CN107936247A - A kind of difficulty soluble salt and polyimide aerogels composite photo-catalyst and preparation method thereof - Google Patents
A kind of difficulty soluble salt and polyimide aerogels composite photo-catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN107936247A CN107936247A CN201711193341.5A CN201711193341A CN107936247A CN 107936247 A CN107936247 A CN 107936247A CN 201711193341 A CN201711193341 A CN 201711193341A CN 107936247 A CN107936247 A CN 107936247A
- Authority
- CN
- China
- Prior art keywords
- soluble salt
- halogen group
- preparation
- catalyst
- polyimide aerogels
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004642 Polyimide Substances 0.000 title claims abstract description 135
- 229920001721 polyimide Polymers 0.000 title claims abstract description 135
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 150000003839 salts Chemical class 0.000 title claims abstract description 58
- 239000004964 aerogel Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 108
- 125000005843 halogen group Chemical group 0.000 claims description 57
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 36
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000000352 supercritical drying Methods 0.000 claims description 24
- 230000001699 photocatalysis Effects 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 14
- 239000000499 gel Substances 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000011240 wet gel Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 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 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-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
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- JXMZUNPWVXQADG-UHFFFAOYSA-N 1-iodo-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1I JXMZUNPWVXQADG-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 101100074988 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) nmp-1 gene Proteins 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 235000011194 food seasoning agent Nutrition 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 14
- 239000011147 inorganic material Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 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 compound 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 compound C1=C(I)C(N)=CC=C1C1=CC=C(N)C(I)=C1 IKWZVCLCVMQAMF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound 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
- QYYJDHYBOUCZGR-UHFFFAOYSA-N 6-(4-aminophenyl)cyclohexa-3,5-diene-1,1,3-triamine Chemical class NC1(N)CC(N)=CC=C1C1=CC=C(N)C=C1 QYYJDHYBOUCZGR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 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
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004332 silver 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
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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 present invention relates to a kind of difficulty soluble salt and polyimide aerogels composite photo-catalyst and preparation method thereof.The problems such as present invention regulates and controls for compound uniformity existing for current organo-mineral complexing catalysis material and interface hetero-junctions, PI aerogel materials are combined with each other with difficulty soluble salt using the MOLECULE DESIGN of diversification, inorganic nanostructures in composite material are made to be evenly distributed in PI aeroges, the two is effectively combined together by hetero-junctions.The PI/MX composite aerogel catalysts being prepared by the method for the present invention both had had specific surface area, efficient adsorptivity, good stability, the recuperability of superelevation, also there is the peculiar property of inorganic material, there is good application potential in heavy metal adsorption, contaminant degradation etc..
Description
Technical field
The invention belongs to organic/inorganic composite material preparation field, and in particular to a kind of difficulty soluble salt and polyimide aerogels
Composite photo-catalyst and preparation method thereof.
Background technology
Composite organic-inorganic material was widely used in the various aspects of photocatalysis field, such as photocatalysis drop in recent years
Solve organic pollution, photocatalytic water ammonia, carbon dioxide reduction, selective organic synthesis etc..General composite organic-inorganic material
It is largely focused on conducting polymer and TiO2、ZnO、Fe2O3、Cu2On the oxide semiconductors such as O.Such as Deng by polypyrrole and
Polyaniline introduces TiO at the same time2In synthesized PPy-PANI/TiO2Composite photocatalyst material, has effectively expanded TiO2Visible ray inhale
Receive scope, under visible light can efficient-decomposition p-nitrophenol (referring to：Nanoscale,2013,5,8703).Some metals-
Organic composite material also shows good photocatalysis performance, such as the Cu base porphyrin MOF materials that Cortex Phellodendri mark problem is combined into
High-efficiency carbon dioxide can be reduced into methanol (referring to：Mater.Lett.,2016,164,640).It is organic in these compounds
The mutually better performances in photocatalytic process, but such dusty material is mostly difficult to recycle, and is damaged in actual application
Consume larger.And aeroge not only facilitates and recycles, also have to photocatalysis as a kind of solid matter with extremely-low density
Efficiency influences great superhigh specific surface area, adsorptivity and good stability, and flexible aeroge may also be fabricated which device
For in industrialized production.
Polyimides (PI) aeroge is because of the pliability and adsorptivity of superelevation at present, as the outstanding person in aeroge, its
Performance is constantly being explored exploitation.PI polymer is as a kind of novel photocatalyst, due to higher chemical stability, cost
Low and abundant reserves, being reported can be with light degradation organic pollution, and under visible light illumination, photodegradation water system
Hydrogen, shows great advantage in terms of photocatalysis.If using PI aeroges having as Organic-inorganic composite catalysis material
Machine phase, has the following advantages：(1) specific surface area of superelevation can be greatly enhanced the quantity of avtive spot, and good adsorptivity exists
Largely absorption pollutant has facilitation in catalyst surface, the raising to photocatalysis efficiency in photocatalytic process；(2) PI gas
Carrier of the good three-dimensional net structure of gel as inorganic phase, can preferably realize and be combined with the uniform of inorganic phase, favorably
In the more avtive spots of exposure inorganic phase, photocatalysis efficiency is improved；(3) PI aeroges solid material is light, flexible, is expected to set
Count device of the synthesis application in terms of photocatalysis.
