CN114479771A - Metal organic framework derivative-based photothermal phase change material and application thereof - Google Patents
Metal organic framework derivative-based photothermal phase change material and application thereof Download PDFInfo
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- 239000012782 phase change material Substances 0.000 title claims abstract description 151
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 38
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 claims description 2
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002904 solvent Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 230000031700 light absorption Effects 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to the field of phase-change materials, in particular to a metal organic framework derivative-based photothermal phase-change material and application thereof. The zinc oxide/hierarchical pore carbon composite material is a carbon material which is obtained by high-temperature carbonization of a zinc-metal organic framework and is highly and uniformly distributed with zinc oxide nanoparticles, and the zinc oxide nanoparticles account for 20-50% of the total weight of the zinc oxide/hierarchical pore carbon composite material. According to the invention, the zinc oxide/hierarchical pore carbon composite is used as a base material to package the phase-change material, the zinc oxide nanoparticles with ultrahigh dispersion in the zinc oxide/hierarchical pore carbon composite have better photon capturing capability, can realize efficient and rapid heat transfer and light absorption, have higher photo-thermal conversion efficiency under the synergistic action with the phase-change material, have higher stability, can obviously improve the photo-thermal conversion and storage capability of the phase-change material, and effectively promote the utilization of solar energy.
Description
Technical Field
The invention relates to the field of phase-change materials, in particular to a metal organic framework derivative-based photothermal phase-change material and application thereof.
Background
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 skilled in the art.
Solar energy has the advantages of abundant resources, no pollution and the like as an ideal renewable energy source, and in recent years, the photothermal conversion technology is a way for effectively utilizing the solar energy and can convert the solar energy into heat energy. However, the photothermal conversion technology is limited by the problems of intermittency, instability, dispersion and low energy conversion efficiency of solar energy. Therefore, the continuous and reliable utilization of solar energy can be realized by integrating the advanced energy storage technology and the photo-thermal conversion technology. The PCMs perform heat energy storage and release through absorption and release of phase change latent heat in the phase state transition process of the materials, have the characteristics of high heat storage density, stable working temperature and the like, and are the key points of the current research on solar heat storage utilization. However, the inherent weak photon capturing capability of pure PCMs is always a bottleneck restricting the application of photothermal conversion, so that the development of high-efficiency photothermal conversion materials is urgently needed to further improve the solar energy photo-thermal phase change energy storage performance.
Disclosure of Invention
Object of the Invention
In order to solve the technical problems, the invention aims to provide a metal organic framework derivative-based photothermal phase change material and application thereof, the composite phase change material takes a zinc oxide/hierarchical pore carbon composite as a base material to package the phase change material, and zinc oxide nanoparticles with ultrahigh dispersion in the zinc oxide/hierarchical pore carbon composite have better photon capturing capacity, can realize efficient and rapid heat transfer and light absorption, have higher photothermal conversion efficiency under the synergistic action with the phase change material, have higher stability, can obviously improve the photothermal conversion and storage capacity of the phase change material, and effectively promote the utilization of solar energy.
Solution scheme
In order to achieve the purpose of the invention, the embodiment of the invention provides a metal organic framework derivative-based photothermal phase change material, which comprises a zinc oxide/hierarchical pore carbon composite and a phase change material adsorbed on the surface and/or in pore channels of the zinc oxide/hierarchical pore carbon composite, wherein the zinc oxide/hierarchical pore carbon composite is a carbon material which is obtained by carbonizing a zinc-metal organic framework at high temperature and is uniformly distributed with zinc oxide nanoparticles, and the zinc oxide nanoparticles account for 20-50% of the total weight of the zinc oxide/hierarchical pore carbon composite.
Further, in the composite phase change material, the mass ratio of the phase change material to the zinc oxide/hierarchical pore carbon composite is 1-99: 99-1, optionally 50-90: 50-10, optionally 55-85: 45-15, optionally 55-80: 45-20, preferably 55-70: 45-30.
Further, the zinc oxide nanoparticles comprise optionally from 24 to 40%, optionally from 24 to 35%, optionally from 28 to 35%, optionally from 29 to 35%, preferably from 29 to 30% by weight of the total zinc oxide/nanoporous carbon composite.
