CN114774085A - Bimetallic MOF (Metal organic framework) derived graphitized carbon-based photothermal composite phase change material as well as preparation method and application thereof - Google Patents
Bimetallic MOF (Metal organic framework) derived graphitized carbon-based photothermal composite phase change material as well as preparation method and application thereof Download PDFInfo
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- 239000012782 phase change material Substances 0.000 title claims abstract description 119
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 109
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 239000013246 bimetallic metal–organic framework Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- 150000003839 salts Chemical class 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000013110 organic ligand Substances 0.000 claims abstract description 32
- 239000006249 magnetic particle Substances 0.000 claims abstract description 16
- 239000002923 metal particle Substances 0.000 claims abstract description 15
- 239000013384 organic framework Substances 0.000 claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 15
- 229940011182 cobalt acetate Drugs 0.000 claims description 14
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 238000005338 heat storage Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000004246 zinc acetate Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011162 core material Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
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- 239000012071 phase Substances 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
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- 229920006395 saturated elastomer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004781 supercooling Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012221 photothermal agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013111 pure metal metal-organic framework Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
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- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- 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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- 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
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S60/00—Arrangements for storing heat collected by solar heat collectors
- F24S60/10—Arrangements for storing heat collected by solar heat collectors using latent heat
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Abstract
The invention relates to the field of phase change materials, in particular to a bimetallic MOF (metal organic framework) derived graphitized carbon-based photo-thermal composite phase change material as well as a preparation method and application thereof. The composite material comprises bimetallic MOF-derived graphitized carbon and a phase-change material adsorbed on the surface and/or in a pore channel of the bimetallic MOF-derived graphitized carbon, wherein the bimetallic MOF-derived graphitized carbon is a nano material containing magnetic metal particles obtained by carbonizing a bimetallic organic framework at high temperature, and the magnetic metal particles are selected from one or more of iron, nickel and cobalt magnetic particles; the bimetallic organic framework is obtained by reacting metal salt A, metal salt B and an organic ligand through a hydrothermal method, wherein the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-1): 1. the metal salt B is used to form magnetic metal particles. The composite phase change material is of a one-dimensional nano structure, has high phase change latent heat and better stability, and has excellent photo-thermal conversion performance.
Description
Technical Field
The invention relates to the field of phase change materials, in particular to a bimetal MOF (metal organic framework) derived graphitized carbon-based photo-thermal composite phase change material as well as a preparation method 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 that is already known to a person skilled in the art.
Photothermal conversion is a technique for converting light energy (particularly abundant sunlight) into heat energy. In the face of increasing global energy demand and environmental problems arising from fossil energy consumption, the photothermal conversion technology has received increasing attention. However, sunlight is changed by natural conditions such as climate, time and latitude, has the defects of discontinuity, instability and the like, is difficult to be directly absorbed and utilized by the existing storage materials and devices, and needs additional light capture and light-heat conversion materials. Latent heat storage is an environment-friendly energy-saving technology, and can solve the problem of mismatching between energy production and demand in time and space, thereby realizing efficient utilization of energy. Among them, organic PCMs such as paraffin, fatty acid and higher alcohols have been widely studied due to their advantages of stable chemical and thermal properties, small supercooling degree, no phase segregation during phase transition, etc. However, most organic PCMs have low thermal conductivity and low photo-thermal conversion efficiency, and the large-scale practical application of the phase change material in the photo-thermal conversion aspect is severely limited.
Research shows that MOF can be simply and conveniently converted into traditional inorganic functional materials with nano structures through high-temperature pyrolysis: while the organic ligands constituting the MOF structure are converted into porous graphitic carbon materials, metal ions tend to be reduced to metal nanoparticles or metal oxides. Carbon materials and metal materials are common photothermal agents in photothermal conversion. However, the current MOF calcined porous carbon material as a phase change material carrier has the disadvantages of weak light absorption capability and low light-to-heat conversion efficiency, so that it is an important task to construct a MOF-based composite phase change material with strong light absorption capability and high light-to-heat conversion efficiency.
Disclosure of Invention
Object of the Invention
In order to solve the technical problems, the invention aims to provide a bimetal MOF derived graphitized carbon-based photothermal composite phase change material and a preparation method and application thereof, the composite phase change material is obtained by selecting a reasonable raw material proportion, more magnetic sites are exposed in the calcining process, so that magnetic particles in the graphitized carbon material are cooperated with porous carbon and the phase change material, solar energy acquisition and conversion are greatly improved in a synergistic manner within a certain working temperature range (application scene temperature range), and a constructed three-dimensional network structure has high thermal conductivity, affinity and photon capturing capability, provides good light absorption, thermal conductivity and photothermal conversion performance, is expected to show unique advantages in solar energy efficient photothermal utilization, and can solve the problem of low photothermal utilization efficiency of the organic phase change material.
The composite phase change material is of a one-dimensional nano structure, has high phase change latent heat and better stability, and has excellent photo-thermal conversion performance. The highly graphitized carbon (including carbon nano tubes) generated by calcining the bimetallic MOF has excellent light capturing capability, the generated magnetic metal particles cooperate with the highly graphitized carbon to further improve the photo-thermal conversion efficiency of the composite phase-change material, and the photo-thermal conversion performance of the composite phase-change material is improved by using the one-dimensional bimetallic MOF material for the first time.
