes, which is caused by defects on the carbon nanotubes, and the D band is related to the hybrid vibration mode associated with the edges of the graphite layer, which indicates that there is some disorder in the structure of the carbon nanotubes, and this band is also called a disorder band or defect band. At 1579cm -1 The characteristic peaks shown here represent the G bands of carbon nanotubes, also caused by defects.
The noble metal-eggshell membrane photothermal materials prepared in examples 1 to 3, comparative examples 1 to 2, eggshell membrane photothermal materials prepared in comparative example 3, and eggshell membrane photothermal conversion properties in example 1 were tested. Specifically, the photo-thermal conversion performance of the eggshell membrane photo-thermal material is completed in an environment simulating sunlight. Eggshell membrane photo-thermal material was placed on a quartz plate, under a xenon lamp (λ=350-780 nm) as a simulated solar light source), at a distance of 30cm from the xenon lamp. A small thermal imaging camera was used to record the temperature change of the eggshell membrane sample, with data of temperature change recorded every 5min, and temperature change over 30 min.
Fig. 7 shows infrared thermal imaging images of different eggshell membrane photothermal materials under irradiation of a xenon lamp for 0, 2 and 30min before and after illumination. After the eggshell membrane is illuminated, the temperature is improved, a heat distribution area is observed, a sample compounded with carbon nanotubes can be seen, the temperature is obviously improved, and heat is concentrated on the sample. This is because the carbon nanotubes have a high heat conversion ability for near infrared light, and can generate a local high temperature as a photo-thermal conversion material.
Fig. 8 shows the trend of temperature change under irradiation of a xenon lamp of the noble metal-eggshell membrane photo-thermal materials prepared in examples 1 to 3, comparative examples 1 to 2, eggshell membrane photo-thermal material prepared in comparative example 3, and eggshell membrane prepared in example 1.
Specifically, fig. 8 a shows untreated eggshell membrane Pristine ESM of example 1, b shows noble metal-eggshell membrane photo-thermal material Ag/ESM of comparative example 2, c shows noble metal-eggshell membrane photo-thermal material Au/ESM of comparative example 1, d shows eggshell membrane photo-thermal material CNT/ESM of comparative example 3, e shows noble metal-eggshell membrane photo-thermal material Au/CNT/ESM of example 1, f shows noble metal-eggshell membrane photo-thermal material CNT/Au/ESM of example 2, and g shows noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM of example 3.
As can be seen from fig. 8, the untreated eggshell membrane Pristine ESM temperature of example 1 increased from 30.5℃to 46.2℃after 30min of illumination, with only 15.7 ℃. Under the same illumination conditions, the noble metal-eggshell membrane photo-thermal material Au/ESM in comparative example 1 was increased to 75.1 ℃, the eggshell membrane photo-thermal material CNT/ESM in comparative example 3 was increased to 108.9 ℃, the noble metal-eggshell membrane photo-thermal material Ag/ESM in comparative example 2 was increased to 73.9 ℃, and the noble metal-eggshell membrane photo-thermal material Au/CNT/ESM in example 1 was increased to 107.2 ℃, wherein the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM in example 3 and the noble metal-eggshell membrane photo-thermal material CNT/Au/ESM in example 2 were most obvious in temperature increase, reaching 116.8 ℃ and 116.3 ℃, respectively. The LSPR band of the silver nano particles is positioned at 603nm, the LSPR band of the gold nano particles is positioned at 528nm, the light absorption of a visible light region is facilitated, the carbon nano tube has a strong light absorption effect in a near infrared region, and the synergistic effect of the nano particles jointly enhances the photo-thermal conversion efficiency of the film.
The heating and cooling cycle diagrams of the noble metal-eggshell membrane photo-thermal material Ag/CNT/ESM in example 3 and the noble metal-eggshell membrane photo-thermal material CNT/Au/ESM in example 2 were tested as shown in fig. 9.
As can be seen from FIG. 9, in the noble metal-eggshell membrane photo-thermal material CNT/Au/ESM of example 2, after 30s of illumination, the temperature can reach 117.4 ℃, the temperature is basically stable along with the increase of illumination time, the cooling rate is also fast, after 5s of illumination stop, the temperature is quickly reduced to 39.2 ℃, and then the cooling rate is slowed down, and the room temperature is basically reached within 30 s. The noble metal-eggshell membrane photothermal material Ag/CNT/ESM of example 3 also exhibited such properties, and the rate of temperature rise and decrease was faster, and after 15 seconds of illumination, the temperature reached 117.1 ℃, continued illumination, the temperature rise was slower, the change was around 1 ℃, the light source was turned off, the temperature tended to drop suddenly, the temperature was reduced to 39 ℃ within 5 seconds, and the temperature was slowly stabilized in the range of room temperature with the increase of time. And after multiple circulation experiments, the sample basically has no change, the light-heat conversion capability is kept to be certain, and the method has the characteristic of repeated use. After adding the carbon nanotubes, the photo-thermal response of the CNT/Au/ESM and Ag/CNT/ESM dual-functional composite film samples is fast, can be raised to more than 100 ℃ in a few tens of seconds, and the cooling speed is also fast, which can be attributed to the high thermal conductivity of the carbon nanotubes and the strong visible-near infrared light absorption capability, thereby causing a fast illumination conversion response. The device has the characteristics of rapid temperature rise and reduction and obvious photo-thermal effect, and can have certain potential in the aspects of sea water desalination, drug release and the like.
