CN114395375B - Metal organic framework-based photo-thermal composite phase change material and application thereof - Google Patents
Metal organic framework-based photo-thermal composite phase change material and application thereof Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/002—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches with controlled internal environment
- A41D13/005—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches with controlled internal environment with controlled temperature
- A41D13/0051—Heated garments
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The embodiment of the invention relates to the field of phase change materials, in particular to a metal-organic framework-based photo-thermal composite phase change material and application thereof. The metal-organic framework-based composite phase change material comprises a porous metal-organic framework matrix and a phase change material adsorbed on the surface of the metal-organic framework matrix or in a pore canal. The photosensitizer adopted by the invention has high-efficiency light absorption performance, photosensitive particles realize polymerization growth and uniform coating on the surface and/or pores of the metal organic framework-based composite phase change material, which is beneficial to shortening the heat transfer path so as to promote the efficient transfer of photoinitiated heat to the outside, endow the composite material with high-efficiency light-heat conversion performance, widen the spectrum utilization range of a single material and solve the problem of single functionality of the traditional metal organic framework-based phase change heat storage material.
Description
Technical Field
The invention relates to the field of phase change materials, in particular to a metal-organic framework-based photo-thermal composite phase change material and application thereof.
Background
In recent years, because unrecoverable fossil fuels are liable to cause environmental pollution and energy crisis, renewable, abundant and clean solar energy is expected to replace fossil fuels, and the energy crisis is relieved. Therefore, the application of solar energy storage is receiving a great deal of attention. However, it is difficult to directly and effectively utilize solar energy due to the intermittence and instability of solar radiation. Phase change materials have been used to collect and store solar energy due to the amount of latent heat of the phase change material during phase change. Accordingly, developing phase change material-based energy management systems with solar thermal conversion capabilities is considered one of the most promising technologies to overcome solar radiation discontinuities and improve solar energy utilization efficiency.
Various organic compounds (such as polyethylene glycol, esters and paraffins) and inorganic compounds (such as hydroxides, alloys and salts) have been studied for energy storage. Among the various phase change materials, organic alcohols are one of the most attractive and most widely studied candidates due to their high latent heat, good chemical stability and ideal phase change temperature. However, leakage of organic alcohols in the molten state limits their large-scale application in the field of thermal energy storage. Currently, most research is focused on using microencapsulation to solve the leakage problem of phase change materials. However, the core-shell structure and the preparation process of the microcapsules are complex. In addition, since the shell material hardly contributes to the heat storage performance of the composite phase change material, the high proportion of the shell material in the microcapsule will significantly reduce the phase change enthalpy of the composite material. In view of the high specific surface area and high porosity of the three-dimensional metal organic framework, the three-dimensional metal organic framework can be used as a porous carrier to realize encapsulation of an organic alcohol phase change material, and the leakage problem is effectively solved. However, the organic alcohol has low photo-thermal conversion efficiency, which limits the practical application in the solar energy utilization field. Therefore, there is a need to develop a metal-organic framework-based photothermal composite phase change material having a high energy storage density and excellent solar heat conversion properties.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
Object of the Invention
In order to solve the technical problems, the invention aims to provide the metal-organic framework-based photo-thermal composite phase-change material and the application thereof, solve the problem of single function of the metal-organic framework-based phase-change material in the prior art, solve the problem of easy agglomeration of a photosensitizer used for modifying the phase-change composite material, and overcome the defect of low photo-thermal conversion efficiency of the photo-thermal conversion type phase-change composite material.
Solution scheme
In order to achieve the purpose of the invention, the embodiment of the invention provides a metal-organic framework-based photo-thermal composite phase change material, which comprises a metal-organic framework-based composite phase change material and a photosensitizer coated on the metal-organic framework-based composite phase change material, wherein the metal-organic framework-based composite phase change material comprises a porous metal-organic framework matrix and a phase change material adsorbed on the surface or in a pore canal of the metal-organic framework matrix.
The invention encapsulates the phase change material by high capillary adsorption force of the metal organic framework matrix, provides sites for growth cladding of the photosensitizer, avoids agglomeration of photosensitizer particles, and thus realizes functionalization of the structure. The phase change material of the invention is preferably solid-liquid phase change material, solid-liquid phase change can be generated under the drive of external temperature to realize the release/absorption of heat energy, and the invention can cooperate with photosensitizer to play the role of photo-thermal conversion and heat energy storage.
