CN109021246A - A kind of temperature-responsive metal organic frame nanocrystal and preparation method and application - Google Patents
A kind of temperature-responsive metal organic frame nanocrystal and preparation method and application Download PDFInfo
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- CN109021246A CN109021246A CN201810941155.3A CN201810941155A CN109021246A CN 109021246 A CN109021246 A CN 109021246A CN 201810941155 A CN201810941155 A CN 201810941155A CN 109021246 A CN109021246 A CN 109021246A
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- organic frame
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000006210 lotion Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920000208 temperature-responsive polymer Polymers 0.000 claims abstract description 18
- 239000002086 nanomaterial Substances 0.000 claims abstract description 9
- 238000007385 chemical modification Methods 0.000 claims abstract description 4
- 238000001311 chemical methods and process Methods 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 238000006298 dechlorination reaction Methods 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000007098 aminolysis reaction Methods 0.000 claims description 6
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 6
- -1 sulfophenyl Chemical group 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229940031098 ethanolamine Drugs 0.000 claims description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical class CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 150000007970 thio esters Chemical group 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 238000012711 chain transfer polymerization Methods 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 150000003141 primary amines Chemical group 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical group C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
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- 238000009736 wetting Methods 0.000 description 2
- UUWJBXKHMMQDED-UHFFFAOYSA-N 1-(3-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Cl)=C1 UUWJBXKHMMQDED-UHFFFAOYSA-N 0.000 description 1
- QGRPVMLBTFGQDQ-UHFFFAOYSA-N 1-chloro-2-methoxybenzene Chemical compound COC1=CC=CC=C1Cl QGRPVMLBTFGQDQ-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- ANPPGQUFDXLAGY-UHFFFAOYSA-N 2-chloroethyl benzoate Chemical compound ClCCOC(=O)C1=CC=CC=C1 ANPPGQUFDXLAGY-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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- 229910001882 dioxygen Inorganic materials 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
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- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000751 protein extraction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of temperature-responsive metal organic frame nanocrystal and preparation method and application, the temperature-responsive metal organic frame nanocrystal includes metal organic frame nano material and temperature-responsive polymer, for the thioether bond that temperature-responsive polymer is formed by click chemistry method in conjunction with metal organic frame nano material, the metal organic frame nano material is the surface metal-organic framework material containing double bonds obtained by chemical modification.The MOFs nanocrystal has excellent temperature control oil-water separation, MOFs nanocrystal can be separated and be reused by temperature change after the reaction of Pickering lotion catalyst system.
Description
Technical field
The invention belongs to nano-functional material technical fields, are related to a kind of based on temperature-responsive metal organic frame nanometer
The preparation and its catalytic applications of the Pickering lotion of crystal.
Background technique
Metal organic frame (Metal-Organic Frameworks), abbreviation MOFs, be by organic ligand and metal from
The hybrid inorganic-organic materials with molecule inner pore that son or cluster are self-assembly of by coordinate bond.Several years in past is
It is prepared for different types of MOFs material, and in hydrogen storage, gas absorption and separates, sensor, medicament slow release, be catalyzed and react
There is important application in equal fields.With aspect, synthesis is separated there is the MOFs material of excellent absorption property to be used in gas absorption
Hydrogen storage, toxic and harmful gas absorption with separate, the environmental problem got worse that a part of people face can be solved.?
In terms of catalytic applications, using different metal mixing building there is the compound MOFs material of efficient catalytic function will further improve and urge
Change efficiency.In addition, in separation field, preparation, which has magnetic compound MOFs material, can be used for poisonous and harmful substance, heavy metal
Adsorb with separate and complex system in target protein extraction with separate.Especially in field of biomedicine, since it is controllable
Pore size, functional group and good bio-compatibility, preparation nanoscale MOFs material is for drug in living cells
Sustained release and metabolism, the movable real-time monitoring of life entity etc. understand vital movement important in organism (such as protein to people
Interaction between function, protein), the activation mechanism of regulation protein and the relevant protein regulation access of major disease
Deng with great biological significance.Therefore, exploitation has the MOFs and compound MOFs material of functional diversity, and is applied to
Different field will be greatly promoted interdisciplinary mutual development.