Further, the zinc oxide nanoparticles are highly uniformly distributed in the carbon material.
Further, the zinc-metal organic framework is selected from one or more of MOF-5 materials containing zinc ligands, IRMOF series materials containing zinc ligands and ZIF series materials containing zinc ligands.
Further, the phase change material is a solid-liquid phase change material, and is optionally selected from one or more of a polyol phase change material, a paraffin phase change material and a fatty acid phase change material.
Further, the polyol phase-change material is selected from one or more of polyethylene glycol, pentaerythritol and neopentyl glycol; optionally the average molecular weight of the polyethylene glycol is 800-.
Further, the paraffin-based phase change material includes paraffin having a melting point of 20 to 60 ℃.
Further, the fatty acid phase-change material is selected from one or more of stearic acid, myristic acid, palmitic acid, capric acid, lauric acid, pentadecanoic acid and sebacic acid.
Further, the compounding process of the composite phase change material comprises the following steps: soaking the zinc oxide/hierarchical porous carbon composite into a phase-change material solution, and performing vacuum impregnation and drying to obtain a composite phase-change material; optionally, the phase change material solution is prepared by dissolving a phase change material in a solvent.
Further, in the compounding process, the impregnation reaction temperature is higher than the phase change temperature of the phase change material, and optionally, the reaction temperature is 80-120 ℃.
Further, in the compounding process, the drying temperature is higher than the phase change temperature of the phase change material, optionally, the drying temperature is 80-120 ℃; optionally, the drying time is 12-48 h.
Further, the high-temperature carbonization conditions are as follows: under the inert gas atmosphere, raising the temperature to the carbonization temperature at the temperature rise rate of 2-8 ℃/min; keeping the carbonization temperature for 1-6 h, and cooling to obtain the carbon material.
Further, the temperature increase rate was 5 ℃/min.
Further, the carbonization temperature is 500-900 ℃; optionally the carbonization temperature is 600-800 ℃; optionally a carbonization temperature of 600-.
Further, the carbonization temperature is kept for 2-4h, preferably 3 h.
Further, the cooling method comprises the following steps: cooling at a rate of 5-15 ℃/min, optionally at a rate of 10 ℃/min.
Further, the inert gas is nitrogen or argon, preferably nitrogen.
Further, the zinc-metal organic framework is obtained by reacting zinc salt and an organic ligand.
Further, the preparation method of the zinc-metal organic framework comprises the following steps: adding the zinc salt hydrate solution into the organic ligand, stirring, then dripping triethylamine, continuing stirring, collecting the precipitate, washing and drying to obtain the zinc-metal organic framework.
Further, the zinc salt includes Zn (NO)3)2.6H2O and Zn (NO)3)2.4H2One or more of O.
Further, the molar ratio of the zinc salt hydrate to the organic ligand is optionally 10: 1-20, optionally 10: 1-10, preferably 10: 1-10, optionally 10: 3-6, preferably 10: 4 to 5.
In another aspect, an application of the metal organic framework derivative-based photothermal phase change material is provided, wherein the metal organic framework derivative-based photothermal phase change material is used as a photothermal conversion material, and is optionally used in the field of solar heat storage.
Advantageous effects
(1) The composite phase-change material provided by the invention takes the zinc oxide/multi-level pore carbon composite as a base material to package the phase-change material, the zinc oxide nanoparticles with ultrahigh dispersion in the zinc oxide/multi-level pore carbon composite have better photon capture capacity, can realize high-efficiency and rapid heat transfer and light absorption, can convert absorbed light energy into heat energy to be stored in the phase-change material, has higher photo-thermal conversion efficiency under the synergistic action with the phase-change material, has higher stability, can obviously improve the photo-thermal conversion and storage capacity of the phase-change material, and effectively promotes the utilization of solar energy.