Further, the pore canal of the metal organic framework-based composite phase change material also contains a photosensitizer. The photosensitizer can be uniformly dispersed in the pores of the metal organic framework-based composite phase change material, and is favorable for shortening a heat transfer path, so that the photoinitiated heat is promoted to be efficiently transferred to the outside.
The photosensitizer is an organic photosensitizer, and optionally, the photosensitizer is polymerized on the surface or pores of the metal-organic framework-based composite phase change material through the action of an oxidant by using a photosensitizer monomer. The photosensitizer monomer is polymerized on the surface of the metal organic framework-based composite phase-change material, can be uniformly dispersed and polymerized in the pores of the metal organic framework-based composite phase-change material, and is beneficial to shortening the heat transfer path, so that the photoinitiated heat is promoted to be efficiently transferred to the outside.
Further, the photosensitizer is an organic conjugated polymer.
Optionally, the organic conjugated polymer is selected from one or more of organic dye-based polymer and nanoparticle-based polymer.
Further, the organic dye polymer comprises one or more of porphyrin, indocyanine green and heptane.
Further, the nanoparticle polymer comprises one or more of polypyrrole, polydopamine and polyaniline.
Further, the photosensitizer is 2-10% of the weight of the metal-organic framework-based composite phase change material, alternatively 4% -6%, preferably 4%, 5% and 6%.
Further, the metal-organic framework matrix has a three-dimensional structure; optionally one or more selected from MIL-101 (Cr), MIL-100 (Fe), ZIF-8, ZIF-67, MOF-5, and MOF-74.
Further, the metal organic framework substrate encapsulates the phase change material by capillary adsorption.
Further, the phase change material is a solid-liquid phase change material, and is selected from one or more of fatty alcohol, fatty acid, normal alkane and paraffin; alternatively, the fatty alcohol comprises stearyl alcohol. Wherein the weight percentage of each phase change material is adjustable.
Further, the phase change material accounts for 60% -80% of the total weight of the metal organic framework-based composite phase change material, alternatively 65% -80%, alternatively 70%.
Further, the preparation method comprises the following steps: immersing the metal-organic framework-based composite phase change material into an oxidant solution, adding photosensitizer monomers according to a certain amount to realize polymerization reaction, stirring for 1-20 h, centrifuging, and drying to obtain the organic photosensitizer-coated photo-thermal composite phase change material;
Optionally, the weight ratio of the metal-organic framework-based composite phase change material to the photosensitizer monomer is 100: 4-6, alternatively 100:4, 100:5, 100:6.
Alternatively, in the polymerization, the stirring time is 5 to 10 hours, alternatively 8 hours.
Alternatively, in the polymerization reaction, the stirring condition is vigorous stirring, alternatively, the stirring rotation speed is 800r/min, and a magnetic stirrer can be used for stirring.
Alternatively, in the polymerization reaction, stirring is performed at room temperature.
Optionally, the oxidant is selected from one or more of ferric chloride, hydrogen peroxide, ammonium persulfate and potassium permanganate.
Further, the concentration of the oxidizing agent is 0.5% to 2%, alternatively 1%.
Optionally, the preparation method of the metal-organic framework matrix powder comprises the following steps: adding the hydrated metal salt solution into the solution of the organic ligand and the alkali, mixing, transferring into a reaction kettle, treating for 5-20 h at 160-180 ℃, and drying; alternatively, the molar ratio of hydrated metal salt to organic ligand is 1:0.5 to 1.5, alternatively the molar ratio is 1:1.
Further, the metal-organic framework-based composite phase change material is prepared by the following steps: immersing the metal organic framework matrix powder into the phase change material mixed solution after drying, stirring for 1-10 h, and drying the reaction solution to obtain the metal organic framework matrix composite phase change material containing the phase change material;
optionally, before immersing the metal-organic framework matrix powder in the phase change material mixed solution, vacuum drying is performed, and the optional vacuum drying method is as follows: vacuum drying at 60-100 deg.c for 20-28 hr to activate and open pores fully;
Optionally, the method for drying the reaction solution comprises the following steps: vacuum drying at 60-100 deg.c for 20-28 hr;
Optionally, the stirring conditions for immersing the metal-organic framework matrix powder into the phase change material mixed solution are as follows: stirring vigorously at 60-80 ℃ for 1-5 h, optionally at 70 ℃ for 2h;
Optionally, the preparation method of the phase change material mixed solution comprises the following steps: completely dissolving the phase change material in the solvent at a temperature above the phase change point; alternatively, the solvent is absolute ethanol.