Solution scheme
In order to achieve the purpose of the present invention, an embodiment of the present invention provides a bimetal MOF derived graphitized carbon-based photothermal composite phase change material, including bimetal MOF derived graphitized carbon and a phase change material adsorbed on the surface and/or in a pore channel of the bimetal MOF derived graphitized carbon, where the bimetal MOF derived graphitized carbon is a nanomaterial containing magnetic metal particles obtained by carbonizing a bimetal organic framework at a high temperature, and the magnetic metal particles are selected from one or more of iron, nickel, and cobalt magnetic particles;
the bimetallic organic framework is obtained by reacting metal salt A, metal salt B and an organic ligand through a hydrothermal method, wherein the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-1): 1; the metal salt B is used for forming magnetic metal particles; the metal salt A and the metal salt B are salts of different metals.
Further, in the photo-thermal composite phase change material, the loading capacity of the phase change material is 50-70%, optionally 50-65%, optionally 50-60%, optionally 60%.
Further, in the bimetallic organic framework, the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-0.8): 1, optionally (0.5-1.1): (0.1-0.8): 1; optionally (0.5-1.1): (0.1-0.5): 1, optionally (0.8-1.1): (0.1-0.2): 1, optionally (0.9-1.1): (0.1-0.15): 1, optionally (0.9-0.99): (0.1-0.11): 1, optionally (0.945-0.99): (0.105-0.11): alternatively 0.9675: 0.1075: 1.
further, the metal salt A is selected from one or more of zinc salt and copper salt; optionally, the metal salt a is a zinc salt;
and/or the metal salt B is selected from one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, ferric nitrate, ferric chloride, ferric sulfate and ferric acetate.
Further, the phase change material is selected from one or more of lauric acid, octadecanol, polyethylene glycol, octadecylamine and paraffin; optionally, the phase change material is dodecanoic acid;
further, the organic ligand is selected from one or more of 1,3, 5-trimesic acid, terephthalic acid and 2-methylimidazole; optionally, the organic ligand is 1,3, 5-trimesic acid.
Further, the high-temperature carbonization is carried out heat preservation carbonization at 600-900 ℃ in an inert gas atmosphere; optionally the carbonization temperature is 700-850 ℃, optionally 700-800 ℃, optionally 750 ℃;
further, the bimetallic MOF-derived graphitized carbon is a one-dimensional nanostructure.
In another aspect, a preparation method of the bimetallic MOF derived graphitized carbon-based photothermal composite phase change material is provided, which includes:
dispersing the bimetallic MOF derived graphitized carbon in a phase change material solution, mixing and drying to prepare a composite phase change material;
the preparation method of the bimetallic MOF derived graphitized carbon comprises the following steps: adding a salt aqueous solution into an organic ligand aqueous solution at the temperature of 90-110 ℃, stirring, collecting precipitates, and washing to obtain a bimetallic organic frame; the brine solution contains a metal salt A, a metal salt B and water; carbonizing a bimetallic organic frame at 600-900 ℃ under an inert gas atmosphere to obtain bimetallic MOF (Metal organic framework) derived graphitized carbon; alternatively, the temperature of the aqueous organic ligand solution is 100 ℃;
wherein the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-1): 1;
the metal salt B is selected from one or more of nickel salt, iron salt and cobalt salt;
the metal salt A and the metal salt B are salts of different metals.
Further, in the photo-thermal composite phase change material, the loading capacity of the phase change material is 50-70%, optionally 50-65%, optionally 50-60%, optionally 60%.
Further, in the bimetallic organic framework, the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-0.8): 1, optionally (0.5-1.1): (0.1-0.8): 1; optionally (0.5-1.1): (0.1-0.5): 1, optionally (0.8-1.1): (0.1-0.2): 1, optionally (0.9-1.1): (0.1-0.15): 1, optionally (0.9-0.99): (0.1-0.11): 1, optionally (0.945-0.99): (0.105-0.11): optionally 0.9675: 0.1075: 1.
further, the phase change material is selected from one or more of lauric acid, octadecanol, polyethylene glycol, octadecylamine and paraffin; optionally, the phase change material is dodecanoic acid.
Further, the organic ligand is selected from one or more of 1,3, 5-trimesic acid, terephthalic acid and 2-methylimidazole; optionally, the organic ligand is 1,3, 5-trimesic acid.
Further, the phase change material is supported by the bimetallic MOF derived graphitized carbon by a melt impregnation method.
Further, the metal salt A is selected from one or more of zinc salt and copper salt; optionally, the metal salt a is a zinc salt.
Further, the metal salt B is selected from one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, ferric nitrate, ferric chloride, ferric sulfate and ferric acetate.
Further, in the preparation of the bimetallic organic framework, the concentration of the metal salt A in the saline solution is 0.1-0.2 mol/L; the concentration of the metal salt B in the saline solution is 0.1-0.2 mol/L; the concentration of the organic ligand in the organic ligand aqueous solution is 0.02-0.05 mol/L.
Alternatively, the volume ratio of the aqueous salt solution to the aqueous organic ligand solution is 1: (8-10);
optionally, the stirring reaction time is 3-8 min, optionally 5-8 min;
optionally, the bimetallic organic framework is a one-dimensional nanostructure.
Further, the carbonization time is 0.5-10 h; optionally 0.5-6 h, optionally 1-3 h; optionally 1-2 h;
and/or, the inert gas comprises argon, nitrogen or a hydrogen-argon mixed gas;
and/or the carbonization temperature is 700-850 ℃, optionally 700-800 ℃, optionally 750 ℃; optionally, the heating rate is 3-8 ℃/min, optionally 5 ℃/min.
