CN105694820A - 一种水合盐-金属有机骨架复合相变材料的制备方法 - Google Patents
一种水合盐-金属有机骨架复合相变材料的制备方法 Download PDFInfo
- Publication number
- CN105694820A CN105694820A CN201610140102.2A CN201610140102A CN105694820A CN 105694820 A CN105694820 A CN 105694820A CN 201610140102 A CN201610140102 A CN 201610140102A CN 105694820 A CN105694820 A CN 105694820A
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- China
- Prior art keywords
- hydrate
- chloride
- sulfate
- nitrate
- acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000012782 phase change material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011162 core material Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 16
- 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 10
- 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 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 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 8
- 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 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 claims description 6
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 5
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 5
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 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 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 5
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 5
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 5
- 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 4
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 4
- 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 4
- 229940009827 aluminum acetate Drugs 0.000 claims description 4
- 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 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 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 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound 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
- 229940078494 nickel acetate Drugs 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
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- -1 chlorine Copper chloride hydrate Chemical compound 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 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 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 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 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- RHJLXVSECBNOGM-UHFFFAOYSA-N O.[N+](=O)([O-])[O-].[Ti+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound O.[N+](=O)([O-])[O-].[Ti+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] RHJLXVSECBNOGM-UHFFFAOYSA-N 0.000 claims description 2
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 claims description 2
- NMSGLFREHLNYDF-UHFFFAOYSA-K aluminum;triacetate;hydrate Chemical compound O.[Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O NMSGLFREHLNYDF-UHFFFAOYSA-K 0.000 claims description 2
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- JZNZTFFWLZUIKD-UHFFFAOYSA-N chromium(3+);trinitrate;hydrate Chemical compound O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JZNZTFFWLZUIKD-UHFFFAOYSA-N 0.000 claims description 2
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 claims description 2
- QVCGXRQVUIKNGS-UHFFFAOYSA-L cobalt(2+);dichloride;hydrate Chemical compound O.Cl[Co]Cl QVCGXRQVUIKNGS-UHFFFAOYSA-L 0.000 claims description 2
- XZXAIFLKPKVPLO-UHFFFAOYSA-N cobalt(2+);dinitrate;hydrate Chemical compound O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XZXAIFLKPKVPLO-UHFFFAOYSA-N 0.000 claims description 2
- BGORGFZEVHFAQU-UHFFFAOYSA-L cobalt(2+);sulfate;hydrate Chemical compound O.[Co+2].[O-]S([O-])(=O)=O BGORGFZEVHFAQU-UHFFFAOYSA-L 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 claims description 2
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 2
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 claims description 2
- HGGYAQHDNDUIIQ-UHFFFAOYSA-L dichloronickel;hydrate Chemical compound O.Cl[Ni]Cl HGGYAQHDNDUIIQ-UHFFFAOYSA-L 0.000 claims description 2
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 claims description 2
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 claims description 2
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- MSBWDNNCBOLXGS-UHFFFAOYSA-L manganese(2+);diacetate;hydrate Chemical compound O.[Mn+2].CC([O-])=O.CC([O-])=O MSBWDNNCBOLXGS-UHFFFAOYSA-L 0.000 claims description 2
