CN107936247B - Insoluble salt and polyimide aerogel composite photocatalyst and preparation method thereof - Google Patents
Insoluble salt and polyimide aerogel composite photocatalyst and preparation method thereof Download PDFInfo
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- CN107936247B CN107936247B CN201711193341.5A CN201711193341A CN107936247B CN 107936247 B CN107936247 B CN 107936247B CN 201711193341 A CN201711193341 A CN 201711193341A CN 107936247 B CN107936247 B CN 107936247B
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- aerogel
- polyimide
- halogen group
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- salt
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 157
- 229920001721 polyimide Polymers 0.000 title claims abstract description 157
- 239000004964 aerogel Substances 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 150000003839 salts Chemical class 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 118
- 125000005843 halogen group Chemical group 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 35
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- 238000000352 supercritical drying Methods 0.000 claims description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 13
- 239000011240 wet gel Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000499 gel Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 claims description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 4
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 238000006303 photolysis reaction Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 3
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- PAPDRIKTCIYHFI-UHFFFAOYSA-N 4-[3,5-bis(4-aminophenoxy)phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC(OC=2C=CC(N)=CC=2)=CC(OC=2C=CC(N)=CC=2)=C1 PAPDRIKTCIYHFI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N mercury(II) nitrate Inorganic materials [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CRWIOTZGUJAUOZ-UHFFFAOYSA-N ethanol;1-methylpyrrolidin-2-one Chemical compound CCO.CN1CCCC1=O CRWIOTZGUJAUOZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 17
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 11
- 239000011147 inorganic material Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 13
- 229910021607 Silver chloride Inorganic materials 0.000 description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000013329 compounding Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- WOYZXEVUWXQVNV-UHFFFAOYSA-N 4-phenoxyaniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1 WOYZXEVUWXQVNV-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 229910003471 inorganic composite material Inorganic materials 0.000 description 5
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 5
- 229940019931 silver phosphate Drugs 0.000 description 5
- 229910000161 silver phosphate Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- QWUSZGIKGARVEC-UHFFFAOYSA-N 4-(4-amino-3-bromophenyl)-2-bromoaniline Chemical group C1=C(Br)C(N)=CC=C1C1=CC=C(N)C(Br)=C1 QWUSZGIKGARVEC-UHFFFAOYSA-N 0.000 description 2
- IKWZVCLCVMQAMF-UHFFFAOYSA-N 4-(4-amino-3-iodophenyl)-2-iodoaniline Chemical group C1=C(I)C(N)=CC=C1C1=CC=C(N)C(I)=C1 IKWZVCLCVMQAMF-UHFFFAOYSA-N 0.000 description 2
- QYYJDHYBOUCZGR-UHFFFAOYSA-N 6-(4-aminophenyl)cyclohexa-3,5-diene-1,1,3-triamine Chemical compound NC1(N)CC(N)=CC=C1C1=CC=C(N)C=C1 QYYJDHYBOUCZGR-UHFFFAOYSA-N 0.000 description 2
- -1 AgCl and PbBr2 Chemical compound 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical group C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- HQFCOGRKGVGYBB-UHFFFAOYSA-N ethanol;nitric acid Chemical compound CCO.O[N+]([O-])=O HQFCOGRKGVGYBB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/23—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a composite photocatalyst of insoluble salt and polyimide aerogel and a preparation method thereof. Aiming at the problems of composite uniformity, interface heterojunction regulation and control and the like of the existing organic-inorganic composite photocatalytic material, the PI aerogel material and the insoluble salt are compounded together by adopting diversified molecular design, so that the inorganic nano structure in the composite material is uniformly distributed in the PI aerogel, and the PI aerogel and the inorganic nano structure are effectively combined together through heterojunction. The PI/MX composite aerogel catalyst prepared by the method disclosed by the invention has the advantages of ultrahigh specific surface area, high-efficiency adsorption, good stability and recoverability, has the unique properties of inorganic materials, and has good application potential in the aspects of heavy metal adsorption, pollutant degradation and the like.
Description
Technical Field
The invention belongs to the field of preparation of organic-inorganic composite materials, and particularly relates to a composite photocatalyst of insoluble salt and polyimide aerogel and a preparation method thereof.