(2) The zinc oxide/hierarchical porous carbon composite is prepared by carbonizing a zinc-metal organic framework (Zn-MOF for short) at high temperature, and the photosensitive material-zinc oxide nanoparticles generated by the in-situ high dispersion of the Zn-MOF in the carbonization process can be highly dispersed in a hierarchical three-dimensional hierarchical porous carbon framework, so that high-efficiency and rapid heat transfer and light absorption can be realized, the selection of phase-change materials is diversified, the economic performance and the practicability are good, a thought is provided for developing MOF derivative-based photo-thermal composite PCMs with high-performance thermo-physical properties, and infinite possibility is opened for the application of photo-thermal energy conversion.
(3) Zn-MOF is a periodic reticular porous compound formed by taking Zn metal ions as a center and bridging with organic ligands, has the characteristics of ordered and regular pore channels, adjustable pore diameter, ultrahigh porosity and high specific surface area, and has no photosensitivity. According to the invention, a controllable carbonization method is adopted to control the carbonization temperature to treat Zn-MOF, so that a porous structure formed by nucleation, aggregation and evaporation of ZnO nanoparticles in a carbon matrix can be effectively regulated and controlled, the ultrahigh dispersibility and the strong photon capturing capability of a ZnO photosensitizer generated by in-situ high-dispersion in the carbonization process of the Zn-MOF in a layered carbon frame can be ensured, the high-efficiency photo-thermal conversion capability is ensured by the synergistic effect of a graded porous carbon matrix and a ZnO two-photon capturer, the rapid heat transfer can be realized by an ordered three-dimensional structure after the phase change material is loaded, and the high photo-thermal conversion efficiency can be effectively realized.
(4) The invention takes a zinc oxide/hierarchical porous carbon composite as a support material to efficiently match and vacuum impregnate and package PCMs (layered organic semiconductors), so as to construct a Zn-MOF (metal organic framework) -derived three-dimensional hierarchical porous carbon energy storage unit, and obtain a novel composite phase change material with high heat conductivity, high latent heat, high light absorptivity and high photothermal conversion efficiency. The three-dimensional zinc oxide/hierarchical porous carbon composite has high thermal conductivity, affinity and photon capturing capacity, can effectively prevent the phase change material from leaking while providing excellent light absorption, heat conduction and photothermal conversion performances, and the ZnO nano particles of the semiconductor photosensitive material exert the function of Localized Surface Plasmon Resonance (LSPR) in the process of light-heat energy conversion and absorb visible light under the synergistic action of the carbon-based material so as to achieve higher light-heat energy conversion. The composite phase change material disclosed by the invention shows high phase change latent heat, and is expected to show unique advantages in solar efficient photo-thermal utilization. Therefore, the synergistic effect of the three-dimensional graded porous carbon matrix and the ZnO nanoparticles remarkably improves the thermal conductivity and the photothermal conversion capability of the phase change material, solar energy can be quickly converted into heat energy to be stored in PCMs, and the conversion efficiency can reach 93.14%. The invention provides a new idea for further improving the photo-thermal energy conversion efficiency and designing and constructing novel three-dimensional composite PCMs.
(5) The inventor of the invention finds that the metal oxide (namely ZnO) can be better generated only by proper carbonization temperature and proper carbonization temperature holding time, so that ZnO nanoparticles in the carbon material are in a proper range, and the photo-thermal conversion efficiency is ensured.
(6) The inventor of the invention also researches the difference of the content and distribution of ZnO nanoparticles in the carbonization process of MOF and the rule that the content and distribution of ZnO nanoparticles and three-dimensional hierarchical porous carbon matrix material cooperate with each other to enable the photothermal conversion efficiency to present, and the result shows that reasonable carbonization temperature, carbonization time, cooling speed and the like can enable the content and the dispersivity of ZnO nanoparticles in the carbon material to be in a proper range, thereby ensuring the photothermal conversion efficiency.
Drawings
One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively 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 SEM photographs of a zinc oxide/hierarchical porous carbon composite and a composite phase change material according to embodiment 1 of the present invention, wherein a is an SEM photograph of a phase change carrier of a zinc oxide/hierarchical porous carbon composite MOF-5-PC-700 ℃, b is an SEM photograph of a composite phase change material PW @ MOF-5-PC-700 ℃ obtained according to embodiment 1 of the present invention, and PW is an abbreviation of Paraffin (Paraffin wax).