- HBTFASPVVFSRRI-UHFFFAOYSA-N manganese(2+);dinitrate;hydrate Chemical compound O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O HBTFASPVVFSRRI-UHFFFAOYSA-N 0.000 claims description 2
- HIIGGQNLPWIVAG-UHFFFAOYSA-L nickel(2+);diacetate;hydrate Chemical compound O.[Ni+2].CC([O-])=O.CC([O-])=O HIIGGQNLPWIVAG-UHFFFAOYSA-L 0.000 claims description 2
- DWAHIRJDCNGEDV-UHFFFAOYSA-N nickel(2+);dinitrate;hydrate Chemical compound O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DWAHIRJDCNGEDV-UHFFFAOYSA-N 0.000 claims description 2
- LKNLEKUNTUVOML-UHFFFAOYSA-L nickel(2+);sulfate;hydrate Chemical compound O.[Ni+2].[O-]S([O-])(=O)=O LKNLEKUNTUVOML-UHFFFAOYSA-L 0.000 claims description 2
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 2
- ACGYMLSVOJFRAP-UHFFFAOYSA-N octahydrate;hydrochloride Chemical compound O.O.O.O.O.O.O.O.Cl ACGYMLSVOJFRAP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 2
- 229940001593 sodium carbonate Drugs 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229940018038 sodium carbonate decahydrate Drugs 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 2
- LHCLMGWTWKCTAV-UHFFFAOYSA-J titanium(4+) disulfate hydrate Chemical compound O.[Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LHCLMGWTWKCTAV-UHFFFAOYSA-J 0.000 claims description 2
- HOSRYPRYWDKHDZ-UHFFFAOYSA-J titanium(4+);tetrachloride;hydrate Chemical compound O.Cl[Ti](Cl)(Cl)Cl HOSRYPRYWDKHDZ-UHFFFAOYSA-J 0.000 claims description 2
- VITRLXDSBBVNCZ-UHFFFAOYSA-K trichloroiron;hydrate Chemical compound O.Cl[Fe](Cl)Cl VITRLXDSBBVNCZ-UHFFFAOYSA-K 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- CHSMNMOHKSNOKO-UHFFFAOYSA-L zinc;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Zn+2] CHSMNMOHKSNOKO-UHFFFAOYSA-L 0.000 claims description 2
- FOSPKRPCLFRZTR-UHFFFAOYSA-N zinc;dinitrate;hydrate Chemical compound O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FOSPKRPCLFRZTR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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Abstract
本发明属于纳米复合材料和复合相变材料领域，具体涉及一种金属有机骨架基复合相变材料的制备方法。具体方案首先选择合适的金属盐、配体以及无机相变材料基材，根据芯材的种类对金属有机骨架进行孔径孔道大小的设计和调控，以更好的匹配所要负载的相变芯材；将金属盐、配体、无机相变材料及添加剂进行共混，密封保温一段时间后，补充适当的水分，便得到水合盐-金属有机骨架复合相变材料。本发明的优点在于：所制备的复合相变材料，不但能够提高复合相变材料的热存储性能，而且可以有效避免相变相分离和过冷度等问题；用本发明制备的复合相变材料传热性能优异、循环稳定性好；该复合相变材料制备过程工艺简单，一步完成，无副产物，无需后处理，适合规模化生产。