In another aspect, an application of the bimetallic MOF derived graphitized carbon-based photothermal composite phase change material or the bimetallic MOF derived graphitized carbon-based photothermal composite phase change material prepared by the preparation method is provided, and the bimetallic MOF derived graphitized carbon-based photothermal composite phase change material is used as a photothermal conversion material or a thermoelectric conversion test, and is optionally used in the field of solar heat storage.
Advantageous effects
(1) According to the composite phase-change material, more magnetic particle sites are exposed in the calcining process through selecting the reasonable raw material proportion, so that the magnetic particles in the graphitized carbon material are cooperated with the porous carbon and the phase-change material, the composite phase-change material greatly improves the solar energy acquisition and conversion in a cooperative manner within a certain working temperature range (application scene temperature range), the constructed three-dimensional network structure has high thermal conductivity, affinity and photon capturing capability, good light absorption, thermal conductivity and photo-thermal conversion performance are provided, meanwhile, the unique advantages are expected to be shown in the solar energy efficient photo-thermal utilization, and the problem of low photo-thermal utilization efficiency of the organic phase-change material can be solved.
(2) The composite phase change material is of a one-dimensional nano structure, has high phase change latent heat and better stability, and has excellent photo-thermal conversion performance. The high graphitized carbon (including carbon nano tubes) generated by calcining the bimetal MOF has excellent light capture capacity, the generated magnetic metal particles cooperate with the high graphitized carbon to further improve the photo-thermal conversion efficiency of the composite phase change material, and the photo-thermal conversion performance of the composite phase change material is improved by using the one-dimensional bimetal MOF material for the first time.
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 a drawing ofScanning Electron Microscope (SEM) images of the one-dimensional bimetallic ZnCoMOF obtained in the embodiment 1 and the derived highly graphitized carbon obtained after high-temperature calcination of the one-dimensional bimetallic ZnCoMOF; wherein a is bimetallic Zn0.9Co0.1SEM image of MOF; b is Zn carbonized at high temperature0.9Co0.1SEM images of MOF-C bimetallic MOF derived graphitized carbon.
FIG. 2 shows dodecanoic acid @ Zn obtained in comparative example 11Co0MOF-C derived carbon and dodecanoic acid @ Zn of example 1 of the present invention0.9Co0.1DSC curves of MOF-C derived carbons are compared.
FIG. 3 shows example 1 (Zn)0.9Co0.1MOF-C), example 4 (Zn)0.5Co0.5MOF-C), comparative example 1 (Zn)1Co0MOF-C) isothermal adsorption (BET) profile of MOF-derived graphitized carbon.
FIG. 4 shows example 1 (Zn)0.9Co0.1MOF-C), example 4 (Zn)0.5Co0.5-MOF-C), comparative example 1 (Zn)1Co0MOF-C) temperature-time (T-T) profile of the composite of MOF-derived graphitized carbon supported dodecanoic acid under simulated solar radiation.
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 term "comprise" or variations such as "comprises" or "comprising", etc., 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 supported amount of the PCMs is [ mass of PCMs/(mass of PCMs + mass of bimetallic graphitized carbon) ] x 100%.
The technical scheme of the invention is as follows: (1) the method comprises the steps of synthesizing bimetallic MOF by taking metal salt A, metal salt B and an organic ligand as raw materials through a hydrothermal method, and then calcining the bimetallic MOF in a nitrogen atmosphere to obtain highly graphitized carbon (which can be a carbon nano tube) containing magnetic oxide particles. (2) The composite phase-change material is prepared by adopting a melting impregnation method, the phase-change material is placed in an oven and heated to be completely melted, and a proper heating temperature (higher than the phase-change temperature) is selected according to different types of phase-change core materials. Adding a high-graphitization carbon material into the dodecanoic acid melt, and preserving heat for a period of time until the phase-change material is completely impregnated into the high-graphitization carbon (including carbon nano tubes) and the magnetic oxide particle carrier material (so that the carrier material reaches saturated adsorption); and finally, drying at the temperature higher than the phase change temperature, and repeatedly replacing the filter paper in the period until no melting trace of the phase change material exists on the filter paper, thereby finally obtaining the bimetal graphitized carbon-based composite phase change material.
Example 1
A one-dimensional bimetal MOF derived graphitized carbon-based composite phase change material and a preparation method thereof comprise the following steps:
(1) preparation of one-dimensional bimetallic MOF:
adding 0.42g (1.935mmol) of zinc acetate and 0.054g (0.215mmol) of cobalt acetate (9:1) into 10.0mL of deionized water, magnetically stirring the mixture at room temperature for standby, adding 0.42g (2.0mmol) of 1,3, 5-trimesic acid (BTC) into 90.0mL of deionized water, and stirring the mixture for 30min under the condition of 100 ℃ constant temperature water bath to obtain a transparent and uniform solution; and quickly pouring the prepared zinc acetate and cobalt acetate into a 1,3, 5-trimesic acid solution, stirring for 5min, and gradually generating a precipitate. The resulting precipitate was then washed 6 times with ethanol and centrifuged at 3000 rpm. Finally, the washed sample is dried in vacuum and marked as one-dimensional Zn0.9Co0.1MOF。
(2) Preparation of MOF-derived graphitized carbon and magnetic oxides:
0.5g of one-dimensional Zn prepared as described above0.9Co0.1Adding MOF into porcelain boat, heating at 750 deg.C in nitrogen atmosphere for 1h to generate one-dimensional MOF derived graphitized carbon and magnetic oxide, noted as Zn0.9Co0.1MOF-C。
Wherein the heating rate is 5 ℃/min, and black powder is obtained. Heating Rate and N used2The flow rates are respectively 5 ℃/min and 400mL/min-1。
(3) Preparing an MOF (metal organic framework) -derived graphitized carbon-based composite phase-change material:
adding 0.3g of dodecanoic acid into a beaker, putting the beaker into a 60 ℃ oven, and heating the beaker until the dodecanoic acid is completely melted;
0.2g of MOF-derived graphitized carbon (Zn) prepared as described above0.9Co0.1MOF-C) support material was added to the dodecanoic acid melt above and kept at 80 ℃ for 6h until the phase change material was completely impregnated into the MOF derived graphitized carbon support material (saturated adsorption was reached);
and then drying in an oven at 100 ℃ for 8h, and repeatedly replacing the filter paper in the period until no melting trace of the phase change material exists on the filter paper, thereby finally obtaining the one-dimensional bimetal MOF derived high graphitized carbon-based composite phase change material. Wherein the loading amount of the dodecanoic acid is 60 percent.
