CN103180282A - 制备含碳复合材料的方法 - Google Patents
制备含碳复合材料的方法 Download PDFInfo
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- CN103180282A CN103180282A CN2011800514847A CN201180051484A CN103180282A CN 103180282 A CN103180282 A CN 103180282A CN 2011800514847 A CN2011800514847 A CN 2011800514847A CN 201180051484 A CN201180051484 A CN 201180051484A CN 103180282 A CN103180282 A CN 103180282A
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- China
- Prior art keywords
- acid
- dicarboxylic acid
- organic compound
- matrix material
- metal
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 34
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 23
- 239000005864 Sulphur Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000000197 pyrolysis Methods 0.000 claims description 12
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 10
- 125000002524 organometallic group Chemical group 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 150000001455 metallic ions Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000013270 controlled release Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 23
- 230000001681 protective effect Effects 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- -1 preferably Substances 0.000 description 20
- 125000003118 aryl group Chemical group 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 125000001931 aliphatic group Chemical group 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 5
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- 229920002266 Pluriol® Polymers 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000013148 Cu-BTC MOF Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000013206 MIL-53 Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- 150000003463 sulfur Chemical class 0.000 description 3
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005792 Geraniol Substances 0.000 description 2
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 2
- 239000013132 MOF-5 Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000013236 Zn4O(BTB)2 Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
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- LMAQRGNIWKAAFR-UHFFFAOYSA-N benzene;dicarboxy carbonate Chemical compound C1=CC=CC=C1.OC(=O)OC(=O)OC(O)=O LMAQRGNIWKAAFR-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 150000002367 halogens Chemical class 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
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- 239000001683 mentha spicata herb oil Substances 0.000 description 2