On the other hand, the application of the metal-organic framework-based photo-thermal composite phase change material is provided, and the metal-organic framework-based photo-thermal composite phase change material is used as a photo-thermal conversion material, optionally used in the field of solar heat storage and optionally used in self-heating clothes.
Advantageous effects
(1) According to the metal organic framework-based photo-thermal composite phase change material, the metal organic framework with high specific surface area and adjustable aperture is used as an excellent carrier of the phase change material, the phase change material is packaged by high capillary adsorption force of the metal organic framework, the heat storage performance and the circulation stability of the phase change composite material are obviously enhanced, meanwhile, the metal organic framework-based composite phase change material is used as a growth and cladding site of a photosensitizer, the agglomeration of photosensitizer particles is avoided, and the particle size, the dispersion degree and the position of the photosensitizer are effectively controlled; the photosensitizer adopted by the invention has high-efficiency light absorption performance, photosensitive particles realize polymerization growth and uniform coating on the surface and/or pores of the metal organic framework-based composite phase change material, which is beneficial to shortening the heat transfer path so as to promote the efficient transfer of photoinitiated heat to the outside, endow the composite material with high-efficiency light-heat conversion performance, widen the spectrum utilization range of a single material and solve the problem of single functionality of the traditional metal organic framework-based phase change heat storage material.
(2) According to the metal organic framework-based photo-thermal composite phase change material provided by the embodiment of the invention, the adsorbed solid-liquid phase change material can reach 70% without leakage, the phase change enthalpy value can reach 129.50J/g, the photo-thermal composite phase change material obtained by coating the metal organic framework-based composite phase change material with the photosensitizer has stable phase change performance and thermal performance, the ordered assembly of the photosensitizer and the phase change material is realized, the synergistic effect of photo-thermal conversion and thermal energy storage is ensured, the photo-thermal conversion performance is excellent, and the photo-thermal composite phase change material has good application prospect in the field of solar energy storage.
(3) The metal organic framework-based photo-thermal composite phase change material provided by the embodiment of the invention encapsulates the phase change material through the high capillary adsorption force of the metal organic framework matrix, provides sites for growth cladding of the photosensitizer, avoids agglomeration of photosensitizer particles, and thus realizes the functionalization of the structure. The phase change material of the invention is preferably solid-liquid phase change material, solid-liquid phase change can be generated under the drive of external temperature to realize the release/absorption of heat energy, and the invention can cooperate with photosensitizer to play the role of photo-thermal conversion and heat energy storage.
(4) The metal organic framework-based photo-thermal composite phase change material provided by the embodiment of the invention adopts the organic conjugated polymer as the photosensitizer, wherein C-C and C=C in the organic conjugated polymer are alternately arranged. Pi electrons in conjugated double bonds are not fixed to a carbon atom and they can be transferred from one carbon atom to another, i.e., pi electrons have a tendency to cross the entire molecular chain. When exposed to external light, the organic photosensitizer may absorb light energy by means of electron transitions in the molecular orbitals, and then convert the absorbed light energy into heat energy, exhibiting a solar thermal effect. That is, under the induction of light, pi electrons on pi-bond molecular orbitals of the organic photosensitizer absorb light energy and then transition to pi-x-bond molecular orbitals. During the process of exciting electrons to fall back to the ground state, part of the energy is released in the form of heat, thereby generating a solar thermal effect. According to the invention, the metal-organic framework-based composite phase-change material is used as a monomer of an organic conjugated polymer to provide a growth site, and the photosensitizer is coated on the surface of the metal-organic framework-based composite phase-change material in a growth manner, so that excellent light absorptivity can be provided, and the prepared photo-thermal composite phase-change material has high-efficiency solar heat conversion capability.
Drawings
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1 is an SEM image of an MOF and photo-thermal composite material ODA@MOF/PPy-6 in example 3 of the present invention, wherein ODA is an abbreviation of stearyl alcohol, PPy is an abbreviation of polypyrrole, MOF is an abbreviation of metal-organic framework MIL-101 (Cr) prepared in example 3, and PPy-6 is an abbreviation of ODA@MOF/PPy-6 in example 3.