Background
In recent years, organic-inorganic composite materials have been widely used in various fields of photocatalysis, such as photocatalytic degradation of organic pollutants, photolysis of water to produce ammonia, reduction of carbon dioxide, selective organic synthesis, and the like. AThe organic-inorganic composite materials are mostly concentrated on the conductive polymer and TiO2、ZnO、Fe2O3、Cu2O, etc. For example, Deng et al, introduces polypyrrole and polyaniline into TiO at the same time2In the synthesis of PPy-PANI/TiO2The composite photocatalytic material effectively expands TiO2The visible light absorption range of (2) can efficiently decompose p-nitrophenol under visible light (see: Nanoscale,2013,5, 8703). Some metal-organic composite materials also exhibit good photocatalytic properties, for example, Cu-based porphyrin MOF materials composed of cortex Phellodendri subjects can efficiently reduce carbon dioxide to methanol (see: Mater. Lett.,2016,164,640). The organic phase in the compounds has better performance in the photocatalysis process, but most of the powdery materials are difficult to recycle and have larger loss in the practical application process. The aerogel is used as a solid substance with ultralow density, is convenient to recycle, has ultrahigh specific surface area, adsorptivity and good stability which greatly influence the photocatalytic efficiency, and can be made into devices for industrial production.
Polyimide (PI) aerogels have been explored and developed as superior aerogel materials due to their superior flexibility and adsorption properties. As a novel photocatalyst, the PI polymer is reported to be capable of photodegrading organic pollutants due to high chemical stability, low cost and abundant reserves, and shows great advantages in photocatalysis due to the fact that hydrogen is produced by photodecomposition of water under the irradiation of visible light. If the PI aerogel is used as the organic phase of the organic-inorganic composite photocatalytic material, the following advantages are achieved: (1) the ultrahigh specific surface area can greatly improve the number of active sites, and the good adsorbability can adsorb a large amount of pollutants on the surface of the catalyst in the photocatalysis process, thereby promoting the improvement of the photocatalysis efficiency; (2) the good three-dimensional network structure of the PI aerogel is used as a carrier of an inorganic phase, so that the PI aerogel can be well and uniformly combined with the inorganic phase, more active sites of the inorganic phase can be exposed, and the photocatalytic efficiency can be improved; (3) the PI aerogel solid material is light and flexible, and is expected to be designed and synthesized into a device applied to photocatalysis.
In fact, the performance of the organic-inorganic composite material is not only dependent on the characteristics of each component monomer, but is determined to a greater extent by the interfacial structure and morphology between the organic phase and the inorganic phase. In order to obtain organic-inorganic nanocomposites with desirable morphology, size and interfacial properties, many synthetic methods have been attempted to be developed, including sol-gel methods, self-assembly, intercalation, blending, in-situ polymerization, and the like. The PI organic-inorganic composite material greatly makes up the problems of short service life, low quantum efficiency and poor light energy utilization rate of an active carrier of a single-component PI material, and expands the application range of the PI material. For example, in patent CN 105709831 a, PI is added in the preparation process of silver phosphate to prepare a silver phosphate/polyimide visible light composite photocatalyst, this method cannot realize effective recombination of silver phosphate and polyimide, a heterojunction cannot be formed between the silver phosphate and polyimide, which is not favorable for electron transfer in the photocatalytic process, and a powdery material is not favorable for recycling. Ma et al prepared black-MoO by one-step thermal polymerization3the/PI composite material realizes the compounding of organic-inorganic materials in one step, is beneficial to forming heterojunction between the interfaces of the organic-inorganic materials, exerts the synergistic effect between two semiconductors and improves the utilization rate of visible light, but the method for preparing the core-shell structure in one step after mixing the two precursors cannot regulate and control the uniform distribution and effective contact of the two materials and cannot ensure the uniformity of the composite material (see: ACS appl. mater. interfaces,2015,7, 14628). Recent Ma et al in turn grow MoO in situ3The novel preparation method is favorable for compounding MoO with PI3The nano-particles are uniformly distributed in the polymer, so that the effective contact between the polymer and the polymer is enhanced, and the interaction between the composite materials is further improved, but the simple in-situ growth method lacks regulation and control on the size of an interface heterojunction between the two materials (see: Sol. Energ. Mat. Sol. C.,2016,150,102).
In summary, the preparation method of organic-inorganic composite photocatalytic materials in the prior art still has many problems, and especially some key problems affecting photocatalytic properties are still not solved, mainly including: (1) how to design an experiment to realize effective compounding of the organic-inorganic material and ensure the distribution uniformity among the components of the composite material; (2) how to realize effective contact among all components and regulation and control of heterojunction; these problems are crucial to the transfer of electrons and the improvement of photocatalytic efficiency in photocatalytic processes. Therefore, there is a need for an organic-inorganic composite photocatalyst and a method for preparing the same that can overcome the above problems.