- 239000013213 metal-organic polyhedra Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- BSAIUMLZVGUGKX-UHFFFAOYSA-N non-2-enal Chemical compound CCCCCCC=CC=O BSAIUMLZVGUGKX-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N rose oxide Chemical compound CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 2
- 239000010670 sage oil Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
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Abstract
本发明涉及一种制备含碳复合材料的方法,其中使多孔金属-有机骨架在保护气体气氛下热解,所述多孔金属-有机骨架含有与至少一种金属离子配位的至少一种至少双齿有机化合物,并且所述至少一种至少双齿有机化合物是不含氮的。本发明还提供可以此方式获得的复合材料,以及含有它们的硫电极,以及它们的用途。
Description
本发明涉及一种制备含碳复合材料的方法。本发明还涉及以此方式获得的复合材料,以及含有这些复合材料的硫电极,以及它们的用途。
复合材料是含有两种或更多种结合的物质的材料。它们的准确化学组成通常是未知的,所以它们通常必须通过其制备方法和原料来表征。
这些材料可以具有在一定程度上(如果有的话)不能从其原料预期的性能。
一个例子是从由钴离子和含氮配体(1,3,5-三嗪-2,4,6-三基三甘氨酸,TTG)制成的多孔金属-有机骨架制备的复合材料。这种复合材料通过热解制备,并且由于其氮含量而具有用于分离CO2/CH4的优良分离性能(Y.Shen等,Chem.Commun.46(2010),1308-1310)。
尽管在现有技术中有公知的复合材料,但是仍然需要其他材料。
所以,本发明的目的是提供这种材料以及它们的制备方法。
此目的通过一种制备含碳复合材料的方法实现,此方法包括以下步骤:
(a)使多孔金属-有机骨架在保护气体气氛下热解,所述多孔金属-有机骨架含有与至少一种金属离子配位的至少一种至少双齿有机化合物,其中所述至少一种至少双齿有机化合物是不含氮的。
本发明方法可以包括另一个步骤(b)。其中,从在步骤(a)中获得的复合材料至少部分地除去一种或多种金属组分。
此金属组分或这些金属组分是来源于在多孔金属-有机骨架中所含的至少一种金属离子的转变。
此外,本发明方法可以包括步骤(c),其中从步骤(a)或(b)获得的复合材料用硫浸渍。
热解可以通过现有技术公知的方法进行。
在步骤(a)中的热解优选在至少500℃的温度下进行,优选至少600℃。热解更优选在600-1000℃的温度下进行,甚至更优选600-800℃。
工艺步骤(a)在保护气体气氛下进行。保护气体气氛优选是氮气气氛。其它公知的保护气体也是可以的,例如稀有气体。
多孔金属-有机骨架用作原料。其含有与至少一种金属离子配位的至少一种至少双齿有机化合物,其中至少一种至少双齿有机化合物是不含氮的。
这种金属-有机骨架(MOF)是现有技术公知的,例如参见US5,648,508,EP-A-0790253,M.O'Keeffe等,J.Sol.State Chem.,152(2000),3-20页,H.Li等,Nature402,(1999),第276页,M.Eddaoudi等,Topics in Catalysis9,(1999),105-111页,B.Chen等,Science291,(2001),1021-1023页,DE-A-10111230,DE-A102005053430,WO-A2007/054581,WO-A2005/049892和WO-A2007/023134。
作为一类具体的这种金属-有机骨架,近期的文献描述了“受限的”骨架,其中网络不能无限延伸,而是由于有机化合物的特定选择而形成多面体。A.C.Sudik等,J.Am.Chem.Soc.127(2005),7110-7118页描述了这些特定的骨架。在这里,它们称为金属-有机多面体(MOP)以进行区分。
本发明的金属-有机骨架含有孔,尤其是微孔和/或中孔。微孔定义为直径为2nm或更小的孔,中孔定义为直径在2-50nm范围内的孔,在每种情况下对应于在Pure&Applied Chem.57(1983),603–619页,尤其第606页中给出的定义。微孔和/或中孔的存在可以通过吸着检测来检查,这根据DIN66131和/或DIN66134测定了MOF在77开尔文下对于氮的吸收能力。
对于粉末形式的MOF,根据兰格缪尔模型(DIN66131、DIN66134)计算的比表面积是大于100m2/g,更优选大于300m2/g,更优选大于700m2/g,再更优选大于800m2/g,再更优选大于1000m2/g,特别优选大于1200m2/g。
含有金属-有机骨架的成形体可以具有较低的活性表面积,但是这优选大于150m2/g,更优选大于300m2/g,更优选大于700m2/g.
在根据本发明的骨架中的金属组分优选选自族Ia,IIa,IIIa,Iva至VIIIa和Ib至VIb。特别优选Mg,Ca,Sr,Ba,Sc,Y,Ln,Ti,Zr,Hf,V,Nb,Ta,Cr,Mo,W,Mn,Re,Fe,Ro,Os,Co,Rh,Ir,Ni,Pd,Pt,Cu,Ag,Au,Zn,Cd,Hg,Al,Ga,In,TI,Si,Ge,Sn,Pb,As,Sb和Bi,其中Ln表示镧系元素。
镧系元素是La,Ce,Pr,Nd,Pm,Sm,En,Gd,Tb,Dy,Ho,Er,Tm,Yb。