Ultra-fine solid particle can be used as oil-in-water or water-in-oil emulsifier, and this kind of emulsion system is referred to as
The type of Pickering lotion, gained lotion depends on which phase preferential wetting solid particle, usual preferential wetting solid particle
A phase be foreign minister, also referred to as continuous phase.If solid particle is easier to be soaked by oily phase sometimes, emulsion is W/O (Water-In-Oil)
Type；Conversely, emulsion is O/W (oil-in-water) type as solid particle is easier to be soaked by water phase.Particle emulsifying agents are
Key component in Pickering lotion, the solid powder as emulsifier have clay, silica, metal hydroxides, stone
Ink, carbon black etc. have inorganic particle emulsifying agents and organic granular emulsifier.Pickering lotion has many application prospects, especially
It is in medicament slow release, prepares the great interest that the fields such as Janus microballoon and porous material cause people.
Stimulus responsive polymers are a kind of macromolecular systems with " intelligence " behavior.It can receive the thorn of external environment
Energizing signal, such as pH value, light, temperature, voltage, reductant-oxidant and gas make macromolecular conformation or state that larger change occur,
To influence its physicochemical properties, and then embody corresponding function.A large amount of result of study shows stimulus responsive polymers
It has a wide range of applications in nanometer material science, life science and clinical medicine domain, especially temperature-responsive, it is non-
It often is easy, and there is no any destructiveness, research significance with higher to system.
Summary of the invention
In order to solve the deficiencies in the prior art, an object of the present invention, which is to provide a kind of temperature-responsive metal, machine frame
Frame nanocrystal can prepare Pickering lotion using the MOFs nanocrystal as particle emulsifying agents, the biography for being catalyzed MOFs
System grease consolidates three-phase and is converted to Pickering lotion catalyst system, increases reaction interface, increases substantially reaction efficiency, together
When the MOFs nanocrystal have excellent temperature control oil-water separation, can Pickering lotion catalyst system reaction after
MOFs nanocrystal is separated and reused by temperature change.
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of temperature-responsive metal organic frame nanocrystal, including metal organic frame nano material and temperature-responsive
Property polymer, temperature-responsive polymer by click (click) chemical method formed thioether bond and metal organic frame nanometer
Material combines, and the metal organic frame nano material is that the surface metal containing double bonds obtained by chemical modification has machine frame
Frame material.
The second object of the present invention is to provide a kind of preparation side of above-mentioned temperature-responsive metal organic frame nanocrystal
Method the steps include:
(1) to contain the metal organic frame of primary amine group as raw material, by the primary amine group be modified to containing
The group of double bond obtains surface metal-organic framework material containing double bonds；
(2) 2,2'- (thiocarbonyl is bis- (sulfophenyl)) bis- (2 Methylpropionic acids) (CTA) is added into temperature-responsive monomer
Reversible addion-fragmentation chain transfer (RAFT) polymerization is carried out, three thioester groups are reduced into sulfydryl using aminolysis, obtaining end is
The temperature-responsive polymer of sulfydryl；
(3) reaction of sulfydryl-alkene click chemistry is used to contain the temperature-responsive polymer of end sulfydryl with surface
The metal-organic framework material of double bond carries out the addition reaction of sulfydryl and double bond, to obtain temperature-responsive metal organic frame
Nanocrystal.
Further include situ aggregation method in the method for metal-organic framework material surface grafting temperature-responsive polymer, i.e., will
Surface metal-organic framework material containing double bonds and temperature-responsive monomer directly carry out free radical polymerization, however pass through this hair
The previous experiments of bright inventor find, by situ aggregation method be difficult to control the temperature-responsive polymer of grafting the degree of polymerization and
Grafting density, so as to cause preparation temperature-responsive metal organic frame nanocrystal interfacial activity with temperature significant change
It is unobvious, and temperature-responsive is very poor, it is difficult to realize high efficiency temperature controlled water-oil separating.
The third object of the present invention is to provide a kind of above-mentioned temperature-responsive metal organic frame nanocrystal and exists
Application in Pickering emulsion system.
The fourth object of the present invention is to provide a kind of catalyst, with above-mentioned temperature-responsive metal organic frame nanocrystal
As carrier to load metal palladium.
The fifth object of the present invention is to provide a kind of above-mentioned catalyst in Pickering emulsion system to the more of dechlorination reaction
The mutually application of catalysis.
The sixth object of the present invention is to provide a kind of method of catalysis dechlorination, by organic solvent, water, substrate containing chlorine, formic acid
Ammonium and above-mentioned catalyst preparation are reacted at Pickering lotion, and the substrate containing chlorine is that chlorine is directly connected to phenyl ring
Organic matter.