FIG. 2 is a Differential Scanning Calorimetry (DSC) chart of the PW and the PW @ MOF-5-PC-600 ℃ composite phase change material, the PW @ MOF-5-PC-700 ℃ composite phase change material, and the PW @ MOF-5-PC-800 ℃ composite phase change material in embodiment 1 of the present invention.
FIG. 3 shows UV-vis-NIR absorption spectra of the PW @ MOF-5-PC-600 ℃ composite phase change material, the PW @ MOF-5-PC-700 ℃ composite phase change material and the PW @ MOF-5-PC-800 ℃ composite phase change material in example 1 of the present invention.
FIG. 4 is a FT-IR spectrum of the PW @ MOF-5-PC-700 ℃ composite phase change material, the PW, and the zinc oxide/hierarchical porous carbon composite MOF-5-PC-700 ℃ support in example 1 of the present invention.
FIG. 5 is a photo-thermal conversion curve of the PW @ MOF-5-PC-600 ℃ composite phase change material, the PW @ MOF-5-PC-700 ℃ composite phase change material and the PW @ MOF-5-PC-800 ℃ composite phase change material in embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present 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, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
In the following examples, all the raw materials used were commercially available materials.
In the following examples, the photothermal conversion efficiency of the composite phase change material is calculated by the following formula (I):
wherein m is the sample mass, Delta H is the enthalpy value of the sample, P is the light intensity of the sunlight simulated by the experiment, TsAnd TfThe phase change starting time and the phase change ending time are respectively set when the temperature is raised by illumination.
In the following examples, the loading of the Phase Change Materials (PCMs) was calculated as: the loading of PCMs ═ 100% x [ mass of PCMs/(mass of PCMs + mass of zinc oxide/multi-pore carbon composite support material) ].
Example 1
A preparation method of a metal organic framework derivative-based photothermal phase change material specifically comprises the following steps:
(1) preparation of MOF-5:
adding Zn (NO)3)2.6H2A solution of O (12.39g) and terephthalic acid (3.06g) in 360mL Dimethylformamide (DMF) was stirred in a flask for 1h, then triethylamine (14.4g) was slowly added dropwise. After stirring for 30min, 2.7ml of 30% aqueous hydrogen peroxide solution was added and further stirred for 30 min. Finally, the solid obtained by filtration is washed 3 times with DMF,washing with methanol for 3 times, and oven drying at 80 deg.C for 24 hr.
(2) Preparation of MOF-5-PC support material:
directly carbonizing the MOF-5 to obtain the MOF-5-PC. Putting the MOF-5 white powder into an alumina crucible, heating to a certain temperature X at the speed of 5 ℃/min under the flowing of nitrogen, maintaining the temperature X for 3h, and then cooling to room temperature at the speed of 10 ℃/min to prepare a carbon material MOF-5-PC-X;
wherein, the carbonization treatment is respectively carried out at the temperature of 600 ℃, 700 ℃ and 800 ℃ to obtain the carbon materials MOF-5-PC-600 ℃, MOF-5-PC-700 ℃ and MOF-5-PC-800 ℃.
(3) Compounding MOF-5-PC carrier materials with PCMs:
the composite phase-change material is prepared by adopting a vacuum impregnation method: dissolving a phase change material PW in n-hexane, fully stirring for 1h to prepare a phase change material solution, adding a carbon material into the phase change material solution, reacting at the temperature of 80-120 ℃, continuously stirring until ethanol is completely evaporated, placing the obtained composite material in an oven at the temperature of 80 ℃ for drying for 8-24h, and repeatedly replacing filter paper until no trace of PW melting exists on the filter paper, thereby obtaining the composite phase change material.