In fact, the performance of composite organic-inorganic material is not merely to rely on the characteristic of each component monomer in itself, bigger journey
It is to be determined by the interfacial structure between organic phase and inorganic phase and pattern on degree.There is preferable pattern, size in order to obtain
With the organic-inorganic nanocomposite of interface performance, people attempt to develop many synthetic methods, including sol-gel process,
Self assembly, graft process, blending method, situ aggregation method etc..PI composite organic-inorganic materials, greatly compensate for the PI of one pack system
The problem of material activity carrier lifetime is short, quantum efficiency is low, the efficiency of light energy utilization is poor, has expanded the application range of PI materials.Such as
105709831 A of patent CN, by adding PI in the preparation process of silver orthophosphate, that silver orthophosphate/polyimides is prepared is visible
Photoreactivation photochemical catalyst, the method can not realize the effective compound of silver orthophosphate and polyimides, can not be formed therebetween different
Matter knot is unfavorable for the transfer of electronics in photocatalytic process, and dusty material is unfavorable for recycling.Ma etc. passes through step heat
Polymerization methods are prepared for black-MoO3/ PI composite materials, a step realize the compound of organic-inorganic material, are conducive to the two
Hetero-junctions is formed between interface, the cooperative effect played between two kinds of semiconductors improves visible light utilization efficiency, but this by two
Kind of presoma, which mixes the method that latter step prepares core shell structure, can not regulate and control being uniformly distributed and effectively contacting for two kinds of materials, nothing
Method ensure composite material homogeneity (referring to：ACS Appl.Mater.Interfaces,2015,7,14628).Recent Ma etc.
Further through growth in situ by MoO3It is combined with each other with PI, this innovative preparation method is conducive to MoO3It is evenly distributed on poly-
In compound, effective contact therebetween is enhanced, further increases the interaction between composite material, but simple
In situ synthesis between two kinds of materials interface hetero-junctions size lack regulation and control (referring to：Sol.Energ.Mat.Sol.C.,
2016,150,102)。
In conclusion Organic-inorganic composite catalysis material preparation method still has many problems in the prior art, especially
It is that some critical problems for influencing photocatalysis property are not resolved yet, is mainly included：(1) how contrived experiment, which is realized, has
Machine-inorganic material it is effective compound, and ensure the distributing homogeneity between composite material each component；(2) how each component is realized
Between effective contact and the regulation and control to hetero-junctions；Transfer and photocatalysis efficiency of these problems to electronics in photocatalytic process
Improve most important.Therefore, there is an urgent need for a kind of composite organic-inorganic material photocatalysis that can overcome the above problem and its preparation side
Method.
The content of the invention
Can not be effective for organic-inorganic material in the preparation of the above-mentioned photochemical catalyst of organic-inorganic material in the prior art
Can not effectively it be contacted between skewness, each component between compound, composite material each component and can not be effective to hetero-junctions
The problem of regulation and control, the present invention is intended to provide a kind of difficulty soluble salt and polyimides (PI) composite photo-catalyst and preparation method thereof, with
The prior art is compared, and the present invention can be such that difficulty soluble salt is evenly distributed in PI aeroges, makes closely to tie with hetero-junctions therebetween
It is combined, the size that the inorganic indissoluble salt particle to being distributed in polyimides is realized by adjusting experiment parameter regulates and controls.
An object of the present invention is to provide a kind of preparation method of the polyimide aerogels containing halogen group X.
The second object of the present invention is to provide the preparation side of a kind of difficulty soluble salt and polyimide aerogels composite photo-catalyst
Method.
The third object of the present invention is to provide a kind of difficulty soluble salt and polyimide aerogels composite photo-catalyst.
The fourth object of the present invention is to provide above-mentioned difficulty soluble salt and polyimide aerogels composite photo-catalyst and its preparation
The application of method.
For achieving the above object, specifically, the invention discloses following technical scheme：
First, the invention discloses a kind of preparation method of the polyimide aerogels containing halogen group X, the method
Include the following steps：
1) intermediate is obtained into the monomer containing halogen group X under catalysts conditions by organic substitution reaction；
2) monomer containing halogen group X in step 1) is dissolved in organic solvent and obtains mixed solution, then by two
In amine or the above-mentioned mixed solution of dianhydride addition after stirring and dissolving, crosslinking agent is rapidly added, vinegar is sequentially added after stirring evenly
Acid anhydrides and pyridine, by chemical imidization, obtain the polyimides wet gel containing halogen group X；
3) after burin-in process, ethanol is recycled to surpass in ethanol solution the polyimides moisture gel obtained in step 2)
Critical seasoning obtains the polyimide aerogels containing halogen group X；
4) polyimide aerogels containing halogen group X that obtain prepared in step 3) are laminated, to obtain the final product.
In step 1), the intermediate includes o-nitrochlorobenzene, nitro bromobenzene, adjacent nitro iodobenzene.
In step 1), the catalyst includes：NaOH/CH2O、N2H4、HCl/HBr/HI。
In step 1), the mass volume ratio (g/mL) of the intermediate and catalyst is 1~3：5.
In step 1), the halogen group X is：Cl, Br, I element.
Preferably, the halogen group X is Cl elements.