In summary, the gold nanoparticles and silver nanoparticles are successfully assembled on eggshell membranes by in-situ generation and electrostatic self-assembly, and then the carbon nanotubes are successfully assembled on the sample by using an ultrasonic dispersion method. In the process of generating gold nano particles in situ, 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. When the double-functional eggshell membrane is used, gold nano particles are generated in situ, and then the carbon nano tubes are coated, so that the carbon nano tubes are difficult to attach to the eggshell membrane; the existence of the carbon nano tube does not influence the generation of gold nano particles, and the difunctional CNT/Au/ESM prepared by changing the processing sequence has high gold nano particles and carbon nano loading capacity and uniform surface coating. Therefore, the CNT/Au/ESM shows excellent photo-thermal conversion performance, and the temperature is basically stabilized at about 116 ℃ after 5min of illumination. The Ag/CNT/ESM sample also shows good photo-thermal conversion performance, and rapidly rises in temperature after illumination, and the temperature is stabilized at about 115 ℃ after 5 min. The gold nano particles and the silver nano particles have a Localized Surface Plasmon Resonance (LSPR) effect, so that the photo-thermal conversion efficiency of the composite eggshell membrane in a visible light region can be enhanced, and the composite eggshell membrane can be used for rapidly and efficiently converting light energy into heat energy through synergistic action with the carbon nano tubes. The eggshell membrane is used as a green biological membrane, has better biocompatibility, and has great application potential in the aspects of photothermal treatment of diseases and drug release under the synergistic effect of the eggshell membrane and two photothermal conversion materials of carbon nano tubes and gold nano particles or silver nano particles.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. The preparation method of the noble metal-eggshell membrane photo-thermal material is characterized by comprising the following steps of:
adding eggshell membrane into noble metal solution, using aldehyde group on eggshell membrane as reducer, heating in water bath to react to reduce noble metal, and drying to obtain eggshell membrane loaded with noble metal;
adding the noble metal-loaded eggshell membrane into the carbon nanotube solution, performing ultrasonic oscillation dispersion, and drying to obtain a noble metal-eggshell membrane photo-thermal material;
the noble metal solution is silver nitrate solution;
adding eggshell membrane into noble metal solution, and heating in water bath to reduce noble metal, wherein the concentration of noble metal solution is 1×10 -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;
the concentration of the carbon nano tube solution is 1-3 g/L;
the water bath heating reaction temperature is 40-95 ℃ and the reaction time is 2-12 h;
adding the carbon nano tube into an alcohol solvent, and dispersing to obtain a carbon nano tube solution;
or, the method comprises the following steps:
adding the eggshell membrane into the carbon nanotube solution, performing ultrasonic oscillation dispersion, and drying to obtain the eggshell membrane loaded with the carbon nanotubes;
adding the eggshell membrane loaded with the carbon nano tube into a noble metal solution, using aldehyde groups on the eggshell membrane as a reducing agent, carrying out water bath heating reaction to reduce noble metal, and drying to obtain a noble metal-eggshell membrane photo-thermal material;
the noble metal solution is chloroauric acid solution;
adding eggshell membrane loaded with carbon nanotubes into noble metal solution, and heating in water bath to reduce noble metal to obtain a solution with concentration of 1×10 -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;
the concentration of the carbon nano tube solution is 1-3 g/L;
the water bath heating reaction temperature is 40-95 ℃ and the reaction time is 2-12 h;
adding the carbon nano tube into an alcohol solvent, and dispersing to obtain the carbon nano tube solution.
2. The method for preparing a noble metal-eggshell membrane photothermal material as claimed in claim 1, wherein the alcohol solvent comprises at least one of methanol, ethanol, and glycerol.
3. A noble metal-eggshell membrane photo-thermal material, characterized in that it is prepared by the preparation method according to any one of claims 1-2.
4. Use of the noble metal-eggshell membrane photothermal material prepared by the preparation method according to any one of claims 1-2 or the noble metal-eggshell membrane photothermal material according to claim 3 in preparation of photothermal therapeutic drugs and evaporation of seawater.
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