关于这些元素的离子,特别可以提到Mg2+,Ca2+,Sr,Ba2+,Sc3+,Y3+,Ln3+,Ti4+,Zr4+,Hf4+,V4+,V3+,V2+,Nb3+,Ta3+,Cr3+,Mo3+,W3+,Mn3+,Mn2+,Re3+,Re2+,Fe3+,Fe2+,Ru3+,Ru2+,Os3+,Os2+,Co3+,Co2+,Rh2+,Rh+,Ir2+,lr+,Ni2+,Ni+,Pd2+,Pd+,Pt2+,Pt+,Cu2+,Cu+,Ag+,Au+,Zn2+,Cd2+,Hg2+,Al3+,Ga3+,In3+,Tl3+,Si4+,Si2+,Ge4+,Ge2+,Sn4+,Sn2+,Pb4+,Pb2+,As5+,As3+,As+,Sb5+,Sb3+,Sb+,Bi5+,Bi3+和Bi+。
更特别优选Mg,Al,Zr,Ti,V,Cr,Mo,Fe,Co,Cu,Ni,Zn。特别优选Al,Ti,Mg,Fe,Cu和Zn。非常特别优选Mg,Al,Cu和Zn。
术语“至少双齿有机化合物”表示这样的有机化合物,其含有至少一个能与给定的金属离子形成至少两个配位键和/或能与两个或更多个、优选两个金属原子中的每个形成一个配位键的官能团。
作为可以用于形成上述配位键的官能团,可以尤其提到例如以下官能团:-CO2H,-CS2H,-NO2,-B(OH)2,-SO3H,-Si(OH)3,-Ge(OH)3,-Sn(OH)3,-Si(SH)4,-Ge(SH)4,-Sn(SH)3,-PO3H,-AsO3H,-AsO4H,-P(SH)3,-As(SH)3,-CH(RSH)2,-C(RSH)3-CH(ROH)2,-C(ROH)3,其中R例如优选是具有1、2、3、4或5个碳原子的亚烷基,例如亚甲基、亚乙基、亚正丙基、亚异丙基、亚正丁基、亚异丁基、亚叔丁基或亚正戊基,或含有1或2个芳环的芳基,例如2个C6环,其可以任选地稠合和可以合适地各自独立地在每种情况下被至少一个取代基取代,和/或可以各自独立地在每种情况下含有至少一个杂原子,例如O和/或S。在另一个优选实施方案中,可以提到其中不存在上述R的官能团。这些基团尤其是CH(SH)2,-C(SH)3,-CH(OH)2,或-C(OH)3。
至少两个官能团原则上可以与任何合适的有机化合物结合,只要能确保带有这些官能团的有机化合物能形成配位键并制备骨架即可。
含有至少两个官能团的有机化合物优选衍生自饱和或不饱和的脂族化合物或芳族化合物,或衍生自脂族和芳族化合物。
脂族化合物或者脂族和芳族化合物中的脂族结构部分可以是直链和/或支化和/或环状的,其中在每个化合物中也可以存在多个环。脂族化合物或者脂族和芳族化合物中的脂族结构部分优选含有1-15个碳原子,更优选1-14个碳原子,更优选1-13个碳原子,更优选1-12个碳原子,更优选1-11个碳原子,特别优选1-10个碳原子,例如1、2、3、4、5、6、7、8、9或10个碳原子。在这里,特别优选甲烷、金刚烷、乙炔、乙烯或丁二烯。
芳族化合物或者脂族和芳族化合物中的芳族结构部分可以具有一个或多个环,例如2、3、4或5个环,其中这些环可以单独存在和/或其中至少两个环稠合。芳族化合物或者脂族和芳族化合物中的芳族结构部分特别优选具有1、2或3个环,其中特别优选1或2个环。所述化合物的每个环也可以独立地含有至少一个杂原子,例如O、S、B、P、Si、Al,优选N、O和/或S。芳族化合物或者脂族和芳族化合物中的芳族结构部分更优选含有1或2个C6环,其中这些环可以单独存在,或者以稠合形式存在。特别可以提到苯、萘和/或联苯作为芳族化合物。
至少双齿有机化合物更优选是脂族或芳族的、无环或环状的烃,其具有1-18个、优选1-10个和尤其6个碳原子且另外仅仅具有2、3或4个羧基作为官能团。
例如,至少双齿有机化合物是衍生自二羧酸,例如:草酸,琥珀酸,酒石酸,1,4-丁烷二羧酸,1,4-丁烯二羧酸,4-氧杂吡喃-2,6-二羧酸,1,6-己烷二羧酸,癸烷二羧酸,1,8-十七烷二羧酸,1,9-十七烷二羧酸,十七烷二羧酸,乙炔二羧酸,1,2-苯二羧酸,1,3-苯二羧酸,1,3-丁二烯-1,4-二羧酸,1,4-苯二羧酸,p-苯二羧酸,噻吩-3,4-二羧酸,四氢吡喃-4,4-二羧酸,苝-3,9-二羧酸,苝二羧酸,pluriol E200-二羧酸,3,6-二氧杂辛烷二羧酸,3,5-环己二烯-1,2-二羧酸,辛二羧酸,戊烷-3,3-羧酸,1,1'-二萘基二羧酸,聚四氢呋喃-250-二羧酸,1,4,5,6,7,7-六氯-5-降冰片烯-2,3-二羧酸,苯基茚二羧酸,1,4-环己烷二羧酸,萘-1,8-二羧酸,2-苯甲酰基苯-1,3-二羧酸,3,6,9-三氧杂十一烷二羧酸,羟基二苯酮二羧酸,pluriol E300-二羧酸,pluriol E400-二羧酸,pluriol E600-二羧酸,1,4-萘二羧酸,2,6-萘二羧酸,1,3-金刚烷二羧酸,1,8-萘二羧酸,2,3-萘二羧酸,8-甲氧基-2,3-萘二羧酸,8-磺基-2,3-萘二羧酸,蒽-2,3-二羧酸,2',3'-二苯基-p-三联苯-4,4"-二羧酸,(二苯基醚)-4,4'-二羧酸,4(1H)-氧杂硫代色烯-2,8-二羧酸,5-叔丁基-1,3-苯二羧酸,4-环己烯-1,2-二羧酸,三十六烷二羧酸,十四烷二羧酸,1,7-庚烷二羧酸,5-羟基-1,3-苯二羧酸,2,5-二羟基-1,4-二羧酸,呋喃-2,5-二羧酸,1–壬烯-6,9-二羧酸,二十碳烯二羧酸,4,4'-二羟基二苯基甲烷-3,3'-二羧酸,环己烯-2,3-二羧酸,2,4-二氯二苯酮-2',5'-二羧酸,1,3-苯二羧酸,蒽醌-1,5-二羧酸,2-硝基苯-1,4-二羧酸,庚烷-1,7-二羧酸,环丁烷-1,1-二羧酸,1,14-十四烷二羧酸,5,6-脱氢降冰片烷-2,3-二羧酸或樟脑二羧酸。
至少双齿有机化合物甚至更优选是例如上述提到的二羧酸本身之一。
至少双齿有机化合物可以例如衍生自三羧酸,例如:2-羟基-1,2,3-丙烷三羧酸,1,2,3-、1,2,4-苯三羧酸,1,2,4-丁烷三羧酸,2-膦酰基-1,2,4-丁烷三羧酸,1,3,5-苯三羧酸,1-羟基-1,2,3-丙烷三羧酸,5-乙酰基-3-氨基-6-甲基苯-1,2,4-三羧酸,1,2,3-丙烷三羧酸或金精三羧酸.