In the one-dimensional bimetallic MOF-derived graphitized carbon-based composite phase-change material, the load amount of the phase-change core material is [ mass of the phase-change core material/(mass of the phase-change core material + mass of the one-dimensional MOF-derived highly graphitized carbon) ] × 100%.
The enthalpy value of the composite phase change material prepared in the embodiment is 97.4J/g, and the highest photothermal conversion efficiency in the embodiment can reach 85.1% by calculation through a formula.
The one-dimensional bimetal MOF-Zn prepared in the step (1) of the embodiment0.9Co0.1MOF and derived bimetallic graphitized carbon Zn prepared in step (2)0.9Co0.1The Scanning Electron Microscope (SEM) scan of MOF-C is shown in FIG. 1; as can be seen from the SEM scan of FIG. 1a, the one-dimensional bimetallic MOF has a rod-like structure, uniform size, smooth surface and intertwining. As is clear from FIG. 1b, a one-dimensional bimetallic Zn0.9Co0.1After MOF calcination, the surface becomes rough, and the derived one-dimensional rod-shaped structure highly graphitized carbon Zn0.9Co0.1The MOF-C are mutually entangled to form a three-dimensional network structure, and the generated magnetic metal oxide is attached to the surface of a rough one-dimensional rod-shaped structure, so that the light reflectivity is reduced, the light absorption is improved, the generated high-graphitization carbon and the magnetic oxide have a synergistic effect, and the dodecanoic acid @ Zn is synergistically improved0.9Co0.1The MOF-C derived highly graphitized carbon composite phase change material has the photo-thermal conversion performance.
DSC tests of the composite phase change materials of comparative example 1 and example 1 are shown in FIG. 2, which shows that Zn without magnetic particles1Co0The supercooling degree of the MOF-C is higher than that of Zn containing magnetic particles0.9Co0.1MOF-C shows that the bimetallic MOF promotes the formation of crystal nuclei due to the synergistic effect of magnetic particles, reduces the supercooling degree and enhances the heat transfer capacity.
Example 2
A one-dimensional bimetal MOF derived graphitized carbon-based composite phase change material and a preparation method thereof comprise the following steps:
(1) preparation of one-dimensional bimetallic MOF:
adding 0.42g (1.935mmol) of zinc acetate and 0.041g (0.215mmol) (9:1) of ferric acetate into 10.0mL of deionized water, magnetically stirring at room temperature for standby, adding 0.42g (2.0mmol) of 1,3, 5-trimesic acid into 90.0mL of deionized water, and stirring for 30min under the condition of 100 ℃ constant-temperature water bath to obtain a transparent and uniform solution; and quickly pouring the prepared zinc acetate and iron acetate into a 1,3, 5-trimesic acid solution, and stirring for 5min to gradually generate red precipitates. The resulting precipitate was then washed 6 times with ethanol and centrifuged at 3000 rpm. And finally, carrying out vacuum drying on the washed sample, and recording as one-dimensional ZnFeMOF.
(2) Preparation of MOF-derived graphitized carbon and magnetic oxides:
0.5g of the one-dimensional ZnFeMOF prepared in the previous step is added into a porcelain boat, and the porcelain boat is heated for 1h in a nitrogen atmosphere at 750 ℃ to generate one-dimensional MOF derived graphitized carbon and magnetic oxide which are marked as ZnFeMOF-C.
Wherein the heating rate is 5 ℃/min, and black powder is obtained. Heating rate and N used2The flow rates are respectively 5 ℃/min and 400mL/min-1。
(3) Preparing an MOF (metal organic framework) -derived graphitized carbon-based composite phase-change material:
adding 0.3g of dodecanoic acid into a beaker, and heating the beaker in a 60 ℃ oven until the dodecanoic acid is completely melted;
adding 0.2g of the above prepared MOF derived graphitized carbon ZnFeMOF-C support material to the above dodecanoic acid melt, and keeping at 60 ℃ for 6h until the phase change material is completely impregnated into the MOF derived graphitized carbon support material (saturated adsorption is reached);
and then drying in an oven at 100 ℃ for 8h, and repeatedly replacing the filter paper until no melting trace of the phase change material exists on the filter paper, thereby finally obtaining the one-dimensional bimetallic MOF derived high graphitized carbon-based composite phase change material. Wherein the loading amount of the dodecanoic acid is 60%.