Respectively immersing the carbon material MOF-5-PC-600 ℃, MOF-5-PC-700 ℃ and MOF-5-PC-800 ℃ in the phase-change material solution in the step (2) to respectively obtain the composite phase-change material PW @ MOF-5-PC-600 ℃, PW @ MOF-5-PC-700 ℃ and PW @ MOF-5-PC-800 ℃, wherein the proportion of PW in the three composite phase-change materials is about 60 percent through detection (wherein the maximum load capacity of the composite phase-change material PW @ MOF-5-PC-700 ℃ on the phase-change material is also 60 percent). The three composite phase-change materials are detected respectively:
SEM scanning is respectively carried out on the MOF-5-PC-700 ℃ carrier material and the PW @ MOF-5-PC-700 ℃ composite phase change material, and the result is shown in figure 1, and the PW is clearly and uniformly filled in the hierarchical nanopores which are regularly distributed in three dimensions.
In this example, the ratios of ZnO in MOF-5-PC-600 ℃, MOF-5-PC-700 ℃, and MOF-5-PC-800 ℃ were 28.1%, 29.2%, and 24.56%, respectively, as determined by the XPS semi-quantitative calculation method.
Differential Scanning Calorimetry (DSC) was performed on the PW @ MOF-5-PC-600 ℃ composite phase change material, the PW @ MOF-5-PC-700 ℃ composite phase change material, the PW @ MOF-5-PC-800 ℃ composite phase change material, and the PW, respectively, and the results are shown in FIG. 2. DSC test results show that the PW @ MOF-5-PC-700 ℃ composite PCMs have the phase transition temperature of 55.40/48.03 ℃, the melting enthalpy and the solidification enthalpy of 80.37/84.12J/g respectively and excellent latent heat performance. Under the condition that the controlled load (PW) is 60%, the enthalpy value difference between the PW @ MOF-5-PC-600 ℃ composite phase change material and the PW @ MOF-5-PC-800 ℃ composite phase change material and the PW @ MOF-5-PC-700 ℃ composite phase change material is very small and can be almost ignored.
The UV-vis-NIR absorption spectrum in FIG. 3 shows that the light absorption capacity at PW @ MOF-5-PC-700 ℃ is better than that at PW @ MOF-5-PC-600 ℃ and is better than that at PW @ MOF-5-PC-800 ℃, which is consistent with the photo-thermal conversion capacity of the composite phase change material. And PW @ MOF-5-PC-700 ℃ can realize the full-wave-band absorption characteristic of visible light.
Respectively carrying out infrared analysis (FT-IR) on the PW @ MOF-5-PC-700 ℃ composite phase change material, the PW and a zinc oxide/hierarchical porous carbon composite MOF-5-PC-700 ℃ carrier material, wherein characteristic peaks of the PW are respectively 2918cm as shown in figure 4-1、2849cm-1、1467cm-1And 723cm-1. These characteristic peaks also appear at PW @ MOF-5-PC-700 ℃. The ratio of PW to pure PCMs, the ir spectra of the corresponding MOF-derived hierarchical porous carbon-based composite PCMs did not show new peak positions, i.e. no new chemical bonds were generated, and were substantially identical to the peak positions of pure PCMs, indicating that the forces between pure PCMs and MOF-derived hierarchical porous carbon-based composite PCMs are physical interactions, not chemical interactions. This physical interaction successfully prevented the leakage of the melted PCMs molecules.
The photo-thermal energy conversion calculation is carried out on the PW @ MOF-5-PC-600 ℃ composite phase change material, the PW @ MOF-5-PC-700 ℃ composite phase change material and the PW @ MOF-5-PC-800 ℃ composite phase change material, the result is shown in figure 5, the curve shows that the photo-thermal conversion efficiency of the PW @ MOF-5-PC-700 ℃ is the highest, the optimal photo-thermal conversion effect is shown by the three-dimensional hierarchical porous carbon matrix material and ZnO nanoparticles when the carbonization temperature is 700 ℃, the structure is most beneficial to the conversion of photo-thermal energy, and meanwhile, the photo-thermal conversion efficiency in the embodiment can reach 93.14% by calculation through a formula.
The inventor of the invention also finds that the excessive carbonization time can not improve the photothermal conversion efficiency, but can reduce the photothermal conversion efficiency, and probably the excessive carbonization time causes the reduction of the dispersibility and content of ZnO and the change of the pores and the pore diameters of the carbon material.