The invention has the benefit that
(1) the present invention provides a kind of temperature-responsive metal organic frame nanocrystals, with MOFs nanocrystal work
Pickering lotion can be prepared for particle emulsifying agents, the traditional grease for being catalyzed MOFs consolidates three-phase and is converted to Pickering cream
Liquid catalyst system, increases reaction interface, increases substantially reaction efficiency, while the MOFs nanocrystal has excellent temperature control
Oil-water separation can be carried out MOFs nanocrystal by temperature change after the reaction of Pickering lotion catalyst system
It separates and reuses.
(2) catalyst that temperature-responsive metal organic frame nanocrystal provided by the invention is prepared into supported palladium,
There are good catalytic performance and temperature control oil-water separation, and urging by separating for several times rear catalyst for catalysis dechlorination reaction
It is almost unchanged to change effect.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is synthetic route；
Fig. 2 is UiO-66-NH2The TEM of nanocrystal schemes；
Fig. 3 is that the TEM of UiO-66-Met nanocrystal schemes；
Fig. 4 is the nucleus magnetic hydrogen spectrum of PNIPAM-CTA and PNIPAM-SH；
Fig. 5 is the gel permeation chromatogram of PNIPAM-CTA and PNIPAM-SH；
Fig. 6 is the uv atlas of PNIPAM-CTA and PNIPAM-SH；
Fig. 7 is that the TEM of UiO-66-S-PNIPAM nanocrystal schemes；
Fig. 8 is the nucleus magnetic hydrogen spectrum of UiO-66-S-PNIPAM synthesis process；
Fig. 9 is the infrared spectrum of UiO-66-S-PNIPAM；
Figure 10 is that the TEM of Pd@UiO-66-S-PNIPAM nanocrystal schemes；
Figure 11 is that the EDS of Pd@UiO-66-S-PNIPAM nanocrystal schemes；
Figure 12 is that the PXRD of synthesizing nanocrystalline body combines spectrogram；
Figure 13 is the lotion and Laser Scanning Confocal Microscope photo of different Pd@UiO-66-S-PNIPAM contents；
Figure 14 is the lotion and Laser Scanning Confocal Microscope photo of different oil-water ratios；
Figure 15 is emulsion temperature responsiveness photo；
Figure 16 is the model reaction equation of dechlorination reaction；
Figure 17 is that dechlorination reacts gas phase monitoring spectrogram；
Figure 18 is catalysate nucleus magnetic hydrogen spectrum；
Figure 19 is five circulation yields；
Figure 20 is five circulation powder；
Figure 21 is the TEM figure of Pd@UiO-66-S-PNIPAM nanocrystal after catalysis；
Figure 22 is the EDS figure of Pd@UiO-66-S-PNIPAM nanocrystal after catalysis；
Figure 23 is the nucleus magnetic hydrogen spectrum for the nanocrystal that embodiment 12 is prepared by situ aggregation method；
Figure 24 is the gel permeation chromatogram for the nanocrystal that embodiment 12 is prepared by situ aggregation method；
Figure 25 is photograph of the nanocrystal that is prepared by situ aggregation method of embodiment 12 in grease system under different temperatures
Piece.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the application.Unless another
It indicates, 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 specific 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 singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, the prior art realizes metal-organic framework material not over control temperature change
Isolated deficiency is recycled, in order to solve technical problem as above, present applicant proposes a kind of temperature-responsive metal organic frames
Nanocrystal and preparation method and application.
The application's provides a kind of temperature-responsive metal organic frame nanocrystal, including metal organic frame nanometer
Material and temperature-responsive polymer, temperature-responsive polymer is by clicking the thioether bond and gold that (click) chemical method is formed
Belong to organic frame nano material to combine, the metal organic frame nano material is double to contain by the surface that chemical modification obtains
The metal-organic framework material of key.
The metal-organic framework material is the metal organic frame that primary amine group is contained on surface, such as UiO-66-NH2、
UiO-67-NH2、NH2- MIL-101 etc..The temperature-responsive polymer is to experience exterior temperature change to can produce material
Learn the polymer, such as poly-N-isopropyl acrylamide (PNIPAM) etc. of characteristic and conformational state generation compared with big change, the application
A kind of exemplary embodiment, the metal-organic framework material be UiO-66-NH2, the temperature-responsive polymer is poly-
N-isopropyl acrylamide.The degree of polymerization of poly-N-isopropyl acrylamide is 10~300.The number of poly-N-isopropyl acrylamide is equal
Molecular weight is 2000~5000Da.The herein described degree of polymerization is that contained number of repeat unit purpose is average on polymer macromolecule chain
Value.