Disclosure of Invention
Aiming at the problems that organic-inorganic materials cannot be effectively compounded, the distribution of components of the composite materials is not uniform, the components cannot be effectively contacted and heterojunction cannot be effectively regulated in the preparation of the organic-inorganic material photocatalyst in the prior art, the invention aims to provide the composite photocatalyst of the insoluble salt and the Polyimide (PI) and the preparation method thereof.
The invention aims to provide a preparation method of polyimide aerogel containing halogen groups X.
The invention also aims to provide a preparation method of the composite photocatalyst of the insoluble salt and the polyimide aerogel.
The invention also aims to provide a composite photocatalyst of insoluble salt and polyimide aerogel.
The invention also aims to provide the composite photocatalyst of the insoluble salt and the polyimide aerogel and an application of the preparation method.
In order to achieve the above purpose, the invention specifically discloses the following technical scheme:
firstly, the invention discloses a preparation method of polyimide aerogel containing halogen groups X, which comprises the following steps:
1) carrying out organic substitution reaction on the intermediate under the condition of a catalyst to obtain a monomer containing a halogen group X;
2) dissolving the monomer containing the halogen group X in the step 1) in an organic solvent to obtain a mixed solution, then adding diamine or dianhydride into the mixed solution, stirring and dissolving, quickly adding a cross-linking agent, stirring uniformly, then sequentially adding acetic anhydride and pyridine, and performing chemical imidization to obtain polyimide wet gel containing the halogen group X;
3) aging the polyimide moisture gel obtained in the step 2) in an ethanol solution, and then obtaining polyimide aerogel containing halogen groups X by using an ethanol supercritical drying method;
4) preparing the polyimide aerogel containing the halogen group X prepared in the step 3) into a sheet to obtain the halogen-containing polyimide aerogel.
In the step 1), the intermediate comprises o-nitrochlorobenzene, o-nitrobromobenzene and o-nitroiodobenzene.
In step 1), the catalyst comprises: NaOH/CH2O、N2H4、HCl/HBr/HI。
In the step 1), the mass-to-volume ratio (g/mL) of the intermediate to the catalyst is 1-3: 5.
in step 1), the halogen group X is: cl, Br and I elements.
Preferably, the halogen group X is a Cl element.
In step 2), the organic solvent includes N-methylpyrrolidone (NMP).
In the step 2), the mass-to-volume ratio of the diamine or dianhydride to the organic solvent is 1-3: 10 to 15.
In step 2), the diamine comprises: 2, 2-Diaminobenzidine (DMBZ), p-phenylenediamine (PPDA), 4-diaminodiphenyl ether (ODA).
In step 2), the dianhydride comprises: biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), diphenyl ether tetracarboxylic dianhydride (ODPA).
In the step 2), the cross-linking agent is 1,3, 5-tri (4-aminophenoxy) benzene.
In the step 2), the volume ratio of the cross-linking agent to the organic solvent is 1-3: 5.
in the step 2), the volume ratio of the acetic anhydride to the pyridine to the organic solvent is 1: 1: 5 to 10.
In the step 3), the aging treatment includes that ① is used for gelling and aging the polyimide moisture gel for 3 hours, then the polyimide moisture gel is soaked in 50-75% N-methylpyrrolidone (NMP) ethanol solution for 18-24 hours, ② is used for soaking ① medium-humidity aerogel in 10-25% NMP ethanol solution for 20-24 hours, and ③ is used for aging ② medium-humidity aerogel in the ethanol solution for 24 hours.
In the step 3), the ethanol supercritical drying method comprises the following steps: performing ethanol supercritical drying at 536-600K, 6.6-10 MPa and 80-100 ℃/min of temperature rise speed.
In the step 4), the thickness of the aerogel sheet is 1-5 mm.
The invention further discloses a preparation method of the insoluble salt and polyimide aerogel composite photocatalyst, and the method comprises the following steps:
(1) the polyimide moisture gel sheet containing the halogen group X prepared by the invention is taken as a precursor, the precursor is soaked in a soluble salt ethanol solution, and the halogen group X in the precursor reacts with metal cations in the soluble salt to obtain the polyimide composite aerogel containing insoluble salt;
(2) and (2) treating the polyimide composite aerogel containing the insoluble salt obtained in the step (1) by using an ethanol supercritical drying method to form a heterojunction between polyimide and precipitated salt, so as to obtain the insoluble salt and polyimide composite photocatalyst.
In the step (1), the soluble salt is: pb (NO)3)2，AgNO3，Hg(NO3)2。
In the step (1), the mass-to-volume ratio (g/mL) of the precursor to the soluble salt ethanol solution is as follows: 1-3: 10.
in the step (1), the concentration of soluble salt in the soluble salt ethanol solution is 1-2 mol/L.
In the step (1), the reaction time is 1-5 min, and the reaction is carried out at normal temperature.