至少双齿有机化合物甚至更优选是例如上述提到的三羧酸本身之一。
衍生自四羧酸的至少双齿有机化合物的例子是:1,1–二氧苝并[1,12-BCD]噻吩-3,4,9,10-四羧酸,苝-四羧酸,例如苝-3,4,9,10-四羧酸或(苝1,12-砜)-3,4,9,10-四羧酸,丁烷四羧酸,例如1,2,3,4-丁烷四羧酸或内消旋-1,2,3,4-丁烷四羧酸,癸烷-2,4,6,8-四羧酸,1,4,7,10,13,16-六氧杂环十八烷-2,3,11,12-四羧酸,1,2,4,5-苯四羧酸,1,2,11,12-十二烷四羧酸,1,2,5,6-己烷四羧酸,1,2,7,8-辛烷四羧酸,1,4,5,8-萘四羧酸,1,2,9,10-癸烷四羧酸,二苯酮四羧酸,3,3',4,4'-二苯酮四羧酸,四氢呋喃四羧酸,或环戊烷四羧酸,例如环戊烷-1,2,3,4-四羧酸。
至少双齿有机化合物甚至更优选是例如上述提到的四羧酸本身之一。
非常特别优选的是任选地至少单取代的芳族二羧酸、三羧酸或四羧酸,其具有1、2、3、4或更多个环,每个环能含有至少一个杂原子,两个或更多个环能含有相同或不同的杂原子。优选例如单环二羧酸、单环三羧酸、单环四羧酸、双环二羧酸、双环三羧酸、双环四羧酸、三环二羧酸、三环三羧酸、三环四羧酸、四环二羧酸、四环三羧酸和/或四环四羧酸。合适的杂原子是例如O、S、B、P,其中优选的杂原子是S和/或O。作为合适的取代基,可以尤其提到-OH、硝基、烷基或烷氧基。
特别优选使用以下作为至少双齿有机化合物:乙炔二羧酸(ADC),樟脑二羧酸,富马酸,琥珀酸,苯二羧酸例如邻苯二甲酸、间苯二甲酸、对苯二甲酸(BDC),萘二羧酸(NDC),二苯基二羧酸,例如4,4'-二苯基二羧酸(BPDC),苯三羧酸,例如1,2,3-、1,2,4-苯三羧酸或1,3,5-苯三羧酸(BTC),苯四羧酸,金刚烷四羧酸(ATC),金刚烷二苯甲酸酯(ADB),苯三苯甲酸酯(BTB),甲烷四苯甲酸酯(MTB),金刚烷四苯甲酸酯,或二羟基对苯二甲酸,例如2,5-二羟基对苯二甲酸(DHBDC),四氢芘-2,7-二羧酸(HPDC),二苯基四羧酸(BPTC)。
非常特别优选的是邻苯二甲酸,间苯二甲酸,对苯二甲酸,2,6-萘二羧酸,1,4-萘二羧酸,1,5-萘二羧酸,1,2,3-苯三羧酸,1,2,4-苯三羧酸,1,3,5-苯三羧酸,1,2,4,5-苯四羧酸,富马酸,二苯基二羧酸酯,1,5-和2,6-萘二羧酸,叔丁基间苯二甲酸,二羟基苯甲酸,BTB,HPDC,BPTC。
除了这些至少双齿有机化合物,金属-有机骨架还可以含有一种或多种单齿配体和/或一种或多种不是衍生自二羧酸、三羧酸或四羧酸的至少双齿配体。
除了这些至少双齿有机化合物,金属-有机骨架还可以含有一种或多种单齿配体。
用于制备金属-有机骨架的合适溶剂尤其是乙醇、二甲基甲酰胺、甲苯、甲醇、氯苯、二乙基甲酰胺、二甲基亚砜、水、过氧化氢、甲基胺、氢氧化钠溶液、N-甲基吡咯烷酮醚、乙腈、苄基氯、三乙胺、乙二醇以及它们的混合物。其它金属离子、至少双齿有机化合物和用于制备MOF的溶剂例如参见US-A5,648,508或DE-A10111230。
金属-有机骨架的孔径可以通过选择合适的配体和/或至少双齿有机化合物来控制。一般而言,有机化合物越大,孔径就越大。孔径优选是0.2-30nm,特别优选是0.3-3nm,基于结晶材料。
金属-有机骨架的例子如下所示。除了骨架、金属和至少双齿配体的名称之外,也列出了溶剂和孔参数(角α,β和γ,以及间隔A,B和C,单位是)。后者是通过X-射线衍射检测的。
ADC乙炔二羧酸
NDC萘二羧酸
BDC苯二羧酸
ATC金刚烷四羧酸
BTC苯三羧酸
BTB苯三苯甲酸
MTB甲烷四苯甲酸
ATB金刚烷四苯甲酸
ADB金刚烷二苯甲酸