Present invention also provides a kind of preparation method of above-mentioned temperature-responsive metal organic frame nanocrystal, steps
Are as follows:
(1) to contain the metal organic frame of primary amine group as raw material, by the primary amine group be modified to containing
The group of double bond obtains surface metal-organic framework material containing double bonds；
(2) 2,2'- (thiocarbonyl is bis- (sulfophenyl)) bis- (2 Methylpropionic acids) (CTA) is added into temperature-responsive monomer
Reversible addion-fragmentation chain transfer (RAFT) polymerization is carried out, three thioester groups are reduced into sulfydryl using aminolysis, obtaining end is
The temperature-responsive polymer of sulfydryl；
(3) reaction of sulfydryl-alkene click chemistry is used to contain the temperature-responsive polymer of end sulfydryl with surface
The metal-organic framework material of double bond carries out the addition reaction of sulfydryl and double bond, to obtain temperature-responsive metal organic frame
Nanocrystal.
In a kind of preparation method of representative temperature responsiveness metal organic frame nanocrystal of the application, contain primary amine groups
The metal organic frame of group is UiO-66-NH2.Its synthetic method refers to CN106928465A, by 2- amino-Isosorbide-5-Nitrae-terephthaldehyde
Acid, zirconium chloride, acetic acid are dissolved in n,N-Dimethylformamide, 120 DEG C of constant temperature for 24 hours, be down to room temperature, after centrifugal drying to obtain the final product
Metal organic frame.
In a kind of embodiment of the application, in step (1), by metal organic frame and methyl-prop containing primary amine group
Olefin(e) acid acid anhydride is reacted, so that primary amine group and methacrylic acid anhydride reactant generate peptide bond.The specific steps are that: by UiO-66-
NH2Crystal, methacrylic anhydride, triethylamine are dissolved in chloroform, are heated to reflux 1~48h under conditions of 25~88 DEG C.Its
In, chloroform is by drying process, and triethylamine is to prevent impurity effect reaction efficiency through overweight steaming.UiO-66-
NH2Crystal, methacrylic anhydride, triethylamine, chloroform feed ratio be 0.001:0.008:0.001:25, mol:mol:
Mol:mL.
Temperature-responsive monomer described herein is the organic matter for capableing of double-bond polymerization acquisition temperature-responsive polymer,
Such as n-isopropyl acrylamide (NIPAM) etc., in a kind of embodiment of the application, in step (2), the condition of RAFT polymerization
Are as follows: under atmosphere of inert gases, 70~75 DEG C are heated to, reacts 24~36h.Herein described inert gas is that can prevent oxygen
Gas of oxidation, such as nitrogen, argon gas etc..React skeleton symbol are as follows:
In a kind of embodiment of the application, in step (2), the step of aminolysis are as follows: under atmosphere of inert gases, by RAFT
After polymer after polymerization is reacted at room temperature with ethanol amine, tributylphosphine.The room temperature refer to temperature be 15~
35℃.In order to which the polymer after polymerizeing RAFT is uniformly mixed with ethanol amine, tributylphosphine, accelerate reaction rate, aminolysis reaction
It needs to carry out in a solvent, the solvent is preferably Isosorbide-5-Nitrae-dioxane.React skeleton symbol are as follows:
In a kind of embodiment of the application, in step (3), reaction condition are as follows: ultraviolet initiator is added in ultraviolet light
It is reacted under irradiation.The ultraviolet initiator is preferably 2,2- dimethoxy -2- phenyl acetophenone, at this point, ultraviolet light
Broadcasting is 365nm.React skeleton symbol are as follows:
Present invention also provides a kind of above-mentioned temperature-responsive metal organic frame nanocrystals in Pickering lotion body
Application in system.
Present invention also provides a kind of catalyst, using above-mentioned temperature-responsive metal organic frame nanocrystal as carrier
Carried metal palladium.
The application's is a kind of using temperature-responsive metal organic frame nanocrystal as the reality of carrier to load metal palladium
The mode of applying is to remove solvent after temperature-responsive metal organic frame nanocrystal is impregnated palladium acetate solution, then restoring
Divalent palladium is restored under the action of agent.Wherein, the content of Metal Palladium is 3~4% (quality) in catalyst.React skeleton symbol are as follows:
Present invention also provides a kind of above-mentioned catalyst in Pickering emulsion system answering to the catalysis of dechlorination reaction
With.