In step 2), the organic solvent includes 1-methyl-2-pyrrolidinone (NMP).
In step 2), the mass volume ratio of the diamines or dianhydride and organic solvent is 1~3：10~15.
In step 2), the diamines includes：2,2- diaminobenzidines (DMBZ), p-phenylenediamine (PPDA), 4,4- diaminos
Yl diphenyl ether (ODA).
In step 2), the dianhydride includes：Biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic acid anhydride (PMDA), hexichol
Ether tetracarboxylic dianhydride (ODPA).
In step 2), the crosslinking agent is 1,3,5- tri- (4- amino-benzene oxygens) benzene.
In step 2), the volume ratio of the crosslinking agent and organic solvent is 1~3：5.
In step 2), the acetic anhydride, pyridine, the volume ratio of organic solvent are 1：1：5~10.
In step 3), the burin-in process refers to：1. by after polyimides moisture gel gelling aging 3h with 50~75%N-
18~24h of alcohol solution dipping of methyl pyrrolidone (NMP)；2. with the alcohol solution dipping of 10~25%NMP 1. middle moisture
20~24h of gel；3. will 2. middle moisture gel aging 24h in ethanol solution.
In step 3), the ethanol supercritical drying method refers to：In 536~600K of temperature, 6.6~10MPa of pressure, heating speed
Spend to carry out ethanol supercritical drying under the conditions of 80~100 DEG C/min.
In step 4), the thickness of the aeroge thin slice is 1~5mm.
Secondly, the invention discloses the preparation method of a kind of difficulty soluble salt and polyimide aerogels composite photo-catalyst, institute
The method of stating includes the following steps：
(1) the polyimides moisture gel slice containing halogen group X prepared using the present invention is presoma, before described
Drive body and be dipped into soluble salt ethanol solution, the halogen group X in presoma is reacted with the metal cation in soluble salt, is contained
The polyimides composite aerogel of difficulty soluble salt；
(2) the polyimides composite aerogel containing difficulty soluble salt obtained using ethanol supercritical drying method to step (1)
Handled, make to form hetero-junctions between polyimides and deposited salt, up to difficulty soluble salt and polyimides composite photo-catalyst.
In step (1), the soluble salt is：Pb(NO3)2, AgNO3, Hg (NO3)2。
In step (1), the mass volume ratio (g/mL) of the presoma and soluble salt ethanol solution is：1~3：10.
In step (1), the concentration of soluble salt is 1~2mol/L in the soluble salt ethanol solution.
In step (1), the reaction time is 1~5min, and reaction carries out at normal temperatures.
In step (2), the condition of the ethanol supercritical drying is：Programming rate is 80~120 DEG C/min, holding temperature
For 500~600K, soaking time is 2~6h, and pressure is 5~8MPa.
In step (1) and (2), the difficulty soluble salt is metal cation Pb, Ag in halogen group X and above-mentioned nitrate,
The inorganic salts for being insoluble in water that Hg is formed, such as AgCl, PbBr2、HgI2Deng.
Again, the invention discloses a kind of difficulty soluble salt and polyimide aerogels composite photo-catalyst, the catalyst be by
The photochemical catalyst that difficulty soluble salt is combined with polyimides, the difficulty soluble salt are halogen group X and the metal in above-mentioned nitrate
The inorganic salts for being insoluble in water that cation is formed.
Finally, the preparation method the invention discloses the above-mentioned polyimide aerogels containing halogen group X, difficulty soluble salt with
The application of polyimide aerogels composite photo-catalyst and preparation method thereof, the application include being used for the organic dirt of photocatalytic degradation
Contaminate thing, photocatalytic water ammonia, carbon dioxide reduction, selective organic synthesis etc..
The method have the characteristics that：First, halogen group X is incorporated into synthesis polyamides by the present invention by organic substitution reaction
In the diamines or dianhydride monomer of imines (PI), it is prepared by imidizate and supercritical drying containing halogen group X
PI aeroges；The present invention will be firstly introduced into halogen group X, and main cause is：These are evenly distributed on each halogen in PI
Plain atom is all as one " handgrip ", when Ag, Pb, Hg will be caught when metal cation is contacted with halogen atom by these " handgrips "
Obtain, so as to form the slightly solubility deposited salt being evenly distributed in PI.Then, the PI containing halogen group X of the invention by preparation
Aeroge cuts into the thin slice of 1-5mm thickness to impregnate ethanolic nitrate solution, main former why using such method
Because being：Using difficulty soluble salt (MX) solubility it is low the characteristics of, can make generation precipitation reaction formed inorganic difficulty soluble salt uniformly adhere to
In PI aeroges；Although as reaction carry out MX can gradually aggregation forms MX particles in aeroge, but MX particles is big
The small pore size for being limited to aeroge, in this way, the present invention can further be adjusted by adjusting the pore size of PI aeroges
The size of MX particles is controlled, realizes the controllable preparation to hetero-junctions.Finally, handled by Ethanol supercritical, both maintain difficulty soluble salt
With the structure and pattern of polyimides (PI/MX) composite aerogel, and the high temperature in Ethanol supercritical processing procedure can be passed through
Make to form hetero-junctions between PI and MX interfaces, realize therebetween effective compound, this composite material not only photocatalysis efficiency
High and property is extremely stable, and silver ion is not easy to be reduced into elemental silver by the light induced electron of photocatalysis generation, compared to silver orthophosphate/
Polyimides composite photo-catalyst is more suitable for industrial applications.It should be noted that：The PI/MX being prepared by the method for the present invention is answered
Closing aerogel catalyst had both had specific surface area, efficient adsorptivity, good stability, the recuperability of superelevation, also had
Some peculiar properties of inorganic material, as AgX plasma catalysts have efficient catalytic degradation ability, AgX and PI are compound
Cooperative effect can be preferably played afterwards, the material is shown multi-functional, high efficiency and persistence in terms of sewage disposal.