In the step (2), the ethanol supercritical drying conditions are as follows: the temperature rising speed is 80-120 ℃/min, the heat preservation temperature is 500-600K, the heat preservation time is 2-6 h, and the pressure is 5-8 MPa.
In the steps (1) and (2), the insoluble salt is an inorganic salt which is insoluble in water and is formed by a halogen group X and metal cations Pb, Ag and Hg in the nitrate, such as AgCl and PbBr2、HgI2And the like.
The invention further discloses a composite photocatalyst of the insoluble salt and the polyimide aerogel, wherein the photocatalyst is a photocatalyst formed by compounding the insoluble salt and the polyimide, and the insoluble salt is an inorganic salt which is insoluble in water and formed by a halogen group X and metal cations in the nitrate.
Finally, the invention discloses a preparation method of the polyimide aerogel containing the halogen group X, a composite photocatalyst of the insoluble salt and the polyimide aerogel and application of the preparation method of the composite photocatalyst, wherein the application comprises the steps of photocatalytic degradation of organic pollutants, photolysis of water to prepare ammonia, reduction of carbon dioxide, selective organic synthesis and the like.
The invention is characterized in that: firstly, introducing a halogen group X into a diamine or dianhydride monomer for synthesizing Polyimide (PI) through an organic substitution reaction, and preparing a PI aerogel containing the halogen group X through imidization and a supercritical drying method; the invention firstly introduces halogen group X, and the main reasons are as follows: each of these halogen atoms uniformly distributed in the PI acts like a "hand grip" by which metal cations such as Ag, Pb, Hg, etc. are captured when they come into contact with the halogen atoms, thereby forming a poorly soluble precipitated salt uniformly distributed in the PI. Then, the present invention cuts the prepared PI aerogel containing halogen group X into 1-5mm thick sheets for dipping nitrate ethanol solution, so the method is adopted mainly because: by utilizing the characteristic of low solubility of the insoluble salt (MX), the inorganic insoluble salt formed by precipitation reaction can be uniformly attached to the PI aerogel; although MX can gradually aggregate in the aerogel to form MX particles along with the reaction, the size of the MX particles is limited by the pore size of the aerogel, so that the size of the MX particles can be further regulated and controlled by regulating the pore size of the PI aerogel, and the controllable preparation of the heterojunction is realized. Finally, through ethanol supercritical treatment, the structure and the morphology of the insoluble salt and polyimide (PI/MX) composite aerogel are maintained, a heterojunction can be formed between a PI interface and a MX interface through high temperature in the ethanol supercritical treatment process, effective compounding between the PI interface and the MX interface is realized, the composite material is high in photocatalytic efficiency and extremely stable in property, silver ions are not easily reduced into simple substance silver by photo-generated electrons generated by photocatalysis, and the composite material is more suitable for industrial application compared with a silver phosphate/polyimide composite photocatalyst. It should be noted that: the PI/MX composite aerogel catalyst prepared by the method disclosed by the invention has the advantages of ultrahigh specific surface area, high-efficiency adsorbability, good stability and recoverability, and also has some unique properties of inorganic materials, such as high-efficiency catalytic degradation capability of an AgX plasma catalyst, and better synergistic effect of AgX and PI after compounding, so that the material has multifunction, high efficiency and durability in the aspect of sewage treatment. More importantly, the PI aerogel used as a carrier material is light in weight and excellent in flexibility, so that in practical industrial application, the PI aerogel is hopeful to be made into a device to solve a plurality of problems (physical adsorption, chemical degradation, sterilization and disinfection) in sewage at one time, and can be recycled and reused, and the cost is reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) aiming at the problems of composite uniformity, interface heterojunction regulation and control and the like of the existing organic-inorganic composite photocatalytic material, the PI aerogel material and the insoluble salt are compounded together by adopting diversified molecular design, so that inorganic nano structures in the composite material are uniformly distributed in the PI aerogel, and the PI aerogel and the insoluble salt are effectively combined together through heterojunction, so that the PI/MX composite aerogel catalyst prepared by the method has ultrahigh specific surface area and adsorbability, and has good application potential in the aspects of heavy metal adsorption, pollutant degradation and the like.
(2) The specific surface area of the PI aerogel prepared by the method can reach 400-600 m2The pore size distribution is uniform, the average pore diameter is about 40-60 nm, and the ultrahigh specific surface area not only increases the number of exposed photocatalytic active sites, but also is beneficial to adsorbing more pollutants; the uniform pore size distribution can lead the composite inorganic salt particle rulerThe size is more uniform.