FIG. 2 is a DSC cold-hot cycle curve of the photo-thermal composite phase change material ODA@MOF/PPy-6 of example 3 of the invention after 50 cold-hot alternating experiments.
FIG. 3 is a structural representation of MOF and photothermal composite phase change materials of examples 1 to 3 and comparative examples 1 to 3 according to the present invention, wherein (a) is FTIR spectrum and (b) is XRD spectrum. MOF is metal organic framework MIL-101 (Cr) prepared in example 3, ODA@MOF is phase change material of metal organic framework composite ODA prepared in example 3, PPy-4 is ODA@MOF/PPy-4 abbreviation of example 1, PPy-5 is ODA@MOF/PPy-5 abbreviation of example 2, and PPy-6 is ODA@MOF/PPy-6 abbreviation of example 3.
FIG. 4 is a graph showing the latent heat storage performance of the photo-thermal composite phase change materials of examples 1 to 3 and comparative example 1 according to the present invention, wherein (a) is a DSC heating curve and (b) is a DSC cooling curve; ODA is the abbreviation of stearyl alcohol, ODA@MOF is the phase change material of the metal organic framework composite ODA prepared in example 3, PPy-4 is the abbreviation of ODA@MOF/PPy-4 in example 1, PPy-5 is the abbreviation of ODA@MOF/PPy-5 in example 2, and PPy-6 is the abbreviation of ODA@MOF/PPy-6 in example 3.
FIG. 5 is a photo-thermal curve of the photo-thermal composite phase-change material of the embodiment and the comparative example under 150mW/cm 2, wherein ODA@MOF is the abbreviation of the ODA@MOF composite phase-change material of the comparative example 1, PPy-4 is the abbreviation of the ODA@MOF/PPy-4 of the embodiment 1, PPy-5 is the abbreviation of the ODA@MOF/PPy-5 of the embodiment 2, and PPy-6 is the abbreviation of the ODA@MOF/PPy-6 of the embodiment 3.
FIG. 6 is a photograph showing leakage experiments of the photo-thermal composite phase change material of the present invention at 80 ℃ for different times under continuous heating; wherein ODA is the abbreviation of stearyl alcohol, ODA@MOF is the abbreviation of the ODA@MOF composite phase change material of comparative example 1, and PPy-6 is the abbreviation of ODA@MOF/PPy-6 of example 3.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the gist of the present invention.
In the examples described below, the starting materials used were all commercially available materials. Wherein, MIL-101 (Cr) with metal-organic framework can be a commercial product or synthesized by the method of the examples.
In the following examples, MIL-101 (Cr) is used as the metal-organic framework substrate, and in practical application, different metal-organic framework substrates, such as MIL-100 (Fe), ZIF-8, ZIF-67, MOF-5, etc., can be selected according to different requirements.
In the following examples, the phase change material is illustrated by using stearyl alcohol (ODA), and in practical application, different phase change materials can be selected according to different requirements.
In the following embodiments, the specific detection method of the photo-thermal curve is: placing the prepared 200mg photo-thermal phase change energy storage material under a xenon lamp with the intensity of 150mW/cm 2, recording the temperature change of a sample by using a thermal sensor, and finally using a formula(Wherein m is the mass of the photo-thermal phase-change energy storage material, ΔH represents the latent heat of fusion, P is the irradiation intensity of simulated sunlight, S is the area of the photo-thermal phase-change energy storage material exposed to light, and t is the irradiation time.) the photo-thermal conversion efficiency (η) of the photo-thermal phase-change energy storage material in the absorption process is calculated.
In the following examples, the method for detecting the latent heat storage performance is as follows: the solid was first prepared and the latent heat value of the photothermal composite phase change material was measured by differential scanning calorimetry (DSC, mettler DSC822e, japan).
In the following examples, polypyrrole (corresponding to the pyrrole monomer used) was selected as the photosensitizer, and in practical application, different photosensitizers may be selected according to different requirements.