Importantly, the PI aeroges as carrier material, light and flexible fabulous, so in practical application in industry, be expected to by
Such material is made device and disposably solves the problems, such as very much (physical absorption, chemical degradation, sterilizings) in sewage, Er Qieke
Circulating repetition utilizes, and reduces cost.
Compared with prior art, the present invention achieves following beneficial effect：
(1) present invention is for compound uniformity and interface hetero-junctions existing for current Organic-inorganic composite catalysis material
PI aerogel materials, are combined with each other, made in composite material by the problems such as regulation and control using the MOLECULE DESIGN of diversification with difficulty soluble salt
Inorganic nanostructures are evenly distributed in PI aeroges, the two is effectively combined together by hetero-junctions, make preparation of the present invention
PI/MX composite aerogel catalysts have superelevation specific surface area and adsorptivity, heavy metal adsorption, contaminant degradation etc. side
Face has good application potential.
(2) specific surface area of PI aeroges prepared by the present invention can reach 400~600m2/ g, even aperture distribution are average
Bore dia is about 40~60nm, and the specific surface area of superelevation not only increases the quantity in exposed photocatalytic activity site, Er Qieyou
Beneficial to the more pollutants of absorption；Uniform pore-size distribution can make compound inorganic salt particle size more homogeneous.
(3) the difficulty soluble salt particle size in PI aeroges prepared by the present invention is homogeneous, and is evenly distributed on PI aeroges
In aperture, by the design of above-mentioned preparation method and the selection of material, the present invention solves organic-nothing in the prior art well
The skewness that organic-inorganic material can not be between effectively compound, composite material each component in the preparation of machine material light catalysis agent
Can not effectively be contacted between even, each component and to hetero-junctions can not Effective Regulation the problem of.
Brief description of the drawings
Fig. 1 is the optical photograph of 1 gained polyimides moisture gel of embodiment.
Fig. 2 is the specific surface area and pore size distribution curve of 1 gained polyimide aerogels of embodiment.
Fig. 3 is the SEM photograph of 1 gained PI/AgCl aeroges of embodiment.
Embodiment
It is noted that described further below is all illustrative, it is intended to provides further instruction to the application.It is unless another
Indicate, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
As background technology is introduced, in the prior art, there are in the preparation of organic-inorganic material photochemical catalyst
Machine-inorganic material can not be between effectively compound, composite material each component skewness, can not effectively contact between each component
With to hetero-junctions can not Effective Regulation the problem of, to solve the above-mentioned problems, the present invention provides a kind of difficulty soluble salt and polyimides
Composite photo-catalyst and preparation method thereof；With reference to specific embodiment, the present invention is described further.
Embodiment 1：
1st, the preparation of the PI aeroges containing halogen group Cl
(1) by 53g o-nitrochlorobenzenes and catalyst n aOH, N of 160mL2H4, HCl reaction, obtain 3,3'- bis- chloro- 4,4'-
Benzidine, as the monomer containing halogen group Cl.
(2) monomer obtained in 3.99g steps (1) is dissolved in 50mLN- methyl pyrrolidones, stirring and dissolving, is mixed
Close solution；Then 4.79g biphenyl tetracarboxylic dianhydrides are added to stirring and dissolving in above-mentioned mixed solution, and are rapidly added 16mL
The 1 of 0.02mol/L, 3,5- tri- (4- amino-benzene oxygens) benzene, sequentially adds 10.5mL acetic anhydride and 10.5mL after stirring evenly
Pyridine, obtains chloride PI aeroges.
(3) the alcohol solution dipping 24h of 75%NMP will be used after the PI aeroges gelling aging 3h in step (2), then used
The alcohol solution dipping 24h of 25%NMP, finally the aging 24h in ethanol solution, it is wet solidifying to obtain the PI containing halogen group Cl
Glue.
(4) be 536K in temperature by the wet gel obtained in step (3), pressure 6.6MPa, programming rate for 100 DEG C/
Ethanol supercritical drying is carried out under the conditions of min, soaking time 5h, is made the PI aeroges containing halogen group Cl, and will be upper
State aeroge cut into 2mm thickness thin slice it is stand-by.
2nd, the preparation of PI/AgCl composite aerogels
1g prepared by the above method PI aeroge thin slices for containing halogen group Cl are immersed in 30mL 1mol/L's
AgNO3In ethanol solution, taken out after 2min, obtain PI/AgCl composite materials, be then in programming rate by above-mentioned composite material
100 DEG C/min, temperature 536K, pressure 6.6MPa, soaking time are under 5h, carry out ethanol supercritical drying, and PI/ is made
AgCl composite aerogels；The condition of the ethanol supercritical drying is：Programming rate is 80 DEG C/min, holding temperature 500K,
Soaking time is 6h, pressure 8MPa.