(3) The insoluble salt particles in the PI aerogel prepared by the invention are uniform in size and are uniformly distributed in the aperture of the PI aerogel, and through the design of the preparation method and the selection of materials, the problems that the organic-inorganic material cannot be effectively compounded, the distribution of the components of the composite material is not uniform, the components cannot be effectively contacted and the heterojunction cannot be effectively regulated in the preparation of the organic-inorganic material photocatalyst in the prior art are well solved.
Drawings
FIG. 1 is an optical photograph of the polyimide moisture gel obtained in example 1.
FIG. 2 is a specific surface area and pore size distribution curve of the polyimide aerogel obtained in example 1.
FIG. 3 is an SEM photograph of the PI/AgCl aerogel obtained in example 1.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, in the prior art, the problems that the organic-inorganic material cannot be effectively compounded, the distribution of the components of the composite material is not uniform, the components cannot be effectively contacted, and the heterojunction cannot be effectively controlled exist in the preparation of the organic-inorganic material photocatalyst, and in order to solve the problems, the invention provides the composite photocatalyst of the insoluble salt and the polyimide and the preparation method thereof; the present invention will be further described with reference to specific examples.
Example 1:
1. preparation of PI aerogels containing halogen groups Cl
(1) 53g of o-nitrochlorobenzene was mixed with 160mL of NaOH and N catalysts2H4And HCl to obtain 3,3 '-dichloro-4, 4' -diaminobiphenyl as the monomer containing the halogen group Cl.
(2) Dissolving 3.99g of the monomer obtained in the step (1) in 50 mLN-methyl pyrrolidone, and stirring to dissolve to obtain a mixed solution; then 4.79g of biphenyl tetracarboxylic dianhydride is added into the mixed solution to be stirred and dissolved, 16mL of 0.02mol/L1, 3, 5-tri (4-aminophenoxy) benzene is rapidly added, and after uniform stirring, 10.5mL of acetic anhydride and 10.5mL of pyridine are sequentially added to obtain the chlorine-containing PI aerogel.
(3) And (3) gelling and aging the PI aerogel in the step (2) for 3h, soaking the PI aerogel in 75% NMP ethanol solution for 24h, then soaking the PI aerogel in 25% NMP ethanol solution for 24h, and finally aging the PI aerogel in the ethanol solution for 24h to obtain the PI wet gel containing the halogen group Cl.
(4) And (4) carrying out ethanol supercritical drying on the wet gel obtained in the step (3) under the conditions of 536K temperature, 6.6MPa pressure and 100 ℃/min heating rate, keeping the temperature for 5h to obtain the PI aerogel containing the halogen group Cl, and cutting the aerogel into slices with the thickness of 2mm for later use.
2. Preparation of PI/AgCl composite aerogel
1g of PI aerogel sheet containing a halogen group Cl prepared by the above method was immersed in 30mL of 1mol/L AgNO3Taking out the composite material after 2min in an ethanol solution to obtain a PI/AgCl composite material, and then performing ethanol supercritical drying on the composite material at the temperature rise speed of 100 ℃/min, the temperature of 536K, the pressure of 6.6MPa and the heat preservation time of 5h to obtain PI/AgCl composite aerogel; the ethanol supercritical drying conditions are as follows: the heating speed is 80 ℃/min, the heat preservation temperature is 500K, the heat preservation time is 6h, and the pressure is 8 MPa.
FIG. 1 is an optical photograph of the PI wet/aerogel prepared in this example; FIG. 2 is a plot of the specific surface area and pore size distribution of the PI aerogel prepared in this example; fig. 3 is an SEM image of the PI/AgCl composite aerogel, and it can be seen that the AgCl particle size is 40 ± 5nm, the size is uniform, and the AgCl particle size is uniformly distributed in the PI aerogel, and the uniform distribution of the AgCl particle size and the AgCl particle size is favorable for effective transmission of electrons in the photocatalytic process, thereby providing photocatalytic efficiency.
Example 2
1. Preparation of PI aerogel containing halogen group Br
(1) 50g of o-nitrobromobenzene is reacted with 150mL of catalyst CH2O、N2H4And HBr to obtain 3,3 '-dibromo-4, 4' -diaminobiphenyl as the monomer containing the halogen group Br.
(2) Dissolving 3.99g of the monomer obtained in the step (1) in 50 mLN-methyl pyrrolidone (NMP), and stirring to dissolve to obtain a mixed solution; then 5g of pyromellitic dianhydride is added into the mixed solution to be stirred and dissolved, 10mL of 0.02mol/L1, 3, 5-tri (4-aminophenoxy) benzene is rapidly added, and after uniform stirring, 10mL of acetic anhydride and 10mL of pyridine are sequentially added to obtain the chlorine-containing PI aerogel.