The following takes ODA@MOF/PPy-x as an example, wherein "x" represents the relative percentage of photosensitizer added during the phase change composite preparation. The metal-organic framework-based photo-thermal composite phase-change material with photo-thermal conversion performance, which can be applied to the field of solar heat storage, and the preparation method thereof are further described through specific embodiments and with reference to the accompanying drawings.
Example 1
A preparation method of a metal organic framework-based photo-thermal composite phase change material with a photo-thermal conversion function comprises the following steps:
(1) MIL-101 (Cr) is synthesized by adopting a one-step hydrothermal method: 1.44g (8.0 mmol) of 2-aminoterephthalic acid (H 2BDC-NH2)、3.20g(8.0mmol)Cr(NO3)3·9H2 O and 0.80g (20.0 mmol) of NaOH were dissolved in 60mL of deionized water and stirred at room temperature for 30min, then the mixed solution was transferred to a polytetrafluoroethylene-lined autoclave and reacted at 180℃for 12H.
(2) Metal organic framework matrix MILs-101 (Cr) adsorption phase change material: drying the MOF powder in step (1) in a vacuum oven at 80 ℃ for 24 hours to fully activate and open the pores; 1.0g of the MOF powder after vacuum drying was immersed in the ODA mixture of step A) and vigorously stirred at 70℃for 2h. And finally, putting the mixed solution into a vacuum oven, and drying at 80 ℃ for 24 hours to obtain the ODA@MOF composite phase change material, wherein the maximum load capacity of the ODA is 70%.
Wherein, the preparation of the ODA mixed solution comprises the following steps: 2.3g of ODA is completely dissolved in 25mL of absolute ethyl alcohol at 70 ℃ and stirred for 0.5h to obtain a phase change material mixed solution;
(3) Preparation of ODA@MOF/PPy-4: first, 100mgoda@mof composite phase-change material of step (2) is immersed in a 1wt% ferric chloride solution. Then, 4mL of pyrrole monomer was added to the mixture to effect polymerization, and vigorously stirred at 25 ℃ for 8 hours until the solution became black. Finally, ODA@MOF/PPy-4 was obtained by centrifuging and drying the above mixture.
The enthalpy value of the MOF-based photo-thermal composite phase-change material ODA@MOF/PPy-4 prepared in the embodiment is 127.93J/g, and the highest photo-thermal conversion efficiency can reach 79.8%; the leak-proof test result shows that the phase-change composite material hardly leaks after being processed in an oven at 80 ℃ for 1 h.
Example 2
The difference from the preparation of example 1 is that the amount of pyrrole monomer added is 5mL, giving ODA@MOF/PPy-5.
The enthalpy value of the MOF-based photo-thermal composite phase-change material ODA@MOF/PPy-5 prepared in the embodiment is 130.85J/g, and the highest photo-thermal conversion efficiency can reach 85.6%; the leak-proof test result shows that the phase-change composite material hardly leaks after being processed in an oven at 80 ℃ for 1 h.
Example 3
The difference from the preparation of example 1 is that the amount of pyrrole monomer added is 6mL, giving ODA@MOF/PPy-6.
The enthalpy value of the MOF-based photo-thermal composite phase-change material ODA@MOF/PPy-6 prepared in the embodiment is 129.58J/g, and the highest photo-thermal conversion efficiency can reach 88.3%; the leak-proof test result shows that the phase-change composite material hardly leaks after being processed in an oven at 80 ℃ for 1 h.
SEM images of MOF and ODA@MOF/PPy-6 of the composite material of example 3 are shown in FIG. 1, and the morphology of MOF and ODA@MOF/PPy-6 is shown at the same magnification. ODA@MOF/PPy-6 exhibited a larger size than the original MOF due to the coating effect of the PPy particulate polymer on the ODA@MOF surface.
The DSC cycle curve of ODA@MOF/PPy-6 in this example 3 is shown in FIG. 2, and the result shows that the melting point and crystallization point, latent heat of fusion and enthalpy of crystallization of the three curves before and after 50 times of thermal cycles of ODA@MOF/PPy-6 prepared in this example are almost unchanged, so that the ODA@MOF/PPy-6 prepared in this example has good stability.
The leakage test was performed on the oda@mof/PPy-6 photothermal composite phase change material in example 3, and the heating was continued at 80 ℃ far above the phase change point of stearyl alcohol (ODA), and as a result, as shown in fig. 6, the ODA could liquefy with the extension of time, and the phase change material in the oda@mof-PPy photothermal composite phase change material did not flow out, which indicates that the photothermal composite phase change material in this example has good encapsulation.
