CN110484214A - A kind of sizing MOF base composite phase-change material and its preparation method and application - Google Patents
A kind of sizing MOF base composite phase-change material and its preparation method and application Download PDFInfo
- Publication number
- CN110484214A CN110484214A CN201910762614.6A CN201910762614A CN110484214A CN 110484214 A CN110484214 A CN 110484214A CN 201910762614 A CN201910762614 A CN 201910762614A CN 110484214 A CN110484214 A CN 110484214A
- Authority
- CN
- China
- Prior art keywords
- mof
- preparation
- acid
- change material
- foam metal
- Prior art date
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- 239000012782 phase change material Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 238000004513 sizing Methods 0.000 title claims abstract description 23
- 239000006260 foam Substances 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 48
- 229910052802 copper Inorganic materials 0.000 claims description 48
- 239000010949 copper Substances 0.000 claims description 48
- 239000012452 mother liquor Substances 0.000 claims description 44
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 24
- 239000011159 matrix material Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000011162 core material Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical group OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 230000009466 transformation Effects 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000013110 organic ligand Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004146 energy storage Methods 0.000 claims description 4
- 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 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical group OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical group OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229940038384 octadecane Drugs 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical group C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- 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 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
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- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 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 2
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 claims description 2
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- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000000015 thermotherapy Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present embodiments relate to a kind of sizing MOF base composite phase-change materials and its preparation method and application, the preparation method is using the MOF substrate of formation as forming core site, ligand and metal ion is added, MOF can be overcome as phase-change material carrier by way of growing MOF on foam metal and be not easy the shortcomings that forming；Use foam metal as a part in sizing MOF base composite phase-change material in the preparation method, for enhancing the thermal conductivity of composite phase-change material；And the preparation method is widely used, and raw material is cheap and easy to get, is suitble to industrialized production.
Description
Technical field
The present invention relates to composite phase-change material fields, and in particular to a kind of sizing MOF base composite phase-change material and its preparation
Methods and applications.
Background technique
In face of the energy crisis and environmental crisis got worse, developing efficient energy storage and switch technology seems especially
Important, composite phase-change material has attracted more and more attention from people in terms of solving energy supply and conveying, energy conversion.Compound phase
Other than becoming the tradition applications such as input and output of the material in addition to absorbing and releasing a large amount of heat realization energy in using phase transition process, In
It is also developed in innovation and applications in terms of photothermal conversion, electric heating conversion, magnetic hot-cast socket, thermotherapy etc..
But there is leakage in phase transition process in phase-change material, in order to solve leakage problem, SiO 2 molecular sieve,
The phase transformations carrier such as kaolin is used to prepare shaped composite phase-change material.Metal organic framework (MOF) is as a kind of emerging more
Hole organic backbone has a very important status in fields such as catalysis, energy storage, gas separation, the three-dimensional order of MOF it is mutual
The specific surface area for leading to structure, adjustable aperture, modifiable duct, the porosity of superelevation and super large makes it possible to as one kind
Ideal carrier loads phase-change material.
But the very low characteristic of the easy powdering of MOF, not easily molded and thermal conductivity significantly limits it in phase-change material
In application.Although the heat of composite phase-change material can be improved by adding the Heat Conduction Materials such as graphene, carbon nanotube in MOF
Conductance, but still its floury structure can not be changed, and the cost that these Heat Conduction Materials are added is also higher.Therefore, synthesis tool
The MOF base composite phase-change material of regular shape and the thermal conductivity that MOF base composite phase-change material can be improved at low cost
Problem is badly in need of breaking through.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
Goal of the invention
The purpose of the present invention is to provide a kind of sizing MOF base composite phase-change material and its preparation method and application, the systems
Preparation Method effectively overcomes MOF material and is not easy the shortcomings that forming and simultaneously by way of growing MOF on foam metal
The thermal conductivity of MOF base composite phase-change material is improved at low cost.The sizing MOF base composite phase-change obtained using the preparation method
Material has designated shape, thermal conductivity high.