(3) And (3) gelling and aging the PI aerogel in the step (2) for 3h, soaking the PI aerogel in 75% NMP ethanol solution for 24h, then soaking the PI aerogel in 25% NMP ethanol solution for 24h, and finally aging the PI aerogel in the ethanol solution for 24h to obtain the PI wet gel containing the halogen group Br.
(4) And (4) carrying out ethanol supercritical drying on the wet gel obtained in the step (3) under the conditions of temperature of 600K, pressure of 10MPa and heating rate of 80 ℃/min, and keeping the temperature for 5h to obtain the PI aerogel containing the halogen group Br, and cutting the aerogel into slices with the thickness of 1mm for later use.
2. Preparation of PI/AgBr composite aerogel
3g of PI aerogel sheet containing halogen group Br prepared by the method is soaked in 10mL of AgNO with the concentration of 2mol/L3Taking out the composite material after 1min in an ethanol solution to obtain a PI/AgBr composite material, and then performing ethanol supercritical drying on the composite material at the temperature rise speed of 80 ℃/min, the temperature of 500K, the pressure of 5MPa and the heat preservation time of 5h to prepare PI/AgBr composite aerogel; the ethanol supercritical drying conditions are as follows: the rate of temperature rise is120 ℃/min, the heat preservation temperature is 600K, the heat preservation time is 2h, and the pressure is 5 MPa.
Example 3
1. Preparation of PI aerogels containing halogen groups I
(1) 50g of o-nitroiodobenzene and 250mL of catalyst NaOH and N2H4HI reaction to obtain 3,3 '-diiodo-4, 4' -diaminobiphenyl as a monomer containing a halogen group I.
(2) Dissolving 3.99g of the monomer obtained in the step (1) in 75 mLN-methyl pyrrolidone (NMP), and stirring to dissolve to obtain a mixed solution; then 5g of diphenyl ether tetracarboxylic dianhydride is added into the mixed solution to be stirred and dissolved, 15mL of 0.02 mol/L1, 3, 5-tri (4-aminophenoxy) benzene is rapidly added, and after uniform stirring, 7.5mL of acetic anhydride and 7.5mL of pyridine are sequentially added to obtain the chlorine-containing PI aerogel.
(3) And (3) gelling and aging the PI aerogel in the step (2) for 3h, soaking the PI aerogel in an ethanol solution of 50% NMP for 18h, then soaking the PI aerogel in an ethanol solution of 10% NMP for 20h, and finally aging the PI aerogel in the ethanol solution for 24h to obtain the PI wet gel containing the halogen group I.
(4) And (4) carrying out ethanol supercritical drying on the wet gel obtained in the step (3) under the conditions of 560K temperature, 8MPa pressure and 90 ℃/min heating speed, keeping the temperature for 5h to obtain PI aerogel containing Cl, and cutting the aerogel into slices with the thickness of 5mm for later use.
2、PI/HgI2Preparation of composite aerogels
3g of PI aerogel sheet containing a halogen group Br prepared by the above method was immersed in 10mL of 1mol/L Hg (NO)3)2Taking out the mixture after 4min in an ethanol solution to obtain PI/PbI2Performing ethanol supercritical drying on the composite material at the temperature rise speed of 80 ℃/min, the temperature of 550K, the pressure of 7MPa and the heat preservation time of 5h to obtain PI/HgI2Compounding aerogel; the ethanol supercritical drying conditions are as follows: the heating speed is 100 ℃/min, the heat preservation temperature is 550K, the heat preservation time is 4h, and the pressure is 6 MPa.
Example 4
1. Preparation of PI aerogels containing halogen groups I
(1) 50g of o-nitroiodobenzene and 125mL of catalyst CH2O、N2H4HI reaction to obtain 3,3 '-diiodo-4, 4' -diaminobiphenyl as a monomer containing a halogen group I.
(2) Dissolving 3.99g of the monomer obtained in the step (1) in 75 mLN-methyl pyrrolidone (NMP), and stirring to dissolve to obtain a mixed solution; then 22.5g of 2, 2-diaminobenzidine is added into the mixed solution and stirred to be dissolved, 30mL of 0.02 mol/L1, 3, 5-tri (4-aminophenoxy) benzene is rapidly added, and after uniform stirring, 9mL of acetic anhydride and 9mL of pyridine are sequentially added to obtain the chlorine-containing PI aerogel.
(3) And (3) gelling and aging the PI aerogel in the step (2) for 3h, soaking the PI aerogel in an ethanol solution of 60% NMP for 20h, then soaking the PI aerogel in an ethanol solution of 15% NMP for 22h, and finally aging the PI aerogel in the ethanol solution for 24h to obtain the PI wet gel containing the halogen group I.