Comparative example 1
The difference from example 2 is that step (3) is not performed, i.e. this comparative example only an oda@mof composite phase change material is produced.
The enthalpy value of the MOF-based photo-thermal composite phase-change material ODA@MOF prepared in the comparative example is 131.45J/g, and the leak-proof test result shows that the phase-change composite material hardly leaks after being processed in an oven at 80 ℃ for 1h (figure 5).
The results of chemical structure characterization analysis of the photo-thermal composite phase-change materials of examples 1 to 3 and comparative example 1 are shown in fig. 2, and the results show that all characteristic peaks of ODA, MOF and PPy are observed in the oda@mof/PPy composite phase-change material, and no obvious new peak is generated, indicating that no new chemical bond is formed. FTIR spectra show that ODA, PPy and MOF are physical interactions, not chemical interactions. XRD patterns of ODA and ODA@MOF-PPy were characterized to explore the crystallization behavior of ODA in MOF wells, and diffraction peaks of ODA, MOF and PPy were all observed in the composite ODA@MOF-PPy, without significant shift, confirming the physical interaction between the components.
The results of the latent heat storage performance of the photo-thermal composite phase change materials of examples 1 to 3 and comparative example 1 are shown in fig. 3 and 4, and the results show that the enthalpy values of the obtained composites are not greatly different when the addition amount of the photosensitizer is 4mL, 5mL and 6mL, and the enthalpy value of the obtained composite is relatively better when the addition amount of the photosensitizer is 5mL, and the photo-thermal efficiency of the composite is relatively better when the addition amount of the photosensitizer is 6mL, which indicates that the enthalpy value and the photo-thermal efficiency are not completely corresponding.
The photo-thermal composite phase change materials of examples 1 to 3 and comparative example 1 were subjected to photo-thermal conversion test, and the results are shown in fig. 5, and the results show that under the driving of light intensity of 150mW/cm 2, the oda@mof composite material can not reach the phase change point, which means almost no photo-thermal conversion capability, and the photo-thermal conversion efficiency of the photo-thermal composite phase change material is remarkably improved after PPy is introduced, so that the composite material becomes a material with excellent solar thermal conversion performance and high energy storage density, and the photo-thermal conversion efficiency is also improved with the increase of PPy content.
Comparative example 2
(1) MOF powder (MIL-101 (Cr)) was prepared by the method of step (1) of example 1.
(2) The metal organic framework matrix MIL-101 (Cr) was immersed in a 1wt% ferric chloride solution. Then, 5mL of pyrrole monomer was added to the mixture to effect polymerization, and vigorously stirred at 25 ℃ for 8 hours until the solution became black. Finally, MOF/PPy-5 was obtained by centrifuging and drying the above mixture.
(3) The MOF/PPy-5 powder was dried in a vacuum oven at 80℃for 24h to fully activate and open the pores; 1g of the MOF/PPy-5 powder dried in vacuo was immersed in the ODA mixture and vigorously stirred at 70℃for 2 hours. Finally, the mixed solution was placed in a vacuum oven and dried at 80℃for 24 hours to give ODA@MOF/PPy-5-2.
The preparation method of the ODA mixed solution comprises the following steps: 2.3g ODA was completely dissolved in 25mL absolute ethanol at 70℃and stirred for 0.5h to obtain a phase change material mixture.
In this comparative example, the loading of the photosensitizer first causes the photosensitizer to occupy the pore canal of the MOF, and thus the efficient adsorption of the phase change material cannot be realized, and the encapsulation effect on the phase change material is poor.
The inventor of the present invention found that as the concentration of the oxidizing agent increases, the photo-thermal conversion efficiency of the photo-thermal composite phase change material increases and then decreases, and that the concentration of the suitable oxidizing agent is 0.5% to 2%.
The inventor of the present invention found that as the content of the phase change material increases, the photo-thermal conversion efficiency of the photo-thermal composite phase change material increases and then decreases, and in the metal-organic framework-based composite phase change material, the suitable weight ratio of the phase change material is 60% -80%, and optionally 65% -80%.