Example 2
A preparation method of a three-dimensional metal-organic framework derivative-based photo-thermal composite phase-change material specifically comprises the following steps:
(1) preparation of IRMOF-3:
adding Zn (NO)3)2.6H2O (595mg) and 2-aminoterephthalic acid (181mg) were dissolved in 50ml of DMF and stirred vigorously for 5min, then triethylamine (101mg) was added thereto and stirring was continued for 120 min. The resulting precipitate was collected by centrifugation, washed three times with DMF, washed three times with methanol, and then dried in a vacuum oven at 80 ℃ for 24 hours to obtain a sample.
(2) Preparation of IRMOF-3-PC carrier material:
directly carbonizing the IRMOF-3 to obtain the IRMOF-3-PCs. Putting IRMOF-3 white powder into an alumina crucible, heating to a certain temperature X at the speed of 5 ℃/min under the flowing of nitrogen, maintaining for 3h, and then cooling to room temperature at the speed of 10 ℃/min to prepare the carbon material.
Wherein, the carbonization treatment is respectively carried out at the temperature of 650 ℃, 750 ℃ and 850 ℃ to obtain carbon materials of IRMOF-3-PC-650 ℃, IRMOF-3-PC-750 ℃ and IRMOF-3-PC-850 ℃.
(3) Compounding IRMOF-3-PC carrier materials with PCMs:
composite PCMs are prepared by physical blending and vacuum impregnation. Dissolving PEG10000 in ethanol, fully stirring for 1h to prepare a phase-change material solution, adding the carbon material obtained in the step (2) into the phase-change material solution, reacting at the temperature of 80-120 ℃, continuously stirring until the ethanol is completely evaporated, placing the obtained composite material in an oven at the temperature of 80 ℃ for drying for 8-24h, and repeatedly replacing filter paper during the period until no PW melting trace exists on the filter paper, thereby obtaining the composite phase-change material.
Respectively compounding the carbon material IRMOF-3-PC-650 ℃, IRMOF-3-PC-750 ℃ and IRMOF-3-PC-850 ℃ in the step (2) with phase change material solutions to respectively obtain composite phase change materials PEG10000@ IRMOF-3-PC-650 ℃, PEG10000@ IRMOF-3-PC-750 ℃ and PEG10000@ IRMOF-3-PC-850 ℃ composite PCMs. The PEG10000@ IRMOF-3-PC-750 ℃ composite PCMs prepared in the embodiment have the PEG10000 loading capacity of 80%.
Example 3
A preparation method of a three-dimensional metal-organic framework derivative-based photo-thermal composite phase-change material specifically comprises the following steps:
(1) preparation of ZIF-8:
zn (NO) firstly3)2.6H2O (623mg) and 2-methylimidazole (221mg) were dissolved in 25mL of a methanol solution, respectively. Then Zn (NO)3)2.6H2The O methanol solution was poured rapidly into the 2-methylimidazole methanol solution and stirred vigorously for 5 min. After stirring, the samples were aged for 10min, 3h and 24h, respectively. Finally, the white precipitate was centrifuged and washed several times with methanol and dried overnight at room temperature.
(2) Preparing a ZIF-8-PC carrier material:
ZIF-8 is directly carbonized to obtain ZIF-8-PCs. Putting ZIF-8 white powder into an alumina crucible, heating to a certain temperature X at a speed of 5 ℃/min under the flowing of nitrogen, respectively maintaining for 3h, and then cooling to room temperature at a speed of 10 ℃/min to obtain a carbon material;
wherein, the carbon materials are carbonized at the temperature of 600 ℃ and 700 ℃ and 800 ℃ respectively to obtain the carbon materials of ZIF-8-PC-500 ℃, ZIF-8-PC-600 ℃ and ZIF-8-PC-700 ℃.