(4) And (4) carrying out ethanol supercritical drying on the wet gel obtained in the step (3) under the conditions of temperature of 580K, pressure of 7MPa and heating speed of 85 ℃/min, and keeping the temperature for 5h to obtain PI aerogel containing Cl, and cutting the aerogel into slices with the thickness of 3mm for later use.
2. Preparation of PI/AgI composite aerogel
3g of PI aerogel sheet containing halogen group Br prepared by the method is soaked in 10mL of 1mol/L AgNO3Taking out the composite material after 4min in an ethanol solution to obtain a PI/AgI composite material, and then performing ethanol supercritical drying on the composite material at the temperature rising speed of 80 ℃/min, the temperature of 580K, the pressure of 7MPa and the heat preservation time of 5h to prepare PI/AgI composite aerogel; the ethanol supercritical drying conditions are as follows: the heating speed is 110 ℃/min, the heat preservation temperature is 530K, the heat preservation time is 5h, and the pressure is 6 MPa.
Example 5
1. Preparation of PI aerogel containing halogen group Br
(1) 50g of o-nitrobromobenzene is mixed with 150mL of catalyst NaOH and N2H4And HBr to obtain 3,3 '-dibromo-4, 4' -diaminobiphenyl as the monomer containing the halogen group Br.
(2) Dissolving 3.99g of the monomer obtained in the step (1) in 50 mLN-methyl pyrrolidone (NMP), and stirring to dissolve to obtain a mixed solution; then adding 10g of p-phenylenediamine into the mixed solution, stirring and dissolving, quickly adding 10mL of 0.02mol/L1, 3, 5-tri (4-aminophenoxy) benzene, stirring uniformly, and then sequentially adding 12mL of acetic anhydride and 10mL of pyridine to obtain the chlorine-containing PI aerogel.
(3) And (3) gelling and aging the PI aerogel in the step (2) for 3h, soaking the PI aerogel in 75% NMP ethanol solution for 24h, then soaking the PI aerogel in 25% NMP ethanol solution for 24h, and finally aging the PI aerogel in the ethanol solution for 24h to obtain the PI wet gel containing the halogen group Br.
(4) And (4) carrying out ethanol supercritical drying on the wet gel obtained in the step (3) under the conditions of temperature of 600K, pressure of 10MPa and heating rate of 80 ℃/min, and keeping the temperature for 5h to obtain the PI aerogel containing the halogen group Br, and cutting the aerogel into slices with the thickness of 4mm for later use.
2、PI/PbBr2Preparation of composite aerogels
3g of PI aerogel sheet containing halogen group Br prepared by the above method was immersed in 10mL of 1.5mol/L Pb (NO)3)2Taking out the solution after 4min to obtain PI/PbBr2The composite material is subjected to ethanol supercritical drying at the temperature rising speed of 80 ℃/min, the temperature of 580K, the pressure of 7MPa and the heat preservation time of 5h to prepare PI/PbBr2Compounding aerogel; the ethanol supercritical drying conditions are as follows: the heating speed is 90 ℃/min, the heat preservation temperature is 580K, the heat preservation time is 3h, and the pressure is 7 MPa.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of polyimide aerogel containing halogen groups X is characterized by comprising the following steps: the method comprises the following steps:
1) carrying out organic substitution reaction on the intermediate under the condition of a catalyst to obtain a monomer containing a halogen group X;
2) dissolving the monomer containing the halogen group X in the step 1) in an organic solvent to obtain a mixed solution, then adding dianhydride into the mixed solution, stirring and dissolving, quickly adding a cross-linking agent, stirring uniformly, then sequentially adding acetic anhydride and pyridine, and performing chemical imidization to obtain polyimide wet gel containing the halogen group X;
3) aging the polyimide moisture gel obtained in the step 2) in an ethanol solution, and then obtaining polyimide aerogel containing halogen groups X by using an ethanol supercritical drying method;
4) preparing the polyimide aerogel containing the halogen group X prepared in the step 3) into a sheet to obtain the halogen-containing polyimide aerogel;
the intermediate is o-nitrochlorobenzene, o-nitrobromobenzene or o-nitroiodobenzene;
the catalyst is NaOH/CH2O、N2H4A mixture of HCl/HBr/HI.
2. The method for preparing a polyimide aerogel containing a halogen group X as claimed in claim 1, wherein: in the step 1), the step (A) is carried out,
the mass-volume ratio g/mL of the intermediate to the catalyst is 1-3: 5;
the halogen group X is: cl, Br and I elements.
3. The method for preparing a polyimide aerogel containing a halogen group X as claimed in claim 2, wherein: in the step 2), the cross-linking agent is 1,3, 5-tri (4-aminophenoxy) benzene;
the organic solvent comprises N-methyl pyrrolidone;
the dianhydride is: biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, diphenyl ether tetracarboxylic dianhydride.
4. The method for preparing a polyimide aerogel containing halogen groups X as claimed in claim 3, wherein: in the step 2), the mass-to-volume ratio g/mL of the dianhydride to the organic solvent is 1-3: 10-15;
the volume ratio of the cross-linking agent to the organic solvent is 1-3: 5;
the volume ratio of the acetic anhydride to the pyridine to the organic solvent is 1: 1: 5 to 10.
5. The method for preparing polyimide aerogel containing halogen groups X as claimed in any one of claims 1 to 4, wherein in the step 3), the aging treatment is carried out by ① gelling and aging the polyimide moisture gel for 3h, soaking the gel in 50-75% N-methylpyrrolidone ethanol solution for 18-24 h, soaking ② in 10-25% NMP ethanol solution for ① medium wet aerogel for 20-24 h, and aging ③ medium wet aerogel ② in ethanol solution for 24 h;
the ethanol supercritical drying method comprises the following steps: performing ethanol supercritical drying at 536-600K, 6.6-10 MPa and 80-100 ℃/min of temperature rise speed.
6. A preparation method of a composite photocatalyst of insoluble salt and polyimide aerogel is characterized by comprising the following steps: the method comprises the following steps:
(1) taking the polyimide moisture gel sheet containing the halogen group X prepared by the method of claim 1 as a precursor, soaking the precursor into a soluble salt ethanol solution, and reacting the halogen group X in the precursor with metal cations in the soluble salt to obtain a polyimide composite aerogel containing insoluble salt;
(2) and (2) treating the polyimide composite aerogel containing the insoluble salt obtained in the step (1) by using an ethanol supercritical drying method to form a heterojunction between polyimide and precipitated salt, so as to obtain the insoluble salt and polyimide composite photocatalyst.
7. The method for preparing the difficult-soluble salt and polyimide aerogel composite photocatalyst as claimed in claim 6, wherein the method comprises the following steps: in the step (1), the mass-to-volume ratio g/mL of the precursor to the soluble salt ethanol solution is 1-3: 10;
the soluble salt is: pb (NO)3)2，AgNO3，Hg(NO3)2；
The concentration of soluble salt in the soluble salt ethanol solution is 1-2 mol/L; the reaction time is 1-5 min, and the reaction is carried out at normal temperature.
8. The method for preparing the difficult-soluble salt and polyimide aerogel composite photocatalyst as claimed in claim 6, wherein the method comprises the following steps: in the step (2), the ethanol supercritical drying conditions are as follows: the temperature rising speed is 80-120 ℃/min, the heat preservation temperature is 500-600K, the heat preservation time is 2-6 h, and the pressure is 5-8 MPa.
9. The method for preparing the difficult-soluble salt and polyimide aerogel composite photocatalyst as claimed in claim 6, wherein the method comprises the following steps: in the steps (1) and (2), the insoluble salt is an inorganic salt which is insoluble in water and is formed by the halogen group X and metal cations Pb, Ag and Hg in the soluble salt.
10. Use of the preparation method of the polyimide aerogel containing halogen groups X as described in any one of claims 1 to 4 and/or the preparation method of the composite photocatalyst of the insoluble salt and the polyimide aerogel as described in any one of claims 6 to 9 in photocatalytic degradation of organic pollutants, photolysis of water to produce ammonia, reduction of carbon dioxide and selective organic synthesis.
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| CN104693477A (en) * | 2015-03-30 | 2015-06-10 | 上海大音希声新型材料有限公司 | Preparation method for crosslinking type polyimide aerogel |
| CN105968354A (en) * | 2016-05-30 | 2016-09-28 | 南京工业大学 | Preparation method of polyimide aerogel for CO2 adsorption |
| CN106311356A (en) * | 2016-08-12 | 2017-01-11 | 山东省科学院新材料研究所 | Silver halide-titanium silicon aerogel ternary composite photocatalyst and preparation method thereof |
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| CN105968354A (en) * | 2016-05-30 | 2016-09-28 | 南京工业大学 | Preparation method of polyimide aerogel for CO2 adsorption |
| CN106311356A (en) * | 2016-08-12 | 2017-01-11 | 山东省科学院新材料研究所 | Silver halide-titanium silicon aerogel ternary composite photocatalyst and preparation method thereof |
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