Fig. 1 be PI manufactured in the present embodiment it is wet/optical photograph of aeroge；Fig. 2 is PI aeroges manufactured in the present embodiment
Specific surface area and pore size distribution curve；Fig. 3 is the SEM image of PI/AgCl composite aerogels, it can be seen that AgCl granular sizes
For 40 ± 5nm, size ratio is more uniform, and is evenly distributed in PI aeroges, and being uniformly distributed for the two is conducive in photocatalysis
Effective transmission of electronics in journey, and then photocatalysis efficiency is provided.
Embodiment 2
1st, the preparation of the PI aeroges containing halogen group Br
(1) by 50g nitro bromobenzenes and the catalyst CH of 150mL2O、N2H4, HBr reaction, obtain 3,3'- bis- bromo- 4,4'-
Benzidine is as the monomer containing halogen group Br.
(2) monomer obtained in 3.99g steps (1) is dissolved in 50mLN- methyl pyrrolidones (NMP), stirring and dissolving,
Obtain mixed solution；Then 5g pyromellitic acid anhydrides are added to stirring and dissolving in above-mentioned mixed solution, and be rapidly added
The 1 of 10mL0.02mol/L, 3,5- tri- (4- amino-benzene oxygens) benzene, sequentially adds 10mL acetic anhydride and 10mL after stirring evenly
Pyridine, obtains chloride PI aeroges.
(3) the alcohol solution dipping 24h of 75%NMP will be used after the PI aeroges gelling aging 3h in step (2), then used
The alcohol solution dipping 24h of 25%NMP, finally the aging 24h in ethanol solution, it is wet solidifying to obtain the PI containing halogen group Br
Glue.
(4) it is 600K in temperature by the wet gel obtained in step (3), pressure 10MPa, programming rate is 80 DEG C/min
Under the conditions of carry out ethanol supercritical drying, soaking time 5h is made the PI aeroges containing halogen group Br, and by above-mentioned gas
The thin slice that gel cuts into 1mm thickness is stand-by.
2nd, the preparation of PI/AgBr composite aerogels
3g prepared by the above method PI aeroge thin slices for containing halogen group Br are immersed in 10mL 2mol/L's
AgNO3In ethanol solution, taken out after 1min, obtain PI/AgBr composite materials, be then in programming rate by above-mentioned composite material
80 DEG C/min, temperature 500K, pressure 5MPa, soaking time are under 5h, carry out ethanol supercritical drying, and PI/AgBr is made
Composite aerogel；The condition of the ethanol supercritical drying is：Programming rate is 120 DEG C/min, holding temperature 600K, is kept the temperature
Time is 2h, pressure 5MPa.
Embodiment 3
1st, the preparation of the PI aeroges containing halogen group I
(1) by 50g adjacent nitros iodobenzene and catalyst n aOH, N of 250mL2H4, HI reaction, obtain 3,3'- bis- iodo- 4,4'-
Benzidine, as the monomer containing halogen group I.
(2) monomer obtained in 3.99g steps (1) is dissolved in 75mLN- methyl pyrrolidones (NMP), stirring and dissolving,
Obtain mixed solution；Then 5g diphenyl ether tetracarboxylic dianhydrides are added to stirring and dissolving in above-mentioned mixed solution, and be rapidly added
The 1 of 15mL 0.02mol/L, 3,5- tri- (4- amino-benzene oxygens) benzene, sequentially added after stirring evenly 7.5mL acetic anhydride and
7.5mL pyridines, obtain chloride PI aeroges.
(3) the alcohol solution dipping 18h of 50%NMP will be used after the PI aeroges gelling aging 3h in step (2), then used
The alcohol solution dipping 20h of 10%NMP, finally the aging 24h in ethanol solution, obtains the PI wet gels containing halogen group I.
(4) it is 560K in temperature by the wet gel obtained in step (3), pressure 8MPa, programming rate is 90 DEG C/min
Under the conditions of carry out ethanol supercritical drying, soaking time 5h, is made the PI aeroges containing Cl, and above-mentioned aeroge is cut
Thin slice into 5mm thickness is stand-by.
2、PI/HgI2The preparation of composite aerogel
3g prepared by the above method PI aeroge thin slices for containing halogen group Br are immersed in the Hg of 10mL 1mol/L
(NO3)2In ethanol solution, taken out after 4min, obtain PI/PbI2Composite material, is then in programming rate by above-mentioned composite material
80 DEG C/min, temperature 550K, pressure 7MPa, soaking time are under 5h, carry out ethanol supercritical drying, and PI/HgI is made2
Composite aerogel；The condition of the ethanol supercritical drying is：Programming rate is 100 DEG C/min, holding temperature 550K, is kept the temperature
Time is 4h, pressure 6MPa.
Embodiment 4
1st, the preparation of the PI aeroges containing halogen group I
(1) by 50g adjacent nitros iodobenzene and the catalyst CH of 125mL2O、N2H4, HI reaction, obtain 3,3'- bis- iodo- 4,4'-
Benzidine, as the monomer containing halogen group I.