Photo-thermal energy storage application of application example 1 composite material
The MOF-based photo-thermal composite phase-change material has good phase-change energy storage performance, the enthalpy value is 130.85J/g, polypyrrole can be used as a light energy capturer to convert light energy into heat energy, the heat energy is further utilized by the phase-change material to store and release energy, and the photo-thermal conversion efficiency can reach 88.3% under the driving of light intensity of 150mW/cm 2.
For example, the MOF-based photo-thermal composite phase-change material is packaged in fabric fibers to further prepare human body wearable heat energy management equipment, and the equipment can perform photo-thermal conversion under the condition of sufficient sunlight in daytime so as to drive the phase-change material to melt and store heat; during the night, the phase change material is solidified, and the heat energy stored in the phase change material is released, thereby playing a role in regulating the temperature of the human body.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (41)
1. The metal-organic framework-based photo-thermal composite phase change material is characterized by having photo-thermal conversion performance, comprising a metal-organic framework-based composite phase change material and a photosensitizer coated on the metal-organic framework-based composite phase change material, wherein the metal-organic framework-based composite phase change material comprises a porous metal-organic framework matrix and a phase change material adsorbed on the surface or in a pore canal of the metal-organic framework matrix; wherein,
The photosensitizer is an organic photosensitizer, and is polymerized on the surface and pores of the metal-organic framework-based composite phase change material through the action of an oxidant by using a photosensitizer monomer;
The photosensitizer is 2-10% of the weight of the metal organic framework-based composite phase change material;
the phase change material accounts for 60% -80% of the total weight of the metal organic framework-based composite phase change material.
2. The metal-organic framework-based photothermal composite phase change material of claim 1, wherein the photosensitizer is an organic conjugated polymer; the organic conjugated polymer is selected from one or more of organic dye polymer and nanoparticle polymer.
3. The metal-organic framework-based photothermal composite phase change material of claim 2, wherein the organic dye-based polymer comprises one or more of porphyrin, indocyanine green and heptane.
4. The metal-organic framework-based photothermal composite phase change material of claim 2, wherein the nanoparticle-based polymer comprises one or more of polypyrrole, polydopamine and polyaniline.
5. The metal-organic framework-based photothermal composite phase change material of claim 1, wherein the photosensitizer is 4% -6% by weight of the metal-organic framework-based composite phase change material.
6. The metal-organic framework based photothermal composite phase change material of claim 1, wherein the photosensitizer is 4% by weight of the metal-organic framework based composite phase change material.
7. The metal-organic framework based photothermal composite phase change material of claim 1, wherein the photosensitizer is 5% by weight of the metal-organic framework based composite phase change material.
8. The metal-organic framework based photothermal composite phase change material of claim 1, wherein the photosensitizer is 6% by weight of the metal-organic framework based composite phase change material.
9. The metal-organic framework-based photothermal composite phase change material of claim 1, wherein the metal-organic framework matrix is of a three-dimensional structure.
10. The metal-organic framework-based photothermal composite phase change material of claim 1, wherein the metal-organic framework matrix is selected from one or more of MILs-101 (Cr), MILs-100 (Fe), ZIF-8, ZIF-67, MOF-5, MOF-74.
11. The metal-organic framework-based photothermal composite phase change material of claim 1, wherein the metal-organic framework matrix encapsulates the phase change material by capillary adsorption.
12. The metal-organic framework-based photothermal composite phase change material of claim 1, wherein the phase change material is a solid-liquid phase change material.
13. The metal-organic framework-based photothermal composite phase change material of claim 1, wherein the phase change material is selected from one or more of fatty alcohols, fatty acids, normal alkanes, and paraffins.
14. The metal-organic framework-based photothermal composite phase change material of claim 1, wherein the phase change material comprises 65% -80% of the total weight of the metal-organic framework-based composite phase change material.
15. The metal-organic framework based photothermal composite phase change material of claim 1, wherein the phase change material comprises 70% of the total weight of the metal-organic framework based composite phase change material.
16. The metal-organic framework-based photothermal composite phase change material according to any one of claims 1 to 15, characterized in that the preparation steps thereof include: immersing the metal-organic framework-based composite phase change material into an oxidant solution, adding a photosensitizer monomer according to a certain amount to realize polymerization reaction, stirring for 1-20 h, centrifuging, and drying to obtain the organic photosensitizer-coated photo-thermal composite phase change material.