其它金属-有机骨架是MOF-69至80,MOF103至106,MOF-177,MOF-235,MOF-236,MOF-501,MOF-502,MOF-505,IRMOF-1,IRMOF-61,IRMOP-51,MIL-45,MIL-47,MIL-53,MIL-59,MIL-60,MIL-61,MIL-63,MIL-68,MIL-85,它们在文献中已经有描述。
特别优选的金属-有机骨架是MIL-53,Zn-tBu-间苯二甲酸,Al-BDC,MOF-5,MOF-177,MOF-505,IRMOF-8,IRMOF-11,Cu-BTC,Al-NDC,Al-BTC,Cu-BTC,Al-NDC,Mg-NDC,Al-甲酸酯,MOF-74,Sc-对苯二甲酸酯。甚至更优选的是Al-BDC,Al-富马酸酯,Al-NDC,Al-BTC和Cu-BTC。
不含氮的至少一种至少双齿有机化合物优选是衍生自二羧酸、三羧酸或四羧酸。
为了本发明目的,术语“衍生自”表示对于羧基官能而言,至少一种至少双齿有机化合物是以部分或全部脱质子化的形式存在的。此外,术语“衍生自”表示至少一种至少双齿有机化合物可以具有其它取代基。因此,除了羧酸官能团之外,可以另外存在一个取代基或各自独立的多个取代基,例如羟基、甲氧基、卤素或甲基。优选的是没有其它取代基,或仅仅存在一个或多个F取代基。为了本发明目的,术语“衍生自”还表示羧酸官能团可以作为硫类似物存在。硫类似物是-C(=O)SH及其互变异构体,以及-C(S)SH。优选不存在硫类似物。
除了制备MOF的常规方法、例如参见US5,648,508之外,它们也可以通过电化学途径制备。在这方面,可以参见DE-A10355087和WO-A2005/049892。
在步骤(b)中,进行至少部分地除去一种或多种金属组分的操作。优选所述一种或多种金属组分含有至少一种金属氧化物。
至少部分地除去的操作优选通过用碱性液体洗涤出去来进行。也可以使用现有技术中公知的其它方法。合适的碱性液体例如是氢氧化钠水溶液。其它碱金属氢氧化物也是合适的。根据金属化合物,也可以进行酸处理。
在步骤(c)中,对从步骤(a)或(b)获得的复合材料进行浸渍。用化学品进行浸渍是公知的,可以在多孔金属-有机骨架的浸渍中那样进行。这例如参见国际专利申请PCT/EP2010/053530。
浸渍优选通过混合和随后的加热进行。浸渍优选通过机械混合进行。硫可以作为固体引入,或可以从悬浮液或溶液引入,尤其是有机溶液,例如含甲苯的溶液,尤其是甲苯溶液。
本发明还提供一种复合材料,其可以通过本发明方法获得。
本发明还提供通过本发明方法获得的本发明复合材料用于吸收至少一种物质的用途,以用于所述物质的储存、去除、受控释放、化学反应的目的,或用作载体。
所述至少一种物质优选是气体或气体混合物。
使用金属-有机骨架的储存方法一般描述在WO-A2005/003622、WO-A2003/064030、WO-A2005/049484、WO-A2006/089908和DE-A102005012087中。其中描述的方法也可以用于本发明的复合材料。
使用金属-有机骨架的分离或提纯方法一般描述在EP-A1674555,DE-A102005000938和DE-A102005022844中。其中描述的方法也可以用于本发明的复合材料。
如果本发明的复合材料用于储存,则这优选在-200℃至+80℃的温度范围内进行。更优选-40℃至+80℃的温度范围。
为了本发明的目的,为了简洁而使用术语“气体”和“液体”,但是气体混合物和液体混合物或液体溶液也包括在“气体”或“液体”的范围内。
优选的气体是氢气、天然气、城市用气、烃,尤其是甲烷、乙烷、乙烯、乙炔、丙烷、正丁烷以及异丁烷,一氧化碳,二氧化碳,氮氧化物,氧气,氧化硫,卤素,卤代烃,NF3,SF6,氨,硼烷,磷烷,硫化氢,胺,甲醛,稀有气体,尤其是氦、氖、氩、氪和氙。