(2) monomer obtained in 3.99g steps (1) is dissolved in 75mLN- methyl pyrrolidones (NMP), stirring and dissolving,
Obtain mixed solution；Then 22.5g 2,2- diaminobenzidines are added to stirring and dissolving in above-mentioned mixed solution, and rapidly
Add 1,3,5- tri- (4- amino-benzene oxygens) benzene of 30mL 0.02mol/L, sequentially added after stirring evenly 9mL acetic anhydride and
9mL pyridines, obtain chloride PI aeroges.
(3) the alcohol solution dipping 20h of 60%NMP will be used after the PI aeroges gelling aging 3h in step (2), then used
The alcohol solution dipping 22h of 15%NMP, finally the aging 24h in ethanol solution, obtains the PI wet gels containing halogen group I.
(4) it is 580K in temperature by the wet gel obtained in step (3), pressure 7MPa, programming rate is 85 DEG C/min
Under the conditions of carry out ethanol supercritical drying, soaking time 5h, is made the PI aeroges containing Cl, and above-mentioned aeroge is cut
Thin slice into 3mm thickness is stand-by.
2nd, the preparation of PI/AgI composite aerogels
3g prepared by the above method PI aeroge thin slices for containing halogen group Br are immersed in 10mL 1mol/L's
AgNO3In ethanol solution, taken out after 4min, obtain PI/AgI composite materials, be then in programming rate by above-mentioned composite material
80 DEG C/min, temperature 580K, pressure 7MPa, soaking time are under 5h, carry out ethanol supercritical drying, and obtained PI/AgI is answered
Close aeroge；The condition of the ethanol supercritical drying is：Programming rate is 110 DEG C/min, holding temperature 530K, during insulation
Between be 5h, pressure 6MPa.
Embodiment 5
1st, the preparation of the PI aeroges containing halogen group Br
(1) by 50g nitro bromobenzenes and catalyst n aOH, N of 150mL2H4, HBr reaction, obtain 3,3'- bis- bromo- 4,4'-
Benzidine is as the monomer containing halogen group Br.
(2) monomer obtained in 3.99g steps (1) is dissolved in 50mLN- methyl pyrrolidones (NMP), stirring and dissolving,
Obtain mixed solution；Then 10g p-phenylenediamine is added to stirring and dissolving in above-mentioned mixed solution, and is rapidly added 10mL
The 1 of 0.02mol/L, 3,5- tri- (4- amino-benzene oxygens) benzene, sequentially adds 12mL acetic anhydride and 10mL pyridines after stirring evenly,
Obtain chloride PI aeroges.
(3) the alcohol solution dipping 24h of 75%NMP will be used after the PI aeroges gelling aging 3h in step (2), then used
The alcohol solution dipping 24h of 25%NMP, finally the aging 24h in ethanol solution, it is wet solidifying to obtain the PI containing halogen group Br
Glue.
(4) it is 600K in temperature by the wet gel obtained in step (3), pressure 10MPa, programming rate is 80 DEG C/min
Under the conditions of carry out ethanol supercritical drying, soaking time 5h is made the PI aeroges containing halogen group Br, and by above-mentioned gas
The thin slice that gel cuts into 4mm thickness is stand-by.
2、PI/PbBr2The preparation of composite aerogel
3g prepared by the above method PI aeroge thin slices for containing halogen group Br are immersed in the Pb of 10mL 1.5mol/L
(NO3)2In ethanol solution, taken out after 4min, obtain PI/PbBr2Composite material, then by above-mentioned composite material in programming rate
For 80 DEG C/min, temperature 580K, pressure 7MPa, soaking time are under 5h, carry out ethanol supercritical drying, PI/ is made
PbBr2Composite aerogel；The condition of the ethanol supercritical drying is：Programming rate is 90 DEG C/min, holding temperature 580K,
Soaking time is 3h, pressure 7MPa.
The foregoing is merely the preferred embodiment of the application, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
- A kind of 1. preparation method of the polyimide aerogels containing halogen group X, it is characterised in that：The described method includes as follows Step：1) intermediate is obtained into the monomer containing halogen group X under catalysts conditions by organic substitution reaction；2) monomer containing halogen group X in step 1) is dissolved in organic solvent and obtains mixed solution, then by diamines or In the above-mentioned mixed solution of person's dianhydride addition after stirring and dissolving, crosslinking agent is rapidly added, acetic anhydride is sequentially added after stirring evenly And pyridine, by chemical imidization, obtain the polyimides wet gel containing halogen group X；3) the polyimides moisture gel obtained in step 2) after burin-in process, is recycled into Ethanol supercritical in ethanol solution Seasoning obtains the polyimide aerogels containing halogen group X；4) polyimide aerogels containing halogen group X that obtain prepared in step 3) are laminated, to obtain the final product.
- 2. the preparation method of the polyimide aerogels as claimed in claim 1 containing halogen group X, it is characterised in that：Step It is rapid 1) in, the intermediate includes o-nitrochlorobenzene, nitro bromobenzene, adjacent nitro iodobenzene；The catalyst includes：NaOH/CH2O、N2H4、HCl/HBr/HI；The mass volume ratio (g/mL) of the intermediate and catalyst is 1~3：5；The halogen group X is：Cl, Br, I element.