Present invention also provides a kind of method of catalysis dechlorination, by organic solvent, water, substrate containing chlorine, ammonium formate and above-mentioned
Catalyst preparation is reacted at Pickering lotion, and the substrate containing chlorine is directly connected to for chlorine with phenyl ring organic
Object.React skeleton symbol are as follows:
In a kind of embodiment of the application, the solid content in Pickering lotion is 1~2wt%.The solid content
Pickering emulsion state is stablized, wherein Pickering lotion is most stable when solid content is 2wt%.Meanwhile
When oil is mutually 3:1 with the volume ratio of water phase in Pickering lotion, the Pickering lotion of formation is more stable.
The reaction temperature of dechlorination is room temperature.Substrate containing chlorine, ammonium formate molar ratio be 1:10.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment of body.
For convenience of description, the abbreviation of each crystal and polymer is described in table 1 below:
Table 1
1 metal organic frame UiO-66-NH of embodiment2Synthesis
It weighs zirconium chloride (93.2mg, 0.4mmol) to be placed in the conical flask of 25mL, n,N-Dimethylformamide is added
Then acetic acid (1200mg, 20mmol) is added in (16mL), and sonic oscillation 30min makes it completely dissolved, and organic match then is added
Body 2- amino terephthalic acid (TPA) (72.5mg, 0.4mmol), then sonic oscillation 30min, are attached to the high temperature and high pressure kettle of 20mL specification
In, 120 DEG C of constant temperature are cooled to 20 DEG C for 24 hours, by 10h, obtain faint yellow nano crystals (120mg), are centrifuged, and it is dry,；Wherein have
Machine ligand 2- amino terephthalic acid (TPA), zirconium chloride, acetic acid and N,N-dimethylformamide solvent adding amount ratio be
0.4mmol:0.4mmol:20mmol:1.6mL；Obtained UiO-66-NH2 crystal powder is first cleaned 4~5 times with DMF, then
It is cleaned 4~5 times with fresh chloroform, is then placed in chloroform, be stirred at room temperature and impregnate 3d, every changing primary fresh chloroform for 24 hours,
Centrifugal drying；Constant temperature 3h at dried 100 DEG C of crystal takes out for use, and shape is octahedron, and 200nm or so is shown in Fig. 2；5
There are two peaks being clearly separated, the appearance at 25 degree or so peaks, it was demonstrated that be UiO-66-NH between degree and 10 degree2Frame, see figure
12。
The synthesis of 2 UiO-66-Met nanocrystal of embodiment
Weigh UiO-66-NH2Crystal (0.6g, 0.002mol), methacrylic anhydride 2.356mL (2.45g,
0.016mol), the chloroform soln of triethylamine 0.279mL (0.002mol), 50mL are added into the round-bottomed flask of 100mL,
Chloroform therein is by drying process, and triethylamine is heated to reflux for 24 hours under conditions of 55 DEG C through overweight steaming,
Add drying device on condenser pipe.Reaction terminates, and centrifugal treating is carried out after natural cooling, then washs 6 with fresh chloroform
It is secondary, under conditions of 100 DEG C, 5 hours are dried in vacuo, the product after having handled is denoted as UiO-66-Met, yield 90%, shape
For octahedron, 200nm or so is shown in Fig. 3；Have obviously two peaks seeing respectively between 5 degree and 10 degree, 25 degree or so peaks out
It is existing, it was demonstrated that the frame after rear modification does not destroy, and sees Figure 12.
The preparation of 3 PNIPAM-CTA of embodiment
Under nitrogen protection, NIPAM (6.1224g, 53nmol) is taken to be placed in there-necked flask, 16mL Isosorbide-5-Nitrae-dioxane is added
Make solvent, be added RFAT reagent C TA (2,2'- (thiocarbonyl is bis- (sulfophenyl)) bis- (2 Methylpropionic acids)) (0.299g,
1.06mmol) azodiisobutyronitrile (AIBN, 0.0087g, 0.053nmol), for 24 hours, ice-water bath terminates reaction to 70 DEG C of heating stirrings,
80mL ether dissolution precipitating has just started yellow mercury oxide and has been precipitated, filtered, be dried in vacuo to obtain yellow powder 5.3698g, be denoted as
PNIPAM-CTA, yield 82.62%, nucleus magnetic hydrogen spectrum is shown in Fig. 4；GPC tests to obtain number-average molecular weight to be 4748Da, calculates the degree of polymerization
Fig. 5 is seen for 42, GPC curve.