气体特别优选是从含二氧化碳的混合物分离出来的二氧化碳。气体混合物优选含有二氧化碳以及至少H2、CH4或一氧化碳。尤其是,气体混合物含有一氧化碳以及二氧化碳。非常特别优选含有至少10体积%且不超过45体积%的二氧化碳以及至少30体积%且不超过90体积%的一氧化碳的混合物。
一个优选的实施方案是压力变换吸附,其中使用多个平行的吸附器反应器,其中吸附剂排料含有全部或部分的根据本发明的物质。用于CO2/CO分离的吸附阶段优选在0.6-3巴的CO2分压和至少20℃且不超过70℃的温度下进行。为了解析被吸附的二氧化碳,在吸附器反应器中的总压力通常降低到在100毫巴至1巴范围内的值。
本发明的骨架也优选用于在100巴(绝对值)的最小压力下储存气体。最小压力更优选是200巴(绝对值),尤其是300巴(绝对值)。气体特别优选是氢气或甲烷。
但是,至少一种物质也可以是液体。这些液体的例子是消毒剂,无机或有机溶剂,燃料,尤其是汽油或柴油,水力流体,散热器流体,制动液或油,尤其是机油。此外,液体可以是卤代的脂族或芳族的、环状或无环的烃或它们的混合物。尤其是,液体可以是丙酮、乙腈、苯胺、茴香醚、苯、苯甲腈、溴苯、丁醇、叔丁醇、喹啉、氯苯、氯仿、环己烷、二甘醇、乙醚、二甲基乙酰胺、二甲基甲酰胺、二甲基亚砜、二烷、冰醋酸、乙酸酐、乙酸乙酯、乙醇、碳酸亚乙基酯、二氯乙烷、乙二醇、乙二醇二甲基醚、甲酰胺、己烷、异丙醇、甲醇、甲氧基丙醇、3-甲基-1-丁醇、二氯甲烷、甲基乙基酮、N-甲基甲酰胺、N-甲基吡咯烷酮、硝基苯、硝基甲烷、哌啶、丙醇、碳酸亚丙基酯、吡啶、二硫化碳、环丁砜、四氯乙烯、四氯化碳、四氢呋喃、甲苯、1,1,1-三氯乙烷、三氯乙烯、三乙胺、三甘醇、三甘醇二甲醚、水或它们的混合物。
此外,至少一种物质可以是有气味的物质。
有气味的物质优选是挥发性的有机或无机化合物,其含有至少一种以下元素:氮、磷、氧、硫、氟、氯、溴或碘,或是不饱和或芳族的烃,或者饱和或不饱和的醛或酮。更优选的元素是氮、氧、磷、硫、氯、溴;特别优选氮、氧、磷和硫。
尤其是,有气味的物质是氨、硫化氢、氧化硫、氧化氮、臭氧、环状或无环的胺、硫醇、硫醚以及醛、酮、酯、醚、酸或醇。特别优选氨、硫化氢、有机酸(优选乙酸、丙酸、丁酸、异丁酸、戊酸、异戊酸、己酸、庚酸、月桂酸、壬酸),以及环状或无环的含氮或硫的烃,以及饱和或不饱和的醛,例如己醛、庚醛、辛醛、壬醛、癸醛、辛烯醛或壬烯醛,尤其是挥发性醛,例如丁醛、丙醛、乙醛和甲醛,此外是燃料,例如汽油、柴油(成分)。
有气味的物质也可以是香料,其例如用于制备香水。作为香料或能释放这种香料的油,可以提到例如:精油,罗勒油,香叶油,薄荷油,卡南迦树油,豆蔻油,薰衣草油,薄荷油(peppermint oil),肉豆蔻油,甘菊油,桉树油,迷迭香油,柠檬油,白柠檬油,橙油,香柠檬油,麝香洋苏叶油(muscat sage oil),芫荽油,柏木油,1,1–二甲氧基-2-苯基乙烷,2,4-二甲基-4-苯基四氢呋喃,二甲基四氢苯甲醛,2,6-二甲基-7-辛烯-2-醇,1,2-二乙氧基-3,7-二甲基-2,6-辛二烯,苯基乙醛,玫瑰醚,乙基-2-甲基戊酸酯,1-(2,6,6-三甲基-1,3-环己二烯-1-基)-2-丁烯-1-酮,乙基香草醛,2,6-二甲基-2-辛烯醇,3,7-二甲基-2-辛烯醇,叔丁基环己基乙酸酯,乙酸茴香基酯,乙酸烯丙基环己基氧基酯,乙基里哪醇,丁子香酚,香豆素,乙酰乙酸乙基酯,4-苯基-2,4,6-三甲基-1,3-二烷,4-亚甲基-3,5,6,6-四甲基-2-庚酮,乙基四氢藏花酸酯(safranate),香叶腈,顺-3-己烯-1-醇,顺-3-己烯基乙酸酯,顺-3-己烯基甲基碳酸酯,2,6-二甲基-5-庚烯-1–醛,4-(三环[5.2.1.0]亚癸基)-8-丁醛,5-(2,2,3-三甲基-3-环戊烯基)-3-甲基戊烷-2-醇,对-叔丁基α-甲基氢化肉桂醛,乙基[5.2.1.0]三环癸烷羧酸酯,香叶醇,香茅醇,柠檬醛,里哪醇,乙酸芳樟酯,紫罗酮,苯基乙醇或它们的混合物。