Solution
A kind of preparation method for MOF base composite phase-change material of being formed, comprising the following steps:
Organic ligand, soluble metallic salt and sufficiently uniformly dissolving if you need to necessary additive is obtained in a solvent
MOF reaction solution；Then MOF reaction solution is reacted, reaction product obtains MOF matrix after separation, washing, drying, will
MOF matrix is dissolved in solvent that obtain MOF mother liquor spare；
Preheating foam metal simultaneously keeps the temperature, the substrate grown using foam metal as MOF, and the MOF that preparation is added dropwise is female
Liquid covers foam metal surface, and the solvent of MOF mother liquor is then allowed to evaporate, and is washed away with organic solvent in conjunction with unstable MOF, is obtained
To foam metal matrix；Gained foam metal matrix is placed in enough MOF growth-promoting medias with above-mentioned MOF reaction solution same composition
It is reacted, is washed out, dries, obtain MOF base carrier；
Organic phase-change core material is dissolved in acquisition organic phase-change core material solution in solvent, it is organic that MOF base carrier is put into this
In phase transformation core material solution, it is then dried to obtain MOF base composite phase-change material.
Above-mentioned preparation method in alternatively possible implementation, the foam metal include nickel foam, foamed aluminium or
Foam copper it is one or more；It is optionally foam copper.
For above-mentioned preparation method in alternatively possible implementation, the foam metal matrix is being placed in MOF growth-promoting media
In reacted before, cover foam metal surface completely by MOF.
For above-mentioned preparation method in alternatively possible implementation, the organic ligand includes: terephthalic acid (TPA), adjacent benzene
Dioctyl phthalate, trimesic acid, Pyromellitic Acid, mellitic acid, 2- sulfonic group terephthalic acid (TPA), 2- nitroterephthalic, 2-
Amino terephthalic acid (TPA), 1,1':4', 1 "-phenyl -4,4 "-dioctyl phthalate, 1,1'- diphenyl -4,4'- dioctyl phthalate, 2-methylimidazole
One of or it is a variety of.
For above-mentioned preparation method in alternatively possible implementation, the soluble metallic salt includes: chromic nitrate, chlorination
Chromium, chromium sulfate, chromic acetate, zirconium nitrate, zirconium chloride, zirconium sulfate, acetic acid zirconium, copper nitrate, copper chloride, copper sulphate, copper acetate, nitric acid
Zinc, zinc chloride, zinc sulfate, zinc acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, cobalt nitrate, cobalt chloride, cobaltous sulfate, acetic acid
Cobalt, ferric nitrate, iron chloride, ferric sulfate, ferric acetate, aluminum nitrate, aluminium chloride, aluminum sulfate, aluminum acetate, manganese nitrate, manganese chloride, sulfuric acid
One of manganese, manganese acetate, Titanium Nitrate, titanium chloride, titanium sulfate are a variety of.
For above-mentioned preparation method in alternatively possible implementation, the additive includes: hydrofluoric acid, hydroxide
Sodium, formic acid, acetic acid, benzoic acid, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, phloroglucin/first
One of aldehyde and triblock copolymer, triethylamine, methanol are a variety of.
Above-mentioned preparation method in alternatively possible implementation, organic phase-change core material include: octadecyl alcolol, octadecane,
One of stearic acid, paraffin, polyethylene glycol, pentaerythrite, neopentyl glycol, trishydroxymethylaminomethane, trimethylolpropane
Or it is a variety of.
The MOF mother liquor of preparation is added dropwise by foam metal surface in alternatively possible implementation in above-mentioned preparation method
Covering, then allows the solvent of MOF mother liquor to evaporate, and is washed away with organic solvent in conjunction with unstable MOF, obtains foam metal matrix
Step includes: the MOF mother liquor prepared to be added dropwise foam metal surface is completely covered to MOF mother liquor, then allows the solvent of MOF mother liquor
Evaporating completely is repeated several times the process that MOF mother liquor and solvent evaporation is added dropwise, then is washed away with organic solvent in conjunction with unstable MOF,
The process that above-mentioned dropwise addition MOF mother liquor, solvent evaporation and organic solvent are washed is repeated several times later, until it is complete to obtain foam metal surface
The foam metal matrix that site preparation is covered by MOF.
Above-mentioned preparation method has in MOF base carrier and organic phase-change core material solution in alternatively possible implementation
The mass ratio of machine phase transformation core material is 5:3-10；Optionally the mass ratio of MOF base carrier and PEG2000 are 5:4.