Example 3
A one-dimensional bimetallic MOF derived graphitized carbon-based composite phase-change material and a preparation method thereof comprise the following steps:
(1) preparation of one-dimensional bimetallic MOF:
adding 0.42g (1.935mmol) of zinc acetate and 0.054g (0.215mmol) (9:1) of nickel acetate into 10.0mL of deionized water, magnetically stirring the mixture at room temperature for standby, adding 0.42g (2.0mmol) of 1,3, 5-trimesic acid into 90.0mL of deionized water, and stirring the mixture for 30min under the condition of 100 ℃ constant-temperature water bath to obtain a transparent and uniform solution; and quickly pouring the prepared zinc acetate and nickel acetate into a 1,3, 5-trimesic acid solution, and stirring for 5min to gradually generate green precipitates. The resulting precipitate was then washed 6 times with ethanol and centrifuged at 3000 rpm. And finally, carrying out vacuum drying on the washed sample, and recording as one-dimensional ZnNiMOF.
(2) Preparation of MOF-derived graphitized carbon and magnetic oxides:
0.5g of the one-dimensional ZnNiMOF prepared in the previous step is added into a porcelain boat, and the porcelain boat is heated for 1h in a nitrogen atmosphere at 750 ℃ to generate one-dimensional MOF derived graphitized carbon and magnetic oxide which are marked as ZnFe-MOF-C.
Wherein the heating rate is 5 ℃/min, and black powder is obtained. Heating rate and N used2The flow rates are 5 ℃/min and 400mL/min respectively-1。
(3) Preparing an MOF-derived graphitized carbon-based composite phase-change material:
adding 0.3g of dodecanoic acid into a beaker, and heating the beaker in a 60 ℃ oven until the dodecanoic acid is completely melted;
adding 0.2g of the prepared MOF-derived graphitized carbon ZnFe-MOF-C carrier material into the dodecanoic acid melt, and keeping the temperature at 60 ℃ for 6h until the phase change material is completely impregnated into the MOF-derived graphitized carbon ZnFe-MOF-C carrier material (saturated adsorption is achieved);
and then drying in an oven at 100 ℃ for 8h, and repeatedly replacing the filter paper until no melting trace of the phase change material exists on the filter paper, thereby finally obtaining the one-dimensional bimetallic MOF derived high graphitized carbon-based composite phase change material. Wherein the loading amount of the dodecanoic acid is 60 percent.
Example 4
A one-dimensional bimetallic MOF derived graphitized carbon-based composite phase-change material and a preparation method thereof comprise the following steps:
(1) preparation of one-dimensional bimetallic MOF:
0.24g (1.075mmol) of zinc acetate and 027g (1.075mmol) (1:1) of cobalt acetate is added into 10.0mL of deionized water and is stirred evenly by magnetic force at room temperature for standby, 0.42g (2.0mmol) of 1,3, 5-trimesic acid is added into 90.0mL of deionized water and is stirred for 30min under the condition of 100 ℃ constant temperature water bath to obtain transparent and uniform solution; and quickly pouring the prepared zinc acetate and cobalt acetate into a 1,3, 5-trimesic acid solution, stirring for 5min, and gradually generating a precipitate. The resulting precipitate was then washed 6 times with ethanol and centrifuged at 3000 rpm. Finally, the washed sample is dried in vacuum and marked as one-dimensional Zn0.5Co0.5MOF。
(2) Preparation of MOF-derived graphitized carbon and magnetic oxides:
0.5g of one-dimensional Zn prepared as described above0.5Co0.5Adding MOF into porcelain boat, heating at 750 deg.C in nitrogen atmosphere for 1h to generate one-dimensional MOF derived graphitized carbon and magnetic oxide, noted as Zn0.5Co0.5MOF-C。
Wherein the heating rate is 5 ℃/min, and black powder is obtained. Heating Rate and N used2The flow rates are 5 ℃/min and 400mL/min respectively-1。
(3) Preparing an MOF (metal organic framework) -derived graphitized carbon-based composite phase-change material:
adding 0.3g of dodecanoic acid into a beaker, putting the beaker into a 60 ℃ oven, and heating the beaker until the dodecanoic acid is completely melted;
0.2g of the MOF-derived graphitized carbon Zn prepared as described above0.5Co0.5-the MOF-C support material was added to the dodecanoic acid melt described above and incubated at 80 ℃ for 6h until the phase change material was completely impregnated into the MOF derived graphitized carbon support material (saturation adsorption was reached);
and then drying in an oven at 100 ℃ for 8h, and repeatedly replacing the filter paper until no melting trace of the phase change material exists on the filter paper, thereby finally obtaining the one-dimensional bimetallic MOF derived high graphitized carbon-based composite phase change material. Wherein the loading amount of the dodecanoic acid is 60%.
In the one-dimensional bimetallic MOF-derived graphitized carbon-based composite phase-change material, the load amount of the phase-change core material is [ mass of the phase-change core material/(mass of the phase-change core material + mass of the one-dimensional MOF-derived highly graphitized carbon) ] × 100%.
The enthalpy value of the composite phase change material prepared in the embodiment is 101.1J/g, and the highest photothermal conversion efficiency in the embodiment can reach 74.7% by calculation through a formula.