Description
技术领域
本发明属于复合材料和复合相变材料领域，具体涉及一种金属有机骨架基复合相变材料的制备方法。
背景技术
化石燃料的日趋减少和人类对能源的迫切需求使能源短缺成为举世瞩目的重要问题，开发新能源替代传统化石燃料是解决上述问题的必然趋势。目前，人类开发并已经投入使用了一些清洁能源如太阳能、风能、海洋能等。然而此类能源往往存在间断性、波动性等缺陷，增加了使用的局限性，无法满足全天候连续使用的要求。相变储能技术通过相变储能材料(Phasechangematerials，PCMs)发生相转变实现能量的吸收和释放，并同时达到有效控温的目的，是解决上述清洁能源缺陷的有效途径。相变储能材料现已在室内控温，废热再利用，电力移峰填谷，太空航天以及军事领域等得到了广泛的应用。
固-液相变材料由于具有优异的能量储存性能和良好的循环使用性能，目前得到了最为广泛的应用。根据相变材料的性质，一般可分为无机相变材料和有机相变材料二大类。无机相变材料具有相变潜热大、相变温度范围广(可从几摄氏度到上百摄氏度)、价格便宜、导热系数高等优点，然而无机相变材料存在严重的过冷和相分离现象，这大大影响了无机水合盐的使用寿命和储热性能。该问题的解决，可大大延长其使用寿命，增强潜热储热性能，提高其在传统应用领域的使用效果，具有十分重要的意义。例如，专利CN103525373A公开了一种复合定形相变蓄热材料及其制备方法。该专利通过表面活性剂对相变材料的乳化作用后，将相变材料封装于多孔材料中。专利CN103525373A公开了一种Na2HPO4·12H2O储热材料及其制备方法。该专利介绍的相变材料具有热循环性能好，方法可靠性好，应用方便等优点。上诉方法虽然能够解决或部分解决无机相变材料的过冷和相分离等问题，但是制备过程复杂、工艺繁琐，给推广应用带来诸多不便，并且长期性能难以得到保证。
金属有机骨架材料(MOFs)是一种具有周期性无限网络结构的纳米多孔材料，MOFs的孔道可吸附无机相变材料，并为相变材料提供成核点，同时三维的网络结构可有效阻止相变材料的相分离，实现相变材料过冷度的降低和阻止相分离的产生。因此，开发一种新型金属有机骨架基复合相变材料具有广阔的应用前景。
发明内容
本发明的目的在于通过原位合成方法，开发一种新型的复合相变材料，使该类相变材料有效解决无机相变材料存在的过冷度和相分离等问题，同时又具有生产工艺简单，制备方便等特点。
本发明的技术方案是：1)首先根据相变芯材的种类选择合适的金属盐、配体，对金属有机骨架进行孔径孔道大小的设计和调控，以更好的匹配所要负载的相变芯材；2)将金属盐、配体、无机相变材料及添加剂进行共混，加入适当的水，密封保温一段时间后，便得到水合盐-金属有机骨架复合相变材料。
具体制备步骤为：
将金属盐、配体、相变材料及添加剂进行共混，混合均匀后密封，放入烘箱中，在40～220℃条件下保温4～120h，待反应结束后，加入一定量的水，进一步混合均匀，即得到水合盐-金属有机骨架复合相变材料。金属盐：配体：相变材料：添加剂的质量比为1～100：1～100：1～100：1～100。
步骤中所述的可溶性金属盐包括硝酸铬、氯化铬、硫酸铬、醋酸铬、硝酸锆、氯化锆、硫酸锆、醋酸锆、硝酸铜、氯化铜、硫酸铜、醋酸铜、硝酸锌、氯化锌、硫酸锌、醋酸锌、硝酸镍、氯化镍、硫酸镍、醋酸镍、硝酸钴、氯化钴、硫酸钴、醋酸钴、硝酸铁、氯化铁、硫酸铁、醋酸铁、硝酸铝、氯化铝、硫酸铝、醋酸铝、硝酸锰、氯化锰、硫酸锰、醋酸锰、硝酸钛、氯化钛、硫酸钛等其中的一种或几种。
步骤中所述的有机羧酸配体包括对苯二甲酸、邻苯二甲酸、均苯三甲酸，均苯四甲酸，苯六甲酸，2-磺酸基对苯二甲酸，2-羟基对苯二甲酸，2-硝基对苯二甲酸，2-氨基对苯二甲酸，1,1':4',1”-苯基-4,4”-二甲酸，1,1'-二苯基-4,4'-二甲酸，1,2,4-偏三甲酸等其中的一种或几种。
步骤中所述的相变芯材为结晶水合盐、无机盐类中的一种或几种可溶性相变材料。结晶水合盐类，具体包括十水碳酸钠、十水硫酸钠、十二水磷酸氢钠、六水氯化钙、三水醋酸钠、五水硫代硫酸钠、硝酸铬水合盐、氯化铬水合盐、硫酸铬水合盐、醋酸铬水合盐、硝酸锆水合盐、氯化氧化锆(Ⅳ)八水合物、硫酸锆水合盐、醋酸锆水合盐、硝酸铜水合盐、氯化铜水合盐、硫酸铜水合盐、醋酸铜水合盐、硝酸锌水合盐、氯化锌水合盐、硫酸锌水合盐、醋酸锌水合盐、硝酸镍水合盐、氯化镍水合盐、硫酸镍水合盐、醋酸镍水合盐、硝酸钴水合盐、氯化钴水合盐、硫酸钴水合盐、醋酸钴水合盐、硝酸铁水合盐、氯化铁水合盐、硫酸铁水合盐、醋酸铁水合盐、硝酸铝水合盐、氯化铝水合盐、硫酸铝水合盐、醋酸铝水合盐、硝酸锰水合盐、氯化锰水合盐、硫酸锰水合盐、醋酸锰水合盐、硝酸钛水合盐、氯化钛水合盐、硫酸钛水合盐；无机盐类，具体包括氯化钠、硝酸钠、碳酸钠、硫酸钠、硝酸钾、硝酸锂、氯化钾、氯化锂、铬酸锂、碳酸锂、硝酸铬、氯化铬、硫酸铬、醋酸铬、硝酸锆、氯化锆、硫酸锆、醋酸锆、硝酸铜、氯化铜、硫酸铜、醋酸铜、硝酸锌、氯化锌、硫酸锌、醋酸锌、硝酸镍、氯化镍、硫酸镍、醋酸镍、硝酸钴、氯化钴、硫酸钴、醋酸钴、硝酸铁、氯化铁、硫酸铁、醋酸铁、硝酸铝、氯化铝、硫酸铝、醋酸铝、硝酸锰、氯化锰、硫酸锰、醋酸锰、硝酸钛、氯化钛、硫酸钛等。