(3) Compounding ZIF-8-PC carrier materials with PCMs:
composite PCMs were prepared using physical blending and vacuum impregnation: dissolving PEG10000 in ethanol, fully stirring for 1h to prepare a phase-change material solution, adding the carbon material obtained in the step (2) into the phase-change material solution, reacting at the temperature of 80-120 ℃, continuously stirring until the ethanol is completely evaporated, placing the obtained composite material in an oven at the temperature of 80 ℃ for drying for 8-24h, and repeatedly replacing filter paper during the period until no PW melting trace exists on the filter paper, thereby obtaining the composite phase-change material.
Respectively compounding the carbon material ZIF-8-500 ℃, ZIF-8-PC-600 ℃ and ZIF-8-PC-800 ℃ in the step (2) with phase change material solutions to respectively obtain composite phase change materials PEG10000@ ZIF-8-PC-500 ℃, PEG10000@ ZIF-8-PC-600 ℃ and PEG10000@ ZIF-8-PC-700 ℃ composite PCMs. PEG10000 loading in the PEG10000@ ZIF-8-PC-600 ℃ composite PCMs prepared in the embodiment is 75%.
Comparative example 1
Referring to the method of example 1, a composite phase change material is prepared, except that when the carbonization temperature X is 1000 ℃, MOF-5 is completely changed into a carbon material (i.e., when the carbonization temperature is 1000 ℃, ZnO in the carbon material is evaporated), for controlling variables, when 60% paraffin is loaded, the force between the carrier material and the paraffin molecules of the phase change material is too small to perform a photo-thermal energy conversion test, which indicates that MOF-5-PC-1000 ℃ is more suitable for the energy storage field rather than photo-thermal energy conversion, no effective photo-thermal absorbent is contained in the carrier material, and the heat transfer efficiency is affected by too large pore volume.
The inventor of the invention finds that the nucleation, migration aggregation, evaporation and the like of the ZnO nanoparticles in the carbonization process influence the distribution, the number of pores, the pore size and the like of the pores of the carbon material on the one hand, influence the dispersivity and the content of the ZnO nanoparticles in the carbon material on the other hand, the invention reasonably regulates and controls the carbonization temperature, the carbonization time, the cooling time and the like, so that the dispersibility, the content and the pore-level structure of the ZnO nanoparticles in the carbon material are in a proper range, and the synergistic effect with the phase-change material is more remarkable, thereby ensuring the high photothermal conversion efficiency.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A metal organic framework derivative-based photothermal phase change material is characterized by comprising a zinc oxide/multi-stage pore carbon composite and a phase change material adsorbed on the surface and/or in a pore channel of the zinc oxide/multi-stage pore carbon composite, wherein the zinc oxide/multi-stage pore carbon composite is a carbon composite material which is obtained by carbonizing a zinc-metal organic framework at a high temperature and is distributed with zinc oxide nanoparticles in a highly uniform dispersion manner, and the zinc oxide nanoparticles account for 20-50% of the total weight of the zinc oxide/multi-stage pore carbon composite.
2. The metal-organic framework derivative-based photothermal phase change material as claimed in claim 1, wherein the mass ratio of the phase change material to the zinc oxide/hierarchical porous carbon composite in the composite phase change material is 1-99: 99-1, optionally 50-90: 50-10, optionally 55-85: 45-15, optionally 55-80: 45-20, preferably 55-70: 45-30 parts of;
and/or the zinc oxide nanoparticles comprise 24 to 40%, alternatively 24 to 35%, alternatively 28 to 35%, alternatively 29 to 35%, preferably 29 to 30% of the total weight of the zinc oxide/hierarchical pore carbon composite;
and/or the zinc oxide nanoparticles are highly uniformly distributed in the carbon material.
3. The metal-organic framework derivative based photothermal phase change material according to claim 1 or 2, wherein the zinc-metal organic framework is selected from one or more of MOF-5 materials containing zinc ligands, IRMOF series materials containing zinc ligands, and ZIF series materials containing zinc ligands.
4. The metal-organic framework derivative-based photothermal phase change material according to any one of claims 1 to 3, wherein the phase change material is a solid-liquid phase change material, optionally selected from one or more of polyol phase change material, paraffin phase change material and fatty acid phase change material;
optionally, the polyol phase-change material is selected from one or more of polyethylene glycol, pentaerythritol and neopentyl glycol; optionally the average molecular weight of the polyethylene glycol is 800-;
optionally, the paraffin-based phase change material comprises paraffin with a melting point of 20-60 ℃;
optionally, the fatty acid phase-change material is selected from one or more of stearic acid, myristic acid, palmitic acid, capric acid, lauric acid, pentadecanoic acid and sebacic acid.