The preparation of 4 PNIPAM-SH of embodiment
It under nitrogen protection, weighs PNIPAM-CTA (5.00g, 1.009mol) and is placed in there-necked flask, 16mL Isosorbide-5-Nitrae-two is added
Six ring of oxygen makees solvent, ethanol amine (1.209mL, 10.09mmol), tributylphosphine (530.6 μ L, 1.009mmol) is added, room temperature is anti-
2h is answered, with the molten precipitating of 80mL ether, vacuum drying obtains brownish red jelly, is denoted as PNIPAM-SH, about 5.6g.Nucleus magnetic hydrogen spectrum
Seeing that Fig. 4, GPC obtain number-average molecular weight is 2395Da, and calculating the degree of polymerization is that 21, GPC curve is shown in that Fig. 5, reduction front and back nuclear-magnetism have poly-
Close the presence at object peak；Ultraviolet figure is shown in Fig. 6, and the peak 310nm disappears after reduction, the enhancing at the peak 250nm, it was demonstrated that reduction is thorough.
The preparation of 5 UiO-66-S-PNIPAM of embodiment
Claim PNIPAM-SH (3.7g, 1.5mmol), be placed in the beaker of 20mL, the tetrahydrofuran that 10mL is added makes it completely
Then UiO-66-Met (0.3g, 1mmol) is added in dissolution, 2,2- dimethoxy -2- phenyl acetophenones (30mg), ultrasonic vibration
It is stirred at 25 DEG C 0.5 hour, then the illumination 1.5h under the ultraviolet lamp of 365nm, centrifugation are washed three times, under conditions of 60 DEG C
It is stand-by to be dried in vacuo 3h, nuclear-magnetism yield about 50%.Powder does not become, and sees Figure 12, Electronic Speculum is shown in Fig. 6,200 ran of scale, octahedral
Body, nuclear-magnetism constitutional diagram are shown in Fig. 8, the appearance at the peak of polymer, and the reduction proof of double bond has connected a part, infrared to see Fig. 9,2950
And 2840cm-1The appearance at peak, it was demonstrated that the presence of the methylmethylene of polymer.
The preparation of 6 Pd@UiO-66-S-PNIPAM of embodiment
The palladium acetate for weighing 60mg, is dissolved in the toluene of 30mL, takes stand-by UiO-66-S-PNIPAM (100mg), room temperature
Stir 6h；After 6h, washed 3 times with fresh toluene, it is dry, it is to be restored；Weigh 20mg NaBH4It is dissolved in 20mL secondary water, it will
The MOF for loading divalent palladium impregnates 0.5h wherein, and after having restored, with fresh secondary rinsing agent 3 times, dried for standby is obtained
The crystal of supported palladium is stand-by, and TEM is shown in that Figure 10, one layer of palladium particle of area load, palladium lattice are 0.24nm；EDS is shown in Figure 11, is to have palladium
Existing for element, ICP measures palladium content 3.5%, and Examples 1 to 6 overall reaction equation is shown in Fig. 1.
7 MOFs particle preparation pickering lotion of embodiment
Pd@UiO-66-S-PNIPAM crystal 15mg, 30mg, 60mg, 90mg are weighed, toluene/water (2mL/1mL) is placed in
In solution, under conditions of high-shear homogenizer revolving speed is 5000r/min, 1min is emulsified, stands 30min, obtaining mass fraction is
The pickering lotion of 0.5wt%, 1.0wt%, 2.0wt%, 3.0wt% are shown in Figure 13.
Weigh Pd@UiO-66-S-PNIPAM crystal 60mg, be placed in toluene/water (2.4mL/0.6mL, 2.25mL/0.75mL,
2mL/1mL, 1.5mL/1.5mL) solution in, high-shear homogenizer revolving speed be 5000r/min under conditions of, emulsify 1min, it is quiet
30min is set, the mass fraction for obtaining the different conditions under different oil-water ratios is the lotion of 2.0wt%, and Pickering lotion is shown in
Figure 14,2.25mL/0.75mL form most stable emulsion.
Embodiment 8 is copolymerized burnt characterization
During preparing pickering lotion, fluorescein(e) dye is added in water phase, it is micro- using laser co-focusing
The one after another drop of on glass slide of stable emulsion is shot using the excitation light source of 20%, 488nm, sees Figure 13 and 14 by mirror,
It is emulsion oil-in-water, toluene: water 3:1, the lotion that mass fraction is 2% are most stable from copolymerization coke；With quality point
Several increases, emulsion particle diameter are gradually reduced, and 0.5% lotion is most unstable, can be agglomerated into big drop.1% it is slightly good,
2% it is best, 3% emulsion viscosity is excessively high, is not suitable for doing reaction system.
The reaction of 9 catalysis dechlorination of embodiment
In toluene (2.25mL)/water (0.75mL), Pd@UiO-66-S-PNIPAM (60mg), being prepared into mass fraction is
The lotion of 2.0wt%；M chloroacetophenone (0.25mmol), ammonium formate (2.5mmol), at 25 DEG C, reaction, gas phase monitoring reaction,
2.5h has reacted completely, and reaction equation is shown in Figure 16, and temperature is increased to 45 DEG C of holding 5min demulsifications, and catalyst goes to oily phase, ice
Water-bath cooling keeps 10min catalyst to return to water phase, is stored at room temperature half an hour, catalyst sedimentation water phase bottom, water-oil separating, breaks
Newborn process is shown in Figure 15, and product is in oily phase, and product nuclear-magnetism is shown in that Figure 18, gas phase yields 99.5%, monitoring yield are shown in Figure 17, and recycling is urged
Agent does five catalytic cycles, and yield, which is basically unchanged, sees Figure 19, and powder is shown in Figure 20, and powder does not destroy after circulation five times, is catalyzed
Agent is reusable, and TEM is shown in that Figure 21, palladium lattice do not become, and SEM-EDS photo is shown in Figure 22.
10 heat filtering of embodiment
After reaction 1.5, heating demulsification, cooling catalyst-falling to water phase, filtering removal catalyst, the reaction was continued, yield
Do not increase, it was demonstrated that the heterocatalysis characteristic of catalyst is shown in Figure 17.
The reaction of 11 catalysis dechlorination of embodiment
In toluene (2.25mL)/water (0.75mL), Pd@UiO-66-SH-PNIPAM (60mg), it is prepared into mass fraction
For the lotion of 2.0wt%；Substrate containing chlorine (0.25mmol), ammonium formate (2.5mmol), at 25 DEG C, reaction, gas phase monitoring reaction,
Yield results are shown in Table 2.The result shows that: identical substituent group different location (such as: o-chlorphenol, m-Chlorophenol, parachlorophenol) is to de-
Chlorine reaction influences little；Different substituents substrate (such as: parachlorophenol, parachloroanilinum, to chloroanisole, the chloro- benzoic acid first of 4-
Ester, the chloro- ethyl benzoate of 4-), electron-withdrawing group is significantly better than to (phenol, the aniline) of the effect electron-donating group of dechlorination reaction
(methyl phenyl ethers anisole, lipid) substrate；Reaction efficiency is dropped condensed ring substrate (such as: the chloro- biphenyl of 4-, the chloro- naphthalene of 1-) for dechlorination reaction
It is low；From the point of view of more chlorine substrates (such as 2,4- dichloro-phenol, 2,4,6- trichlorophenol, 2,4,6,-Ts) are to the effect of dechlorination reaction, reaction efficiency is more single
The substrate that chlorine replaces decreases, and the number of chlorine is more, and the reaction time is longer.
The different tables of substrate yield containing chlorine of table 2
Embodiment 12
Under nitrogen protection, UiO-66-Met (0.3g, 1mmol), NIPAM (6.1224g, 53nmol), potassium peroxydisulfate are taken
(9mg, about 1.25mol%), 20mL isopropanol are placed in there-necked flask, 70 DEG C of heating stirring 72h, centrifugation, and THF is washed three times, are done
It is dry stand-by.Nucleus magnetic hydrogen spectrum is shown in Figure 23, and the corresponding proton peak content of polymer is very low, and GPC spectrogram is shown in Figure 24, and number-average molecular weight is only
1300Da, and molecular weight distribution is very wide (PDI=2.16), in water-oil phase, (lower layer is water phase to particle, and upper layer is under different temperatures
Toluene phase) state it is as shown in figure 25, be warming up to 45 DEG C and do not occur mutually overturning.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (10)
1. a kind of temperature-responsive metal organic frame nanocrystal, characterized in that including metal organic frame nano material and
Temperature-responsive polymer, the thioether bond and metal organic frame nanometer that temperature-responsive polymer is formed by click chemistry method
Material combines, and the metal organic frame nano material is that the surface metal containing double bonds obtained by chemical modification has machine frame
Frame material；
Preferably, the metal-organic framework material is UiO-66-NH2, the temperature-responsive polymer is poly-N-isopropyl third
Acrylamide.