- 3. the preparation method of the polyimide aerogels as claimed in claim 2 containing halogen group X, it is characterised in that：Step It is rapid 2) in, the crosslinking agent is 1,3,5- tri- (4- amino-benzene oxygens) benzene；The organic solvent includes 1-methyl-2-pyrrolidinone；The diamines is：2,2- diaminobenzidines, p-phenylenediamine, 4,4- diaminodiphenyl ethers；The dianhydride is：Biphenyl tetracarboxylic dianhydride, pyromellitic acid anhydride, diphenyl ether tetracarboxylic dianhydride.
- 4. the preparation method of the polyimide aerogels as claimed in claim 3 containing halogen group X, it is characterised in that：Step It is rapid 2) in, the mass volume ratio of the diamines or dianhydride and organic solvent is 1~3：10~15；The volume ratio of the crosslinking agent and organic solvent is 1~3：5；The acetic anhydride, pyridine, the volume ratio of organic solvent are 1：1：5~10.
- 5. as claim 1-4 any one of them contains the preparation method of the polyimide aerogels of halogen group X, its feature It is：In step 3), the burin-in process refers to：1. by after polyimides moisture gel gelling aging 3h with 50~75%N- methyl 18~24h of alcohol solution dipping of pyrrolidones；2. with the alcohol solution dipping of 10~25%NMP 1. middle moisture gel 20~ 24h；3. will 2. middle moisture gel aging 24h in ethanol solution；The ethanol supercritical drying method refers to：In 536~600K of temperature, 6.6~10MPa of pressure, programming rate is 80~100 DEG C/min under the conditions of carry out ethanol supercritical drying.
- A kind of 6. preparation method of difficulty soluble salt and polyimide aerogels composite photo-catalyst, it is characterised in that：The method bag Include following steps：(1) the polyimides moisture gel slice containing halogen group X prepared in the method described in claim 1 is forerunner Body, is dipped into soluble salt ethanol solution, the halogen group X in presoma and the metal cation in soluble salt are anti-by the presoma Should, obtain the polyimides composite aerogel containing difficulty soluble salt；(2) the polyimides composite aerogel containing difficulty soluble salt obtained using ethanol supercritical drying method to step (1) is carried out Processing, makes to form hetero-junctions between polyimides and deposited salt, up to difficulty soluble salt and polyimides composite photo-catalyst.
- 7. a kind of difficulty soluble salt as claimed in claim 6 and the preparation method of polyimide aerogels composite photo-catalyst, its feature It is：In step (1), the presoma is 1~3 with the mass volume ratio (g/mL) of soluble salt ethanol solution：10；The soluble salt is：Pb(NO3)2, AgNO3, Hg (NO3)2；The concentration of soluble salt is 1-2mol/L in the soluble salt ethanol solution；The reaction time is 1~5min, is reacted normal Temperature is lower to be carried out.
- 8. a kind of difficulty soluble salt as claimed in claim 6 and the preparation method of polyimide aerogels composite photo-catalyst, its feature It is：In step (2), the condition of the ethanol supercritical drying is：Programming rate is 80~120 DEG C/min, and holding temperature is 500~600K, soaking time are 2~6h, and pressure is 5~8MPa.
- 9. a kind of difficulty soluble salt as claimed in claim 6 and the preparation method of polyimide aerogels composite photo-catalyst, its feature It is：In the step (1) and (2), difficulty soluble salt is halogen group X and metal cation Pb, Ag, Hg shape in above-mentioned nitrate Into the inorganic salts for being insoluble in water.
- 10. the preparation method of the polyimide aerogels containing halogen group X as described in claim 1-4 and/or such as right It is required that the preparation method of the difficulty soluble salt and polyimide aerogels composite photo-catalyst described in 6-9 is in photocatalytic degradation organic contamination Application in thing, photocatalytic water ammonia, carbon dioxide reduction, selective organic synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711193341.5A CN107936247B (en) | 2017-11-24 | 2017-11-24 | Insoluble salt and polyimide aerogel composite photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711193341.5A CN107936247B (en) | 2017-11-24 | 2017-11-24 | Insoluble salt and polyimide aerogel composite photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107936247A true CN107936247A (en) | 2018-04-20 |
| CN107936247B CN107936247B (en) | 2020-04-17 |
Family
ID=61948747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711193341.5A Active CN107936247B (en) | 2017-11-24 | 2017-11-24 | Insoluble salt and polyimide aerogel composite photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107936247B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529933A (en) * | 2018-12-06 | 2019-03-29 | 怀化学院 | ZIF loaded catalyst and the preparation method and application thereof |
| CN109622043A (en) * | 2018-12-18 | 2019-04-16 | 山东省科学院新材料研究所 | A kind of PI/Ag aeroge composite photocatalyst material and its preparation method and application |
| JP2022516281A (en) * | 2019-01-02 | 2022-02-25 | デリム カンパニー リミテッド | A method for producing a polyamic acid composition, a polyamic acid composition, a method for producing a polyimide film using the same, and a polyimide film produced by the method for producing the same. |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040132845A1 (en) * | 2002-07-22 | 2004-07-08 | Aspen Aerogels, Inc. | Polyimide aerogels, carbon aerogels, and metal carbide aerogels and methods of making same |