5. The metal-organic framework derivative-based photothermal phase change material according to any of claims 1 to 4, wherein the process for compounding the composite phase change material comprises the following steps: soaking the zinc oxide/hierarchical pore carbon composite into a phase change material solution, and carrying out vacuum impregnation and drying to obtain a composite phase change material; optionally, the phase-change material solution is prepared by dissolving a phase-change material in a solvent;
optionally, in the compounding process, the impregnation reaction temperature is higher than the phase change temperature of the phase change material, and optionally, the reaction temperature is 80-120 ℃;
optionally, in the compounding process, the drying temperature is higher than the phase change temperature of the phase change material, and optionally, the drying temperature is 80-120 ℃; optionally, the drying time is 12-48 h.
6. The metal-organic framework derivative-based photothermal phase change material according to any of claims 1 to 5, wherein the high temperature carbonization conditions are as follows: under the protection of inert gas atmosphere, raising the temperature to the carbonization temperature at the heating rate of 2-8 ℃/min; keeping the carbonization temperature for 1-6 h, and cooling to obtain the carbon material.
7. The metal-organic framework derivative-based photothermal phase change material according to claim 6, wherein the temperature increase rate is 5 ℃/min;
and/or the carbonization temperature is 400-900 ℃; optionally the carbonization temperature is 600-800 ℃; optionally a carbonization temperature of 600-;
and/or the carbonization temperature is kept for 2 to 4 hours, preferably 3 hours;
and/or the inert gas is nitrogen or argon, preferably nitrogen.
8. The metal-organic framework derivative-based photothermal phase change material according to claim 6 or 7, wherein the cooling method comprises: cooling at the speed of 5-15 ℃/min, optionally cooling at the speed of 10 ℃/min.
9. The metal-organic framework derivative-based photothermal phase change material according to any of claims 1 to 7, wherein the zinc-metal organic framework is obtained by reacting a zinc salt with an organic ligand;
optionally, the preparation method of the zinc-metal organic framework comprises the following steps: adding the zinc salt hydrate solution into an organic ligand, stirring, then dripping triethylamine, continuing stirring, collecting the precipitate, washing and drying to obtain a zinc-metal organic framework;
optionally, the zinc salt comprises Zn (NO)3)2.6H2O and Zn (NO)3)2.4H2One or more of O;
alternatively, the molar ratio of the zinc salt hydrate to the organic ligand is 10: 1-20, optionally 10: 1-10, optionally 10: 3-6, preferably 10: 4 to 5.
10. Use of a metal-organic framework derivative-based photothermal phase change material according to any of claims 1 to 9 as a photothermal conversion material, optionally in the field of solar thermal storage.
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| CN115159606A (en) * | 2022-08-10 | 2022-10-11 | 浙江大学 | Method for treating organic sewage by utilizing solar energy photo-thermal catalysis |
| CN115724604A (en) * | 2022-11-23 | 2023-03-03 | 南京航空航天大学 | Preparation method of composite antibacterial cementing material |
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| CN114231256A (en) * | 2021-12-31 | 2022-03-25 | 苏州阿德旺斯新材料有限公司 | Magnetic high-graphitization carbon-based photo-thermal composite phase change material and application thereof |
| CN114231256B (en) * | 2021-12-31 | 2024-05-10 | 苏州荣格君新材料有限公司 | Magnetic high graphitization carbon-based photo-thermal composite phase change material and application thereof |
| CN115159606A (en) * | 2022-08-10 | 2022-10-11 | 浙江大学 | Method for treating organic sewage by utilizing solar energy photo-thermal catalysis |
| CN115159606B (en) * | 2022-08-10 | 2024-01-26 | 浙江大学 | Method for treating organic sewage by utilizing solar photo-thermal catalysis |
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