Above-mentioned preparation method is in alternatively possible implementation, and when preparing MOF mother liquor, solvent for use is water, MOF base
The molar ratio of body and water is 1:10-40；It is optionally 1:20-30；It is still optionally further 1:25.
For above-mentioned preparation method in alternatively possible implementation, the temperature for preheating foam metal is 95-105 DEG C.
For above-mentioned preparation method in alternatively possible implementation, the temperature that MOF reaction solution is reacted is 25-100
℃。
Above-mentioned preparation method is placed in MOF growth-promoting media in alternatively possible implementation, by gained foam metal matrix
The middle temperature reacted is 25-100 DEG C.
Above-mentioned preparation method is in alternatively possible implementation, and foam metal is in preheating using preceding by processing, institute
State the step of processing includes: by the substrate that MOF can be grown is obtained after foam metal cleaning, drying；Optionally, it cleans as difference
It is successively immersed in acetone, methanol, is cleaned by ultrasonic in deionized water.
The present invention also provides the sizing MOF base composite phase-change materials that above-mentioned preparation method obtains.
A kind of sizing MOF base composite phase-change material, including MOF base carrier and the organic phase-change being supported in MOF base carrier
Core material, in which: the MOF base carrier includes foam metal and the MOF for being covered on foam metal surface.
Above-mentioned sizing MOF base composite phase-change material, the foam metal include one kind of nickel foam, foamed aluminium or foam copper
Or it is a variety of；It is optionally foam copper.
Above-mentioned sizing MOF base composite phase-change material, organic phase-change core material include: octadecyl alcolol, octadecane, stearic acid, paraffin,
One of polyethylene glycol, pentaerythrite, neopentyl glycol, trishydroxymethylaminomethane, trimethylolpropane are a variety of.
Above-mentioned sizing MOF base composite phase-change material, MOF includes Cu-BTC, Cr-MIL-101-NH2、MOF-5、UIO-66、
One of Al-MIL-53, ZIF-67 or a variety of.
Above-mentioned sizing MOF base composite phase-change material, in the MOF base carrier, foam metal surface is completely covered by MOF
Lid.
Application of the above-mentioned sizing MOF base composite phase-change material in energy storage and release.
Beneficial effect
1) a kind of preparation method of the sizing MOF base composite phase-change material of simplicity is developed in the present invention；The preparation method
Using the MOF substrate of formation as forming core site, ligand and metal ion is added, by way of growing MOF on foam metal
MOF can be overcome as phase-change material carrier and be not easy the shortcomings that forming, by controlling shape, the size of foam metal to make
Gained MOF base composite phase-change material has shape, the size of foam metal；Use foam metal as sizing in the preparation method
A part in MOF base composite phase-change material, for enhancing the thermal conductivity of composite phase-change material, since foam metal itself has
Higher heat-conductivity, so can also enhance the thermal conductivity of composite phase-change material；And the preparation method is widely used, and raw material is inexpensively easy
, it is suitble to industrialized production.
2) sizing MOF can more effectively be solved by selection nickel foam, foamed aluminium and foam copper in preparation method of the present invention
The low problem of base composite phase-change material thermal conductivity；Further, foam copper is for nickel foam and foamed aluminium, and cost is more
Low, heating conduction is more preferable, for the basis material of phase-change material, has better heat transmission ability.
3) in preparation method of the present invention, by determining the content of phase-change material packaged by MOF base carrier, so that encapsulation
Phase transformation core material No leakage.
4) present invention sizing MOF base composite phase-change material has designated shape, thermal conductivity height, phase transformation core material No leakage.
Detailed description of the invention
Fig. 1 is differential scanning calorimetry (DSC) curve of sizing MOF base composite phase-change material obtained by the embodiment of the present invention 1,
In: the exotherm of lines expression composite phase-change material, the lines of lower section of top indicate the endothermic curve of composite phase-change material；
Fig. 2 is sizing MOF base composite phase-change material scanning electron microscopy under 2 micro-meter scales obtained by the embodiment of the present invention 1
Mirror (SEM) figure, shows that phase-change material is successfully carried in carrier material；
Fig. 3 is that the scanning electron under 20 micro-meter scales of sizing MOF base composite phase-change material obtained by the embodiment of the present invention 1 is aobvious
Micro mirror (SEM) figure, shows that phase-change material is successfully carried in carrier material.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
In the present invention, shape, the size of foam metal are not specially limited, those skilled in the art can be according to the present invention
Goal of the invention and application demand adjust its shape or correspondingly sized.
In the present invention, the aperture of foam metal is not specially limited, those skilled in the art according to the present invention can send out
Improving eyesight and application demand selection foam metal aperture.It is only to selection to the explanation in foam copper aperture in following embodiment
A kind of objective description of foam copper, 500 mesh copper sieve refer to that mean pore size is the foam copper of 500 mesh.
In the present invention, the effect of special additive is embodied in MOF and prepares, in growth course, the preparation of some MOF,
Growth needs under certain condition, such as alkaline condition (such as being realized by providing the sodium hydroxide in embodiment 1) or acid
Under condition (such as being realized by providing the glacial acetic acid in embodiment 3), and some MOF are not needed then, according to MOF to be prepared
Come determine additive addition whether and additive amount number.
In the present invention, three's adding proportion of organic ligand, soluble metallic salt and special additive will be according to made
Standby MOF is determined.
In the present invention, the composition of MOF reaction solution is identical as the composition of MOF growth-promoting media, has numerically both included complete in substance
It is identical, be also included within reasonable fluctuation range in the understanding of those skilled in the art, comprising: within ± 3%, within ± 1% or
Within ± 0.5%.
In the present invention, simple mode can be used by judging whether MOF growth-promoting media is enough, it may be assumed that by gained foam metal base
Body, which is placed in MOF growth-promoting media, to be reacted, and not only has MOF growth on foam metal matrix, is also had in MOF growth-promoting media more
Remaining MOF is generated.
Case study on implementation 1
Cu-BTC base composite phase-change material
1) choose 500 mesh copper of volume 2cm × 2cm × 1mm sieve, by copper screening be not immersed in successively acetone, methanol, go from
Ultrasound 30min in sub- water, every time 60 DEG C of dryings in convection oven obtain the substrate of Cu-BTC growth；
2) trimesic acid of the copper nitrate of 7.021g and 3.063g is substantially dissolved in 25mL water and the ethyl alcohol of 25mL
In mixed solution, it is vigorously stirred 30min at room temperature and obtains uniform solution, then moves it into reaction kettle, is put into
15h is reacted in baking oven at 95 DEG C, and reaction product obtains Cu- after dry 8h is put into baking oven at 80 DEG C after centrifuge washing
BTC obtains Cu-BTC mother liquor for the Cu-BTC after drying is soluble in water, wherein the molar ratio of Cu-BTC powder and water after dry
For 1:25.
3) copper in step 1) is sieved in 100 DEG C of preheating 10min, at such a temperature, the Cu-BTC that will be prepared in step 2)
Mother liquor drips to the surface of copper sieve until whole surface is completely covered dropwise, then proceedes to dry 15min removing at this temperature
Solvent in Cu-BTC mother liquor repeats the process that three-wheel mother liquor is added dropwise and removes solvent, then simultaneously ultrasonic with the ethanol washing sample
1min repeats four-wheel mother liquor and is added dropwise, removes the whole process of solvent and supersound washing until copper sieves surface completely by Cu-
BTC covering.Above-mentioned manufactured copper sieve matrix is put into the 25mL of the copper nitrate containing 7.021g and the trimesic acid of 3.063g
In the mixed solution of the ethyl alcohol of water and 25mL, moves into reaction kettle and be put into 95 DEG C of reaction 15h in baking oven, then slowly cool to room
Temperature, after washing, 80 DEG C of dryings for 24 hours, obtain the final Cu-BTC base carrier for becoming material for load organic phases.
4) 0.5g PEG2000 is dissolved in 50mL dehydrated alcohol, 60 DEG C of heating stirrings, will be in step 3) to being completely dissolved
0.4g Cu-BTC base carrier is put into above-mentioned solution, is then placed in 80 DEG C of dry 8h in baking oven, it is compound to finally obtain Cu-BTC base
Phase-change material.
Under differential scanning calorimetry (DSC) curve of 1 gained Cu-BTC base composite phase-change material of the present embodiment, 2 micro-meter scales
Scanning electron microscope (SEM) figure difference is as shown in Figure 1-Figure 3 under scanning electron microscope (SEM) figure, 2 micro-meter scales.Such as Fig. 1
Shown in, the composite phase-change material releases heat at lower temperature such as 20-40 DEG C, should at higher temperature such as 50-70 DEG C
Composite phase-change material absorbs heat, shows that phase-change material is successfully carried in carrier material.Also, it can also be with from Fig. 2-Fig. 3
Intuitively see that phase-change material is successfully carried in carrier material.
Case study on implementation 2
Cr-MIL-101-NH2Base composite phase-change material
1) choose 500 mesh copper of volume 2cm × 2cm × 1mm sieve, by copper screening be not immersed in successively acetone, methanol, go from
Ultrasound 30min in sub- water, every time 60 DEG C of dryings in convection oven obtain Cr-MIL-101-NH2The substrate of growth；
2) Chromium nitrate (Cr(NO3)3),nonahydrate of the 2- amino terephthalic acid (TPA) of 3.2g and 3.2g is substantially dissolved in 60mL deionized water
In, it is added after the sodium hydroxide of 0.8g and is vigorously stirred the uniform solution of 30min acquisition at room temperature, then move it into anti-
It answers in kettle, is put into baking oven and reacts 12h at 150 DEG C, reaction product is put into baking oven at 80 DEG C dry after centrifuge washing
Cr-MIL-101-NH is obtained after 8h2, by the Cr-MIL-101-NH after drying2It is soluble in water to obtain Cr-MIL-101-NH2Mother liquor,
Cr-MIL-101-NH after wherein drying2The molar ratio of powder and water is 1:25.
3) copper in step 1) is sieved in 100 DEG C of preheating 10min, at such a temperature, the Cr-MIL- that will be prepared in step 2)
101-NH2Mother liquor drips to the surface of copper sieve until whole surface is completely covered dropwise, then proceedes to dry at this temperature
15min removes Cr-MIL-101-NH2Solvent in mother liquor repeats the process that three-wheel mother liquor is added dropwise and removes solvent, then uses ethyl alcohol
The sample and ultrasound 1min are washed, four-wheel mother liquor is repeated and is added dropwise, removes the whole process of solvent and supersound washing until copper sieves
Surface is completely by Cr-MIL-101-NH2Covering.Above-mentioned manufactured copper sieve matrix is put into the 2- amino containing 5.3g to benzene two
In the uniform deionized water solution of the 100mL of the sodium hydroxide of formic acid, the Chromium nitrate (Cr(NO3)3),nonahydrate of 5.3g and 1.3g, moves into reaction kettle and put
Enter 150 DEG C of reaction 12h in baking oven, be then slowly cooled to room temperature, after washing, 60 DEG C of dry 48h are obtained final for loading
The Cr-MIL-101-NH of organic phase change material2Base carrier.
4) 0.5g PEG2000 is dissolved in 50mL dehydrated alcohol, 60 DEG C of heating stirrings, will be in step 3) to being completely dissolved
0.4g Cr-MIL-101-NH2Base carrier is put into above-mentioned solution, is then placed in 80 DEG C of dry 8h in baking oven, is finally obtained Cr-
MIL-101-NH2Base composite phase-change material.
Case study on implementation 3
MOF-5 base composite phase-change material
1) choose 500 mesh copper of volume 2cm × 2cm × 1mm sieve, by copper screening be not immersed in successively acetone, methanol, go from
Ultrasound 30min in sub- water, every time 60 DEG C of dryings in convection oven obtain the substrate of MOF-5 growth；
2) zinc nitrate hexahydrate of the terephthalic acid (TPA) of 0.69g and 3.41g is substantially dissolved in 100mL DMF, in room
It is vigorously stirred 30min under the conditions of temperature and obtains uniform solution, then moves it into reaction kettle, is put into baking oven at 100 DEG C anti-
18h is answered, and reaction product obtains MOF-5 after dry 8h is put into baking oven at 80 DEG C, after drying after centrifuge washing
MOF-5 is soluble in water to obtain MOF-5 mother liquor, wherein the molar ratio of MOF-5 powder and water after dry is 1:25.
3) copper treated in step 1) is sieved in 100 DEG C of preheating 10min, at such a temperature, will be prepared in step 2)
MOF-5 mother liquor drip to copper sieve dropwise surface until whole surface is completely covered, then proceed to dry at this temperature
15min removes the solvent in MOF-5 mother liquor, repeats the process that three-wheel mother liquor is added dropwise and removes solvent, then with the ethanol washing sample
Product and ultrasound 1min repeat four-wheel mother liquor and are added dropwise, remove the whole process of solvent and supersound washing until copper sieve surface is complete
Ground is covered by MOF-5.Above-mentioned manufactured copper sieve matrix is put into the terephthalic acid (TPA) containing 0.69g and the six hydration nitre of 3.41g
In the uniform DMF solution of the 100mL of sour zinc, moves into reaction kettle and is put into 100 DEG C of reaction 18h in baking oven, be then slowly cooled to room temperature,
After washing, 80 DEG C of dry 48h obtain the final MOF-5 base carrier for becoming material for load organic phases.
4) 0.5g PEG2000 is dissolved in 50mL dehydrated alcohol, 60 DEG C of heating stirrings, will be in step 3) to being completely dissolved
0.4g MOF-5 base carrier is put into above-mentioned solution, is then placed in 80 DEG C of dry 8h in baking oven, is finally obtained MOF-5 base compound phase
Become material.
Case study on implementation 4
UIO-66 base composite phase-change material
1) choose 500 mesh copper of volume 2cm × 2cm × 1mm sieve, by copper screening be not immersed in successively acetone, methanol, go from
Ultrasound 30min in sub- water, every time 60 DEG C of dryings in convection oven obtain the substrate of UIO-66 growth；
2) by the ZrCl of the glacial acetic acid of 2.85mL and 0.4g4It is substantially dissolved in 75mL DMF, the terephthaldehyde of 0.285g
Acid dissolution is vigorously stirred 30min at room temperature respectively and obtains uniform solution, above-mentioned solution is mixed in 25mL DMF
After move into reaction kettle, be put into baking oven 120 DEG C of reactions for 24 hours, reaction product is put into vacuum oven after centrifuge washing
Drying obtains UIO-66 afterwards for 24 hours at 80 DEG C, obtains UIO-66 mother liquor for the UIO-66 after drying is soluble in water, wherein after dry
The molar ratio of UIO-66 powder and water is 1:25.
3) copper treated in step 1) is sieved in 100 DEG C of preheating 10min, at such a temperature, will be prepared in step 2)
UIO-66 mother liquor drip to copper sieve dropwise surface until whole surface is completely covered, then proceed to dry at this temperature
15min removes the solvent in UIO-66 mother liquor, repeats the process that three-wheel mother liquor is added dropwise and removes solvent, then with the ethanol washing sample
Product and ultrasound 1min repeat four-wheel mother liquor and are added dropwise, remove the whole process of solvent and supersound washing until copper sieve surface is complete
Ground is covered by UIO-66.By above-mentioned manufactured copper sieve matrix be put into the glacial acetic acid containing 11.4mL, 1.14g terephthalic acid (TPA) and
The ZrCl of 1.6g4The uniform DMF solution of 100mL in, move into reaction kettle and be put into baking oven 120 DEG C of reactions for 24 hours, then Slow cooling
To room temperature, after washing, 80 DEG C of dryings for 24 hours, obtain the final UIO-66 base carrier for becoming material for load organic phases.
4) 0.5g PEG2000 is dissolved in 50mL dehydrated alcohol, 60 DEG C of heating stirrings, will be in step 3) to being completely dissolved
0.4g UIO-66 base carrier is put into above-mentioned solution, is then placed in 80 DEG C of dry 8h in baking oven, it is compound to finally obtain UIO-66 base
Phase-change material.
Case study on implementation 5
Al-MIL-53 base composite phase-change material
1) choose 500 mesh copper of volume 2cm × 2cm × 1mm sieve, by copper screening be not immersed in successively acetone, methanol, go from
Ultrasound 30min in sub- water, every time 60 DEG C of dryings in convection oven obtain the substrate of Al-MIL-53 growth；
2) ANN aluminium nitrate nonahydrate of the terephthalic acid (TPA) of 0.533g and 0.787g is substantially dissolved in 50mL DMF, is added
30min is vigorously stirred after the surface agent poloxamer F127 of 0.64g at room temperature and obtains uniform solution, then
It moves it into reaction kettle, is put into baking oven and reacts 36h at 120 DEG C, reaction product is put into baking oven after centrifuge washing
Al-MIL-53 is obtained after dry 12h at 70 DEG C, obtains Al-MIL-53 mother liquor for the Al-MIL-53 after drying is soluble in water,
The molar ratio of Al-MIL-53 powder and water after middle drying is 1:25.
3) copper treated in step 1) is sieved in 100 DEG C of preheating 10min, at such a temperature, will be prepared in step 2)
Al-MIL-53 mother liquor drip to copper sieve dropwise surface until whole surface is completely covered, then proceed to do at this temperature
Dry 15min removes the solvent in Al-MIL-53 mother liquor, repeats the process that three-wheel mother liquor is added dropwise and removes solvent, then washed with ethyl alcohol
The sample and ultrasound 1min are washed, four-wheel mother liquor is repeated and is added dropwise, removes the whole process of solvent and supersound washing until copper sieve table
Face is completely covered by Al-MIL-53.Above-mentioned manufactured copper sieve matrix is put into the surface agent poloxamer containing 1.28g
In the uniform DMF solution of 100mL of the ANN aluminium nitrate nonahydrate of the terephthalic acid (TPA) and 1.574g of F127,1.066g, reaction kettle is moved into
120 DEG C of reaction 36h in baking oven are put into, are then slowly cooled to room temperature, after washing, 70 DEG C of dry 12h are obtained final for bearing
Carry the Al-MIL-53 base carrier of organic phase change material.
4) 0.5g PEG2000 is dissolved in 50mL dehydrated alcohol, 60 DEG C of heating stirrings, will be in step 3) to being completely dissolved
0.4g Al-MIL-53 base carrier is put into above-mentioned solution, is then placed in 80 DEG C of dry 8h in baking oven, is finally obtained Al-MIL-53
Base composite phase-change material.
Case study on implementation 6
ZIF-67 base composite phase-change material
1) choose 500 mesh copper of volume 2cm × 2cm × 1mm sieve, by copper screening be not immersed in successively acetone, methanol, go from
Ultrasound 30min in sub- water, every time 60 DEG C of dryings in convection oven obtain the substrate of ZIF-67 growth；
2) the four hydration cobalt acetates of the 2-methylimidazole of 3.284g and 3.321g are substantially dissolved in 125mL ethyl alcohol, In
It is vigorously stirred 30min under room temperature and obtains uniform solution, then moves it into reaction kettle, is put into baking oven at 120 DEG C
72h is reacted, and reaction product obtains ZIF-67 after dry 8h is put into baking oven at 150 DEG C, after drying after centrifuge washing
ZIF-67 it is soluble in water obtain ZIF-67 mother liquor, wherein the molar ratio of ZIF-67 powder and water after dry is 1:25.
3) copper treated in step 1) is sieved in 100 DEG C of preheating 10min, at such a temperature, will be prepared in step 2)
ZIF-67 mother liquor drip to copper sieve dropwise surface until whole surface is completely covered, then proceed to dry at this temperature
15min removes the solvent in ZIF-67 mother liquor, repeats the process that three-wheel mother liquor is added dropwise and removes solvent, then with the ethanol washing sample
Product and ultrasound 1min repeat four-wheel mother liquor and are added dropwise, remove the whole process of solvent and supersound washing until copper sieve surface is complete
Ground is covered by ZIF-67.Above-mentioned manufactured copper sieve matrix is put into the 2-methylimidazole containing 2.63g and the four hydration vinegar of 2.66g
In the uniform ethanol solution of the 100mL of sour cobalt, moves into reaction kettle and be put into 120 DEG C of reaction 72h in baking oven, then slowly cool to room
Temperature, after washing, 150 DEG C of dry 8h obtain the final ZIF-67 base carrier for becoming material for load organic phases.
4) 0.5g PEG2000 is dissolved in 50mL dehydrated alcohol, 60 DEG C of heating stirrings, will be in step 3) to being completely dissolved
0.4g ZIF-67 base carrier is put into above-mentioned solution, is then placed in 80 DEG C of dry 8h in baking oven, it is compound to finally obtain ZIF-67 base
Phase-change material.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method for MOF base composite phase-change material of being formed, it is characterised in that: the following steps are included:
It is dissolved organic ligand, soluble metallic salt and sufficiently uniformly if you need to necessary additive and obtains MOF in a solvent
Reaction solution；Then MOF reaction solution is reacted, reaction product obtains MOF matrix after separation, washing, drying, by MOF
Matrix is dissolved in solvent that obtain MOF mother liquor spare；
Preheating foam metal simultaneously keeps the temperature, the substrate grown using foam metal as MOF, and the MOF mother liquor that preparation is added dropwise will
The covering of foam metal surface, then allows the solvent of MOF mother liquor to evaporate, and is washed away with organic solvent in conjunction with unstable MOF, is steeped
Foam metallic matrix；Gained foam metal matrix is placed in enough MOF growth-promoting medias with the MOF reaction solution same composition and is carried out
Reaction, is washed out, dries, obtain MOF base carrier；
Organic phase-change core material is dissolved in acquisition organic phase-change core material solution in solvent, MOF base carrier is put into the organic phase-change
In core material solution, it is then dried to obtain MOF base composite phase-change material.
2. preparation method according to claim 1, it is characterised in that: the foam metal include nickel foam, foamed aluminium or
Foam copper it is one or more；It is optionally foam copper.
3. preparation method according to claim 1, it is characterised in that: the foam metal matrix is being placed in MOF growth-promoting media
In reacted before, cover foam metal surface completely by MOF.
4. preparation method according to claim 1, it is characterised in that: the organic ligand includes: terephthalic acid (TPA), adjacent benzene
Dioctyl phthalate, trimesic acid, Pyromellitic Acid, mellitic acid, 2- sulfonic group terephthalic acid (TPA), 2- nitroterephthalic, 2-
One of amino terephthalic acid (TPA), 1,1':4', 1 "-phenyl -4,4 "-dioctyl phthalate, 1,1'- diphenyl -4,4'- dioctyl phthalate or
It is a variety of.
5. preparation method according to claim 1, it is characterised in that: the soluble metallic salt includes: chromic nitrate, chlorination
Chromium, chromium sulfate, chromic acetate, zirconium nitrate, zirconium chloride, zirconium sulfate, acetic acid zirconium, copper nitrate, copper chloride, copper sulphate, copper acetate, nitric acid
Zinc, zinc chloride, zinc sulfate, zinc acetate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, cobalt nitrate, cobalt chloride, cobaltous sulfate, acetic acid
Cobalt, ferric nitrate, iron chloride, ferric sulfate, ferric acetate, aluminum nitrate, aluminium chloride, aluminum sulfate, aluminum acetate, manganese nitrate, manganese chloride, sulfuric acid
One of manganese, manganese acetate, Titanium Nitrate, titanium chloride, titanium sulfate are a variety of.
6. preparation method according to claim 1, it is characterised in that: the additive includes: hydrofluoric acid, hydroxide
Sodium, formic acid, acetic acid, benzoic acid, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, phloroglucin/first
One of aldehyde and triblock copolymer, triethylamine, methanol are a variety of.
7. preparation method according to claim 1, it is characterised in that: organic phase-change core material include: octadecyl alcolol, octadecane,
One of stearic acid, paraffin, polyethylene glycol, pentaerythrite, neopentyl glycol, trishydroxymethylaminomethane, trimethylolpropane
Or it is a variety of.
8. preparation method according to claim 1, it is characterised in that: have in MOF base carrier and organic phase-change core material solution
The mass ratio of machine phase transformation core material is 5:3-10；Optionally the mass ratio of MOF base carrier and organic phase-change core material PEG2000 are 5:4；
And/or when preparation MOF mother liquor, solvent for use is water, the molar ratio of MOF matrix and water is 1:10-40；It is optionally 1:
20-30；It is still optionally further 1:25；
And/or preheating the temperature of foam metal is 95-105 DEG C；
And/or the temperature that MOF reaction solution is reacted is 25-100 DEG C；
And/or it is 25-100 DEG C that gained foam metal matrix is placed in the temperature reacted in MOF growth-promoting media.
9. a kind of sizing MOF base composite phase-change material that preparation method described in one of -8 according to claim 1 obtains.
10. a kind of application of sizing MOF base composite phase-change material according to claim 9 in energy storage and release.
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