为了本发明的目的,挥发性的有气味的物质优选具有低于300℃的沸点或沸程。有气味的物质更优选是可挥发的化合物或混合物。有气味的物质特别优选具有低于250℃的沸点或沸程,更优选低于230℃,特别优选低于200℃。
也优选具有高挥发性的有气味的物质。蒸气压可以用作衡量挥发性的手段。为了本发明目的,挥发性的有气味的物质优选具有大于0.001kPa的蒸气压(20℃)。有气味的物质更优选是可挥发的化合物或混合物。有气味的物质特别优选具有大于0.01kPa的蒸气压(20℃),更优选大于0.05kPa的蒸气压(20℃)。有气味的物质特别优选具有大于0.kPa的蒸气压(20℃)。
其中化学反应可以在本发明金属-有机骨架存在下进行的例子是一元醇和多元醇的烷氧基化反应。进行这种烷氧基化的方法参见WO-A03/035717和WO-A2005/03069。同样,本发明的多孔金属-有机骨架可以用于环氧基化反应和制备聚亚烷基碳酸酯和过氧化氢。这些反应参见WO-A03/101975、WO-A2004/037895和US-A2004/081611。
特别优选的是催化反应。
另外,本发明的金属-有机骨架可以用作载体,尤其是作为用于催化剂的载体。
本发明的被硫浸渍的复合材料尤其适合用作硫电极。
所以,本发明还提供一种含有本发明复合材料的硫电极。
本发明还提供本发明的硫电极在Li-硫电池中的用途,以及提供含有这种硫电极的Li-硫电池。
实施例
实施例1:Al-对苯二甲酸MOF的热解
实验方法:
将20g的Al-MOF(Al-对苯二甲酸MOF:1100m2/g,通过兰格缪尔方法检测)引入熔凝硅石管中。将此管置于管式炉中,并用氮气吹扫过夜。将此管随后在2小时内在氮气流中加热到600℃。在此过程中,将管缓慢旋转(45rpm)。粉末在600℃下热解1小时。在冷却(约1.5小时)之后,从管取出黑色的粉末。
获得的重量:8.7g
分析:
表面积:387m2/g,通过兰格缪尔方法检测
元素分析:Al30重量%
实施例2:用NaOH洗涤经过热解的Al-对苯二甲酸酯
原料:6.47g的来自实施例1的经过热解的材料
100g的10%浓度的氢氧化钠溶液
实验工序
a)合成:来自实施例1的经过热解的材料用氢氧化钠溶液在80℃下在250ml四颈烧瓶中搅拌10小时。
b)处理:将固体在玻璃滤料No.4上在室温下过滤,每次用50ml去离子水搅拌,共搅拌3次,静置5分钟,过滤出来;每次用50ml去离子水洗涤,共洗涤7次。最后,用25ml丙酮搅拌,并吸干。
c)干燥:在真空干燥烘箱中于100℃干燥16小时
颜色:黑色
产率:2.61g
分析:
堆积密度:186g/l
表面积:1620m2/g,通过兰格缪尔方法检测
元素分析:Al0.1重量%;Na0.61重量%
实施例3:用硫负载来自实施例1的材料
将1.0g的来自实施例1的材料和6g硫均匀地混合,并在开放设备中于180℃加热6小时。这得到5.3g的固体的深灰色物质,将其用球磨机研磨成细粉末。
元素分析:
C=6.6重量%
S=83重量%
实施例4:用硫负载来自实施例2的材料
将1.0g的来自实施例2的材料和6g硫均匀地混合,并在开放设备中于180℃加热6小时。这得到5.7g的多孔的深灰色物质,将其用球磨机研磨成细粉末。
元素分析:
C=12.5重量%
S=86重量%
实施例5:生产根据本发明的电化学电池(电极)
将2.30g的来自实施例3或4的材料、0.80g的Super P、0.11g的KS6、0.15g的Celvol粘合剂一起混合。将混合物分散在65%水、30%异丙醇、5%1-甲氧基-2-丙醇的溶剂混合物中。将分散液搅拌10小时。