The results of examples 1 and 4 show that the photothermal conversion efficiency is greatly different when the molar ratio of the zinc particles to the cobalt magnetic particles is different, and the photothermal conversion efficiency is better than that of 1:1 when the molar ratio of the Zn to the Co is 9:1, which indicates that a small amount of magnetic metal particles can synergistically improve the photothermal conversion efficiency due to the plasma resonance effect. The inventors have also found that when the amount of magnetic metal particles is too large, agglomeration is caused, which is disadvantageous to the action of the plasmon resonance effect and the absorption of light by the derived carbon, and the photothermal conversion efficiency is rather decreased.
Example 5
A one-dimensional bimetallic MOF derived graphitized carbon-based composite phase-change material and a preparation method thereof comprise the following steps:
(1) preparation of one-dimensional bimetallic MOF:
adding 0.42g (1.935mmol) of zinc acetate and 0.054g (0.215mmol) of cobalt acetate (9:1) into 10.0mL of deionized water, magnetically stirring at room temperature for later use, adding 0.42g (2.0mmol) of 1,3, 5-trimesic acid into 90.0mL of deionized water, and stirring for 30min under the condition of 100 ℃ constant-temperature water bath to obtain a transparent and uniform solution; and quickly pouring the prepared zinc acetate and cobalt acetate into a 1,3, 5-trimesic acid solution, stirring for 5min, and gradually generating a precipitate. The resulting precipitate was then washed 6 times with ethanol and centrifuged at 3000 rpm. And finally, carrying out vacuum drying on the washed sample, and recording as one-dimensional ZnCoMOF.
(2) Preparation of MOF-derived graphitized carbon and magnetic oxides:
0.5g of one-dimensional ZnCoMOF prepared as described above was added to a porcelain boat and heated at 750 ℃ for 1h in a nitrogen atmosphere to produce one-dimensional MOF derived graphitized carbon and magnetic oxides, noted as ZnCoMOF-C.
Wherein the heating rate is 5 ℃/min, and black powder is obtained. Heating Rate and N used2The flow rates are 5 ℃/min and 400mL/min respectively-1。
(3) Preparing an MOF-derived graphitized carbon-based composite phase-change material:
adding 0.2g of dodecanoic acid into a beaker, and heating the beaker in an oven at the temperature of 60 ℃ until the dodecanoic acid is completely melted;
adding 0.2g of the prepared MOF-derived graphitized carbon ZnCo-MOF-C carrier material into the dodecanoic acid melt, and keeping the temperature at 80 ℃ for 6 hours until the phase change material is completely impregnated into the MOF-derived graphitized carbon carrier material (saturated adsorption is achieved);
and then drying in an oven at 100 ℃ for 8h, and repeatedly replacing the filter paper in the period until no melting trace of the phase change material exists on the filter paper, thereby finally obtaining the one-dimensional bimetal MOF derived high graphitized carbon-based composite phase change material. Wherein the loading amount of the dodecanoic acid is 50%.
In the one-dimensional bimetallic MOF-derived graphitized carbon-based composite phase-change material, the load amount of the phase-change core material is [ mass of the phase-change core material/(mass of the phase-change core material + mass of the one-dimensional MOF-derived highly graphitized carbon) ] × 100%.
DSC tests of the composite phase change materials of example 1 and example 5 show that the bimetallic MOF derived carbon-based composite phase change material with 60% loading has higher enthalpy value of 104.4J/g and higher photothermal conversion efficiency of 83.1%, and the enthalpy value of 89J/g and photothermal conversion efficiency of 81.4% of a sample with 50% of comparative loading.
Comparative example 1
A one-dimensional bimetallic MOF derived graphitized carbon-based composite phase-change material and a preparation method thereof comprise the following steps:
(1) preparation of one-dimensional monometallic MOF:
adding 0.47g (2.15mmol) of zinc acetate into 10.0mL of deionized water, magnetically stirring at room temperature for uniform standby, adding 0.42g (2.0mmol) of 1,3, 5-trimesic acid into 90.0mL of deionized water, and stirring for 30min at 100 ℃ in a constant-temperature water bath to obtain a transparent and uniform solution; then quickly pouring the prepared zinc acetate into a 1,3, 5-trimesic acid solution, stirring for 5min, and gradually generating a white precipitate. The resulting precipitate was then washed 6 times with ethanol and centrifuged at 3000 rpm. Finally, the washed sample is dried in vacuum and recordedOne-dimensional Zn1Co0MOF。
(2) Preparation of MOF-derived graphitized carbon:
0.5g of one-dimensional Zn prepared as described above1Co0Adding MOF into porcelain boat, heating at 750 deg.C in nitrogen atmosphere for 1h to generate one-dimensional MOF derived graphitized carbon and magnetic oxide, noted as Zn1Co0MOF-C。
Wherein the heating rate is 5 ℃/min, and black powder is obtained. Heating Rate and N used2The flow rates are 5 ℃/min and 400mL/min respectively-1。
(3) Preparing an MOF (metal organic framework) -derived graphitized carbon-based composite phase-change material:
adding 0.3g of dodecanoic acid into a beaker, and heating the beaker in a 60 ℃ oven until the dodecanoic acid is completely melted;
adding 0.2g of the prepared MOF-derived graphitized carbon support material into the dodecanoic acid melt, and keeping the temperature at 60 ℃ for 6h until the phase change material is completely impregnated into the MOF-derived graphitized carbon support material (saturated adsorption is achieved);
and then drying in an oven at 100 ℃ for 8h, and repeatedly replacing the filter paper until no melting trace of the phase change material exists on the filter paper, thereby finally obtaining the one-dimensional single metal MOF-derived high-graphitization carbon-based composite phase change material. Wherein the loading amount of the dodecanoic acid is 60%.
The enthalpy value of the composite phase-change material of the comparative example is 106.57J/g, and the photothermal conversion efficiency is 67.3%.
Example 1 (Zn)0.9Co0.1MOF-C), example 4 (Zn)0.5Co0.5-MOF-C), comparative example 1 (Zn)1Co0Comparison of the isothermal adsorption curves of MOF-derived graphitized carbons of different ratios of zinc and cobalt in MOF-C) results are shown in FIG. 3 by adjusting the Co2+With Zn2+Molar ratio of (B), optimum Co2+With Zn2+Molar ratio of (Zn)0.9Co0.1MOF-C) was successfully obtained with the highest specific surface area and pore volume. Zn0.9Co0.1MOF-C shows the best overall performance, Zn0.9Co0.1MOF-C(1027.7m2A specific surface area of/g) is farGreater than Zn1Co0MOF-C(525.2m2/g) and Zn0.5Co0.5MOF-C(446.7m2Per g) and an average pore diameter (6.0nm) and Zn0.5Co0.5MOF-C (6.8nm) is close to and much larger than Zn1Co0MOF-C (4.7nm), which can increase the number of exposed metal particle sites and can facilitate heat transport. This is probably due to Zn at a heat treatment temperature of 850 deg.C1Co0Zinc oxide, Zn is also present in MOF-C0.9Co0.1MOF-C and Zn0.5Co0.5The zinc oxide in MOF-C has volatilized to provide more specific surface area, but Zn0.5Co0.5Severe agglomeration of Co nanoparticles in MOF-C. The results show that Zn0.9Co0.1The specific surface area and pore size of the MOF-C are alternated to facilitate high thermal conversion efficiency.
Example 1 (Zn)0.9Co0.1MOF-C), example 4 (Zn)0.5Co0.5-MOF-C), comparative example 1 (Zn)1Co0MOF-C) dodecanoic acid-loaded composite phase-change material is compared in temperature and time changes under the irradiation of one light intensity, and the result is shown in figure 4, which shows that the one-dimensional single metal Zn of the comparative example 11Co0Only high graphitized carbon is obtained after MOF calcination, no magnetic metal ions are generated, and the photothermal conversion efficiency after the phase change material is loaded is lower, while the one-dimensional Zn in the embodiment 10.9Co0.1MOF and Zn of example 40.5Co0.5The MOF is calcined to obtain a carbon material with high graphitized carbon synergistically generating magnetic metal particles, and the photo-thermal conversion efficiency after the phase change material is loaded is obviously superior to that of 1Zn in proportion1Co0MOF-C based composite phase change materials due to the plasma enhanced effect of magnetic particles. But Zn of example 10.9Co0.1The photo-thermal conversion efficiency of the MOF-C based composite phase change material is better than that of Zn in example 40.5Co0.5The photothermal conversion efficiency of the MOF-C loaded phase change material shows that the photothermal conversion efficiency can be greatly improved by selecting a proper bimetal proportion, and also shows that the higher the proportion of the magnetic particles is, the higher the photothermal conversion efficiency is not necessarily, and the inventor speculates that the magnetic particles are excessive and the calcination is performed when the magnetic particles are excessiveAgglomeration is easily generated in the process, and the enhancement of the surface plasma effect on the photo-thermal conversion efficiency and the absorption of graphitized carbon on light are weakened. .
Comparative example 2
Zn (NO)3)2·6H2O (4.7g) and polyvinylpyrrolidone (PVP) (2.4g) were dissolved in methanol (300 mL). 1,3, 5-trimesic acid (2.58g) in methanol (300mL) was then added to the zinc nitrate solution with vigorous magnetic stirring at 28 ℃. After vigorous stirring for 10 minutes, the reaction was continued at room temperature for 4 hours with gentle stirring. The resulting precipitate was collected by centrifugation (10000 rpm, 5 minutes), and then washed several times with methanol to remove PVP. Finally, the product was dried in an oven at 70 ℃ for 12 hours. The prepared metal organic framework is of a regular octahedral structure and does not belong to a one-dimensional structure. It is shown that the formation of the one-dimensional structure is influenced by the reaction conditions and the starting materials.
The inventor of the invention finds that the proportion of the metal magnetic particles in the metal organic framework has a great influence on the photo-thermal conversion capability, and the photo-thermal conversion capability can be improved by increasing the content of the metal magnetic particles within a certain range.
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. The bimetallic MOF-derived graphitized carbon-based photothermal composite phase-change material is characterized by comprising bimetallic MOF-derived graphitized carbon and a phase-change material adsorbed on the surface and/or in a pore channel of the bimetallic MOF-derived graphitized carbon, wherein the bimetallic MOF-derived graphitized carbon is a nano material containing magnetic metal particles obtained by carbonizing a bimetallic organic framework at high temperature, and the magnetic metal particles are selected from one or more of iron, nickel and cobalt magnetic particles;
the bimetallic organic framework is obtained by reacting metal salt A, metal salt B and an organic ligand through a hydrothermal method, wherein the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-1): 1; the metal salt B is used for forming magnetic metal particles;
the metal salt A and the metal salt B are salts of different metals.
2. The bimetallic MOF derived graphitized carbon-based photothermal composite phase change material of claim 1, wherein the loading of the phase change material in the photothermal composite phase change material is 50-70%, optionally 50-65%, optionally 50-60%, optionally 60%;
and/or in the bimetallic organic framework, the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-0.8): 1, optionally (0.5-1.1): (0.1-0.8): 1; optionally (0.5-1.1): (0.1-0.5): 1, optionally (0.8-1.1): (0.1-0.2): 1, optionally (0.9-1.1): (0.1-0.15): 1, optionally (0.9-0.99): (0.1-0.11): 1, optionally (0.945-0.99): (0.105-0.11): alternatively 0.9675: 0.1075: 1.