步骤(1)所述的添加剂包括强氧化钠、氢氧化钾等其中的一种或几种。
本发明的优点在于：所制备的复合相变材料，不但能够提高复合相变材料的热存储性能，而且可以有效避免相变相分离和过冷度等问题；用本发明制备的复合相变材料传热性能优异、循环稳定性好；该复合相变材料制备过程工艺简单，一步完成，无副产物，无需后处理，适合规模化生产。
附图说明
图1为本发明实施例1得到的十水合硫酸钠-CuBTA复合相变材料的扫描电镜照片。
图2为本发明实施例1得到的十水合硫酸钠-CuBTA复合相变材料的DSC图。
具体实施方式
下面结合具体的实施方式对本发明的技术方案做进一步说明。
实施案例1
将1.25g五水合硫酸铜、0.7g偏苯三甲酸、2g十水合硫酸钠及0.4g强氧化纳进行共混，加入0.5g水，混合均匀后密封，放入烘箱中，在100℃条件下保温4h，待反应结束后，进一步混合均匀，便得到十水合硫酸钠-CuBTA复合相变材料。
实施案例2
将1.25g五水合硫酸铜、0.7g均苯三甲酸、2.5g十水合硫酸钠及0.4g强氧化纳进行共混，加入1g水，混合均匀后密封，放入烘箱中，在100℃条件下保温4h，待反应结束后，进一步混合均匀，便得到十水合硫酸钠-CuBTC复合相变材料。
实施案例3
将1.96g六水合硫酸铬、0.64g均苯四甲酸、2.5g十水合硫酸钠及0.4g强氧化纳进行共混，加入1g水，混合均匀后密封，放入烘箱中，在100℃条件下保温4h，待反应结束后，进一步混合均匀，便得到十水合硫酸钠-CrBTEC复合相变材料。
Claims (5)
1.一种水合盐-金属有机骨架复合相变材料的制备方法，其特征在于具体制备步骤为：
将金属盐、配体、相变材料及添加剂进行共混，加入一定量的水，混合均匀后密封，放入烘箱中，在40～220℃条件下保温4～120h，待反应结束后，进一步混合均匀，便得到水合盐-金属有机骨架复合相变材料；金属盐：配体：相变材料：添加剂的质量比为1～100：1～100：1～100：1～100。
2.如权利要求1所述的一种水合盐-金属有机骨架复合相变材料的制备方法，其特征在于所述的金属盐包括硝酸铬、氯化铬、硫酸铬、醋酸铬、硝酸锆、氯化锆、硫酸锆、醋酸锆、硝酸铜、氯化铜、硫酸铜、醋酸铜、硝酸锌、氯化锌、硫酸锌、醋酸锌、硝酸镍、氯化镍、硫酸镍、醋酸镍、硝酸钴、氯化钴、硫酸钴、醋酸钴、硝酸铁、氯化铁、硫酸铁、醋酸铁、硝酸铝、氯化铝、硫酸铝、醋酸铝、硝酸锰、氯化锰、硫酸锰、醋酸锰、硝酸钛、氯化钛、硫酸钛中的一种或几种。
3.如权利要求1所述的一种水合盐-金属有机骨架复合相变材料的制备方法，其特征在于所述的有机羧酸配体包括对苯二甲酸、邻苯二甲酸、均苯三甲酸，均苯四甲酸，苯六甲酸，2-磺酸基对苯二甲酸，2-羟基对苯二甲酸，2-硝基对苯二甲酸，2-氨基对苯二甲酸，1,1':4',1”-苯基-4,4”-二甲酸，1,1'-二苯基-4,4'-二甲酸，1,2,4-偏三甲酸中的一种或几种。
4.如权利要求1所述的一种水合盐-金属有机骨架复合相变材料的制备方法，其特征在于所述的相变芯材为结晶水合盐、无机盐类中的一种或几种可溶性相变材料；结晶水合盐类，具体包括十水碳酸钠、十水硫酸钠、十二水磷酸氢钠、六水氯化钙、三水醋酸钠、五水硫代硫酸钠、硝酸铬水合盐、氯化铬水合盐、硫酸铬水合盐、醋酸铬水合盐、硝酸锆水合盐、氯化氧化锆(Ⅳ)八水合物、硫酸锆水合盐、醋酸锆水合盐、硝酸铜水合盐、氯化铜水合盐、硫酸铜水合盐、醋酸铜水合盐、硝酸锌水合盐、氯化锌水合盐、硫酸锌水合盐、醋酸锌水合盐、硝酸镍水合盐、氯化镍水合盐、硫酸镍水合盐、醋酸镍水合盐、硝酸钴水合盐、氯化钴水合盐、硫酸钴水合盐、醋酸钴水合盐、硝酸铁水合盐、氯化铁水合盐、硫酸铁水合盐、醋酸铁水合盐、硝酸铝水合盐、氯化铝水合盐、硫酸铝水合盐、醋酸铝水合盐、硝酸锰水合盐、氯化锰水合盐、硫酸锰水合盐、醋酸锰水合盐、硝酸钛水合盐、氯化钛水合盐、硫酸钛水合盐；无机盐类，具体包括氯化钠、硝酸钠、碳酸钠、硫酸钠、硝酸钾、硝酸锂、氯化钾、氯化锂、铬酸锂、碳酸锂、硝酸铬、氯化铬、硫酸铬、醋酸铬、硝酸锆、氯化锆、硫酸锆、醋酸锆、硝酸铜、氯化铜、硫酸铜、醋酸铜、硝酸锌、氯化锌、硫酸锌、醋酸锌、硝酸镍、氯化镍、硫酸镍、醋酸镍、硝酸钴、氯化钴、硫酸钴、醋酸钴、硝酸铁、氯化铁、硫酸铁、醋酸铁、硝酸铝、氯化铝、硫酸铝、醋酸铝、硝酸锰、氯化锰、硫酸锰、醋酸锰、硝酸钛、氯化钛、硫酸钛。
5.如权利要求1所述的一种水合盐-金属有机骨架复合相变材料的制备方法，其特征在于所述的添加剂包括强氧化钠、氢氧化钾中的一种或几种。
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| CN111097385A (zh) * | 2019-12-26 | 2020-05-05 | 江苏大学 | 一种微孔水稳定染料吸附剂及制备方法 |
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