用刮刀将此分散液施用在铝箔上,并于40℃减压干燥10小时。
实施例6:生产基准电化学电池
将3.310g的硫、2.39g的Super P、0.19g的KS6、0.25g的Celvol粘合剂一起混合。将混合物分散在65%水、30%异丙醇、5%1-甲氧基-2-丙醇的溶剂混合物中。将分散液搅拌10小时。
实施例7:检测根据本发明的电化学电池
为了对复合材料进行电化学表征,建立电化学电池。阳极:Li箔50μm厚,分离器Tonen15μm厚;具有上述复合材料的阴极。电解质:8重量%的LiTFSI(LiN(SO2CF3)2),4重量%的LiNO3,44重量%的二氧戊环,和44重量%的二甲氧基乙烷。
电池的充电和放电是在7.50mA电流下在1.8-2.5的电势范围内进行。电池容量是75.1mAh。结果列在表1中。
表1
Claims (15)
1.一种制备含碳复合材料的方法,此方法包括以下步骤:
(a)使多孔金属-有机骨架在保护气体气氛下热解,所述多孔金属-有机骨架含有与至少一种金属离子配位的至少一种至少双齿有机化合物,其中所述至少一种至少双齿有机化合物是不含氮的。
2.根据权利要求1的方法,其中热解在至少500℃的温度下进行。
3.根据权利要求1或2的方法,其中保护气体气氛含有氮气。
4.根据权利要求1-3中任一项的方法,其中至少一种金属离子是选自以下的金属的离子:Mg,Al,Zr,Ti,V,Cr,Mo,Fe,Co,Cu,Ni,以及Zn。
5.根据权利要求1-4中任一项的方法,其中不含氮的至少一种至少双齿有机化合物是衍生自二羧酸、三羧酸或四羧酸。
6.根据权利要求1-5中任一项的方法,其中还包括步骤:
(b)从在步骤(a)中获得的复合材料至少部分地除去一种或多种金属组分。
7.根据权利要求6的方法,其中一种或多种金属组分含有至少一种金属氧化物。
8.根据权利要求6或7的方法,其中至少部分地除去的操作是通过用碱性或酸性液体洗涤出去进行的。
9.根据权利要求1-8中任一项的方法,其中还包括步骤:
(c)将从步骤(a)或(b)获得的复合材料用硫浸渍。
10.根据权利要求9的方法,其中浸渍是通过混合和随后加热进行的。
11.根据权利要求9或10的方法,其中硫用作固体或以溶液的形式使用。
12.一种复合材料,其可以通过根据权利要求1-11中任一项的方法获得。
13.可通过根据权利要求1-11中任一项的方法获得的复合材料用于吸收至少一种物质的用途,以用于所述至少一种物质的储存、去除、受控释放、化学反应的目的,或用作载体。
14.一种硫电极,其含有可通过根据权利要求9-11中任一项的方法获得的复合材料。
15.权利要求14的硫电极在Li-硫电池中的用途。
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CA2809928A1 (en) | 2012-03-08 |
BR112013004984A2 (pt) | 2016-05-31 |
WO2012028989A1 (en) | 2012-03-08 |
EP2611766A1 (en) | 2013-07-10 |
JP2013537877A (ja) | 2013-10-07 |
AU2011298030A1 (en) | 2013-03-21 |
MX2013002219A (es) | 2013-06-03 |
KR20130101038A (ko) | 2013-09-12 |
RU2013114186A (ru) | 2014-10-10 |
TW201223962A (en) | 2012-06-16 |
EP2611766A4 (en) | 2014-04-30 |
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