3. the bimetallic MOF derived graphitized carbon-based photothermal composite phase change material according to claim 1 or 2, wherein the metal salt A is selected from one or more of zinc salt and copper salt; optionally, the metal salt a is a zinc salt;
and/or the metal salt B is selected from one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, ferric nitrate, ferric chloride, ferric sulfate and ferric acetate.
4. The bimetallic MOF derived graphitized carbon-based photothermal composite phase change material according to any one of claims 1 to 3, wherein the phase change material is selected from one or more of dodecanoic acid, octadecanol, polyethylene glycol, octadecylamine, paraffin; optionally, the phase change material is dodecanoic acid;
and/or the organic ligand is selected from one or more of 1,3, 5-trimesic acid, terephthalic acid and 2-methylimidazole; optionally the organic ligand is 1,3, 5-trimesic acid;
and/or, the high-temperature carbonization is carried out heat preservation carbonization at 600-900 ℃ in an inert gas atmosphere; optionally the carbonization temperature is 700-850 ℃, optionally 700-800 ℃, optionally 750 ℃;
and/or, the bimetallic MOF-derived graphitized carbon is a one-dimensional nanostructure.
5. A preparation method of a bimetallic MOF derived graphitized carbon-based photothermal composite phase change material is characterized by comprising the following steps:
dispersing the bimetallic MOF derived graphitized carbon in a phase-change material solution, mixing and drying to prepare a composite phase-change material;
the preparation method of the bimetallic MOF derived graphitized carbon comprises the following steps: adding a salt water solution into an organic ligand water solution at the temperature of 90-110 ℃, stirring, collecting precipitates, and washing to obtain a bimetallic organic frame; the brine solution contains a metal salt A, a metal salt B and water; carbonizing a bimetallic organic frame at 600-900 ℃ under an inert gas atmosphere to obtain bimetallic MOF (Metal organic framework) derived graphitized carbon;
wherein the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-1): 1;
the metal salt B is selected from one or more of nickel salt, iron salt and cobalt salt;
the metal salt A and the metal salt B are salts of different metals.
6. The preparation method according to claim 5, wherein the loading amount of the phase-change material in the photothermal composite phase-change material is 50-70%, optionally 50-65%, optionally 50-60%, optionally 60%;
and/or in the bimetallic organic framework, the molar ratio of the metal salt A to the metal salt B to the organic ligand is (0.5-1.5): (0.1-0.8): 1, optionally (0.5-1.1): (0.1-0.8): 1; optionally (0.5-1.1): (0.1-0.5): 1, optionally (0.8-1.1): (0.1-0.2): 1, optionally (0.9-1.1): (0.1-0.15): 1, optionally (0.9-0.99): (0.1-0.11): 1, optionally (0.945-0.99): (0.105-0.11): optionally 0.9675: 0.1075: 1.
7. the preparation method according to claim 5 or 6, wherein the phase-change material is selected from one or more of dodecanoic acid, octadecanol, polyethylene glycol, octadecylamine and paraffin; optionally, the phase change material is dodecanoic acid;
and/or the organic ligand is selected from one or more of 1,3, 5-trimesic acid, terephthalic acid and 2-methylimidazole; optionally the organic ligand is 1,3, 5-trimesic acid;
and/or, loading the phase change material on the bimetallic MOF derived graphitized carbon by adopting a melt impregnation method;
and/or the metal salt A is selected from one or more of zinc salt and copper salt; optionally, the metal salt a is a zinc salt;
and/or the metal salt B is selected from one or more of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate, ferric nitrate, ferric chloride, ferric sulfate and ferric acetate.
8. The method of any of claims 5 to 7, wherein in the preparation of the bimetallic MOF-derived graphitized carbon,
the concentration of the metal salt A in the saline solution is 0.1-0.2 mol/L;
the concentration of the metal salt B in the saline solution is 0.1-0.2 mol/L;
the concentration of the organic ligand in the organic ligand aqueous solution is 0.02-0.05 mol/L;
alternatively, the volume ratio of the aqueous salt solution to the aqueous organic ligand solution is 1: (8-10);
optionally, the stirring reaction time is 3-8 min, optionally 5-8 min;
optionally, the bimetallic organic framework is a one-dimensional nanostructure;
alternatively, the temperature of the aqueous organic ligand solution is 100 ℃.
9. The method according to any one of claims 5 to 8, wherein the carbonization time is 0.5 to 10 hours; optionally 0.5-6 h; optionally 1-3 h, optionally 1-2 h;
and/or, the inert gas comprises argon, nitrogen or a hydrogen-argon mixed gas;
and/or the carbonization temperature is 700-850 ℃, optionally 700-800 ℃, optionally 750 ℃; optionally, the heating rate is 3-8 ℃/min, optionally 5 ℃/min.
10. Use of the bimetallic MOF derived graphitized carbon-based photothermal composite phase change material according to any one of claims 1 to 4 or the bimetallic MOF derived graphitized carbon-based photothermal composite phase change material prepared by the preparation method according to any one of claims 5 to 9 as a photothermal conversion material or for thermoelectric conversion tests, optionally in the field of solar heat storage.
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| 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 |
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