2. a kind of preparation method of temperature-responsive metal organic frame nanocrystal described in claim 1, characterized in that its
Step are as follows:
(1) using contain primary amine group metal organic frame as raw material, the primary amine group be modified to containing double bond
Group, obtain surface metal-organic framework material containing double bonds；
(2) it is reversible that 2,2'- (thiocarbonyl is bis- (sulfophenyl)) bis- (2 Methylpropionic acids) progress is added into temperature-responsive monomer
Three thioester groups are reduced into sulfydryl using aminolysis, obtain the temperature-responsive that end is sulfydryl by addition-fracture chain transfer polymerization
Property polymer；
(3) use the reaction of sulfydryl-alkene click chemistry that the temperature-responsive polymer of end sulfydryl and surface is made to contain double bond
Metal-organic framework material carry out sulfydryl and double bond addition reaction, to obtain temperature-responsive metal organic frame nanometer
Crystal.
3. preparation method as claimed in claim 2, characterized in that in step (2), the condition of RAFT polymerization are as follows: inert gas
Under atmosphere, 70~75 DEG C are heated to, reacts 24~36h；
Or, in step (2), the step of aminolysis are as follows: under atmosphere of inert gases, polymer and ethanol amine after RAFT is polymerize,
After tributylphosphine is reacted at room temperature；
Or, in step (3), reaction condition are as follows: ultraviolet initiator is added and is reacted under ultraviolet light.
4. a kind of temperature-responsive metal organic frame nanocrystal described in claim 1 is in Pickering emulsion system
Application.
5. a kind of catalyst, characterized in that using temperature-responsive metal organic frame nanocrystal described in claim 1 as
Carrier to load metal palladium.
6. catalyst as claimed in claim 5, characterized in that the method for carried metal palladium is to have temperature-responsive metal
Solvent is removed after machine frame nanocrystal dipping palladium acetate solution, then restores divalent palladium under the action of reducing agent.
7. catalyst as claimed in claim 5, characterized in that the content of Metal Palladium is 3~4% (quality) in catalyst.
8. a kind of any catalyst of claim 5~7 answering to the catalysis of dechlorination reaction in Pickering emulsion system
With.
9. a kind of method of catalysis dechlorination, characterized in that by organic solvent, water, substrate containing chlorine, ammonium formate and claim 5~7
Any catalyst preparation is reacted at Pickering lotion, and the substrate containing chlorine is that chlorine directly connects with phenyl ring
The organic matter connect.
10. method as claimed in claim 9, characterized in that the solid content in Pickering lotion is 1~2wt%.
Priority Applications (1)
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| CN111359587A (en) * | 2020-04-15 | 2020-07-03 | 厦门大学 | Preparation of quartz capillary hybridization monolithic column based on metal organic framework material |
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| CN110484530A (en) * | 2019-07-25 | 2019-11-22 | 山东师范大学 | A kind of Pickering lotion and its preparation method and application based on the load covalent organic frame base hybrid microspheres of enzyme |
| CN111359587A (en) * | 2020-04-15 | 2020-07-03 | 厦门大学 | Preparation of quartz capillary hybridization monolithic column based on metal organic framework material |
| CN111359587B (en) * | 2020-04-15 | 2021-05-14 | 厦门大学 | Preparation of quartz capillary hybridization monolithic column based on metal organic framework material |
| CN111533917A (en) * | 2020-04-30 | 2020-08-14 | 曲靖师范学院 | High-critical-dissolution-temperature-type temperature-sensitive zirconium-based metal organic framework material and preparation method thereof |
| CN114699535A (en) * | 2022-01-29 | 2022-07-05 | 西北工业大学 | Multi-effect synergistic joint lubricant with microgel coated metal organic framework and preparation method thereof |
| CN114699535B (en) * | 2022-01-29 | 2024-05-03 | 西北工业大学 | Multi-effect synergistic joint lubricant with microgel coated with metal-organic framework and preparation method thereof |
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