17. The metal-organic framework-based photothermal composite phase change material of claim 16, wherein a weight ratio of the metal-organic framework-based composite phase change material to the photosensitizer monomer is 100: 4-6.
18. The metal-organic framework based photothermal composite phase change material of claim 16, wherein a weight ratio of the metal-organic framework based composite phase change material to the photosensitizer monomer is 100:4.
19. The metal-organic framework based photothermal composite phase change material of claim 16, wherein a weight ratio of the metal-organic framework based composite phase change material to the photosensitizer monomer is 100:5.
20. The metal-organic framework based photothermal composite phase change material of claim 16, wherein a weight ratio of the metal-organic framework based composite phase change material to the photosensitizer monomer is 100:6.
21. The metal-organic framework-based photothermal composite phase change material according to claim 16, wherein in the polymerization reaction, the stirring time is 5-10 hours.
22. The metal-organic framework based photothermal composite phase change material of claim 16, wherein in the polymerization reaction, the stirring time is 8 h.
23. The metal-organic framework-based photothermal composite phase change material of claim 16, wherein the stirring speed is 800 r/min.
24. The metal-organic framework based photothermal composite phase change material of claim 16, wherein stirring is performed at room temperature during the polymerization.
25. The metal-organic framework-based photothermal composite phase change material of claim 16, wherein the oxidizing agent is selected from one or more of ferric chloride, hydrogen peroxide, ammonium persulfate, and potassium permanganate.
26. The metal-organic framework-based photothermal composite phase change material of claim 25, wherein the concentration of the oxidizing agent is 0.5% -2%.
27. The metal-organic framework based photothermal composite phase change material of claim 25, wherein the concentration of the oxidizing agent is 1%.
28. The metal-organic framework-based photothermal composite phase change material of claim 16, wherein the metal-organic framework-based composite phase change material is prepared by: immersing the metal organic framework matrix powder into the phase change material mixed solution, stirring for 1-10 h, and drying the reaction solution to obtain the metal organic framework matrix composite phase change material containing the phase change material.
29. The metal-organic framework based photothermal composite phase change material of claim 28, wherein the metal-organic framework matrix powder is vacuum dried prior to being immersed in the phase change material mixture.
30. The metal-organic framework-based photothermal composite phase change material of claim 29, wherein the vacuum drying method comprises: and (3) vacuum drying at 60-100 ℃ for 20-28 hours to fully activate and open the pores.
31. The metal-organic framework-based photothermal composite phase change material of claim 28, wherein the reaction liquid drying method comprises the following steps: and (5) vacuum drying at 60-100 ℃ for 20-28 h.
32. The metal-organic framework-based photothermal composite phase change material of claim 28, wherein the stirring conditions for immersing the metal-organic framework matrix powder in the phase change material mixture are: and (3) vigorously stirring for 1-5 h at the temperature of 60-80 ℃.
33. The metal-organic framework-based photothermal composite phase change material of claim 28, wherein the stirring conditions for immersing the metal-organic framework matrix powder in the phase change material mixture are: the mixture was stirred vigorously at 70℃for 2 h.
34. The metal-organic framework-based photothermal composite phase change material of claim 28, wherein the phase change material mixture is prepared by a method comprising: the phase change material is completely dissolved in the solvent at a temperature above the phase change point.
35. The metal-organic framework based photothermal composite phase change material of claim 28, wherein the solvent is absolute ethanol.
36. The metal-organic framework-based photothermal composite phase change material of claim 28, wherein the metal-organic framework matrix powder is prepared by a method comprising: and adding the hydrated metal salt solution into the solution of the organic ligand and the alkali, mixing, transferring into a reaction kettle, treating for 5-20 h at 160-180 ℃, and drying.
37. The metal-organic framework-based photothermal composite phase change material of claim 36, wherein a molar ratio of the hydrated metal salt to the organic ligand is 1:0.5-1.5.
38. The metal-organic framework based photothermal composite phase change material of claim 36, wherein a molar ratio of hydrated metal salt to organic ligand is 1:1.
39. Use of a metal-organic framework-based photothermal composite phase change material according to any of claims 1 to 38 as photothermal conversion material.
40. The use according to claim 39, characterized in that it is used in the field of solar heat storage.
41. The use according to claim 39, in self-heating apparel.
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