| 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 |
| US20170137593A1 (en) * | 2013-05-23 | 2017-05-18 | Nexolve Corporation | Method of Aerogel Synthesis |
-
2017
- 2017-11-24 CN CN201711193341.5A patent/CN107936247B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040132845A1 (en) * | 2002-07-22 | 2004-07-08 | Aspen Aerogels, Inc. | Polyimide aerogels, carbon aerogels, and metal carbide aerogels and methods of making same |
| US20170137593A1 (en) * | 2013-05-23 | 2017-05-18 | Nexolve Corporation | Method of Aerogel Synthesis |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| HAIQUAN GUO ET AL: "Polyimide aerogels cross-linked through amine functionalized polyoligomeric silsesquioxane", 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529933A (en) * | 2018-12-06 | 2019-03-29 | 怀化学院 | ZIF loaded catalyst and the preparation method and application thereof |
| CN109529933B (en) * | 2018-12-06 | 2021-10-22 | 怀化学院 | ZIF supported catalyst and preparation method and application thereof |
| CN109622043A (en) * | 2018-12-18 | 2019-04-16 | 山东省科学院新材料研究所 | A kind of PI/Ag aeroge composite photocatalyst material and its preparation method and application |
| CN109622043B (en) * | 2018-12-18 | 2021-11-02 | 山东省科学院新材料研究所 | PI/Ag aerogel composite photocatalytic material and preparation method and application thereof |
| JP2022516281A (en) * | 2019-01-02 | 2022-02-25 | デリム カンパニー リミテッド | A method for producing a polyamic acid composition, a polyamic acid composition, a method for producing a polyimide film using the same, and a polyimide film produced by the method for producing the same. |
| JP7317122B2 (en) | 2019-01-02 | 2023-07-28 | デリム カンパニー リミテッド | Polyamic acid composition production method, polyamic acid composition, polyimide film production method using the same, and polyimide film produced by the production method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107936247B (en) | 2020-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Deng et al. | Robust catalysis on 2D materials encapsulating metals: concept, application, and perspective | |
| Yilmaz et al. | Atomic‐and Molecular‐Level Design of Functional Metal–Organic Frameworks (MOFs) and Derivatives for Energy and Environmental Applications | |
| Yang et al. | Porous organic polymers for electrocatalysis | |
| Zou et al. | Controllable syntheses of MOF‐derived materials | |
| Liu et al. | Bringing catalytic order out of chaos with nitrogen-doped ordered mesoporous carbon | |
| Yang et al. | Inorganic-organic hybrid photocatalysts: Syntheses, mechanisms, and applications | |
| Xiao et al. | Single metal atom decorated carbon nitride for efficient photocatalysis: synthesis, structure, and applications | |
| CN107936247A (en) | A kind of difficulty soluble salt and polyimide aerogels composite photo-catalyst and preparation method thereof | |
| Rangraz et al. | Recent advances on heteroatom‐doped porous carbon/metal materials: fascinating heterogeneous catalysts for organic transformations | |
| Guo et al. | Degradation of organic contaminants by peroxymonosulfate activated with Zeolitic imidazolate frameworks-based catalysts: performances, mechanisms and stability | |
| Zhao et al. | Metal Sub‐nanoclusters Confined within Hierarchical Porous Carbons with High Oxidation Activity | |
| Ma et al. | Metal-nitrogen-carbon catalysts for peroxymonosulfate activation to degrade aquatic organic contaminants: Rational design, size-effect description, applications and mechanisms | |
| CN108246339A (en) | A kind of preparation method and applications of covalent organic framework/nitridation carbon composite | |
| Nik Zaiman et al. | Developing metal‐organic framework‐based composite for innovative fuel cell application: An overview | |
| CN101244383A (en) | Process for producing absorbent charcoal loading titanium dioxide photocatalyst | |
| Sa et al. | Strategies for enhancing the electrocatalytic activity of M–N/C catalysts for the oxygen reduction reaction | |
| Han et al. | Research progresses in the preparation of Co-based catalyst derived from Co-MOFs and application in the catalytic oxidation reaction | |
| CN111644210B (en) | Application of composite carrier ruthenium-based catalyst in acetylene hydrochlorination | |
| Gao et al. | Metal and metal oxide supported on ordered mesoporous carbon as heterogeneous catalysts | |
| Wang et al. | Synergistic enhancement of the visible-light photocatalytic activity of hierarchical 3D BiOClxBr1-x/graphene oxide heterojunctions for formaldehyde degradation at room temperature | |
| Ma et al. | Protonated supramolecular complex-induced porous graphitic carbon nitride nanosheets as bifunctional catalyst for water oxidation and organic pollutant degradation | |
| Jafari et al. | Carbon‐based nonprecious metal electrocatalysts derived from MOFs for oxygen‐reduction reaction | |
| Li et al. | Metal-organic frameworks (MOFs) as efficient catalysts for electro-Fenton (EF) reactions: Current progress and prospects | |
| Yang et al. | Recent advances in metal-free CDs/g-C3N4 photocatalysts: Synthetic strategies, mechanism insight, and applications | |
| Zhang et al. | Preparation of Heteroatom‐Doped Carbon Materials and Applications in Selective Hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |