CN106905534B - 一种高稳定稀土有机框架材料的分步制备方法及应用 - Google Patents
一种高稳定稀土有机框架材料的分步制备方法及应用 Download PDFInfo
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- CN106905534B CN106905534B CN201710031482.0A CN201710031482A CN106905534B CN 106905534 B CN106905534 B CN 106905534B CN 201710031482 A CN201710031482 A CN 201710031482A CN 106905534 B CN106905534 B CN 106905534B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 97
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 70
- 239000013384 organic framework Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 rare earth oxygen clusters Chemical class 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims description 24
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
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- 235000001968 nicotinic acid Nutrition 0.000 claims description 6
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- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 3
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 claims description 3
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 claims description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- WFNBSLYTFHMPBY-UHFFFAOYSA-N acetic acid;erbium Chemical compound [Er].CC(O)=O WFNBSLYTFHMPBY-UHFFFAOYSA-N 0.000 claims description 2
- ZBGLGVFYHCSILI-UHFFFAOYSA-N acetic acid;europium Chemical compound [Eu].CC(O)=O ZBGLGVFYHCSILI-UHFFFAOYSA-N 0.000 claims description 2
- KNFUDJRDHMKNRO-UHFFFAOYSA-N acetic acid;terbium Chemical compound [Tb].CC(O)=O KNFUDJRDHMKNRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 2
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 2
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 2
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 2
- 239000002178 crystalline material Substances 0.000 claims 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
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- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052771 Terbium Inorganic materials 0.000 description 18
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 16
- 239000013078 crystal Substances 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 9
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- 229910001431 copper ion Inorganic materials 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
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- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Optics & Photonics (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种高稳定稀土有机框架材料的分步制备方法。第一步是采用结构导向剂制备得到六核稀土氧簇的配合物;第二步是将已制得的六核稀土氧簇配合物与有机配体进行反应,得到高稳定稀土有机框架材料。采用的技术方案是:将稀土盐、结构导向剂溶解在二甲基甲酰胺和水的混合溶液中;超声均匀后转移到密封容器中,加热并保持一天;冷却后在室温保持两周得到六核稀土氧簇配合物;洗涤,过滤并干燥。将六核稀土氧簇配合物、有机配体分散在有机溶剂、水和硝酸的混合溶液中,超声均匀后转移到密封容器中,加热保持两天;自然冷却到室温,得到高稳定稀土有机框架材料。该材料可用于苛刻环境、强酸强碱环境中的气体吸附分离、探测传感和污染物移除等。
Description
技术领域
本发明涉及一种高稳定稀土有机框架材料的分步制备方法及其应用。
背景技术
近年来,稀土有机框架材料(LanthanideMetal Organic Frameworks,简称Ln-MOFs)作为一类新型的发光功能材料受到越来越多的关注,其在气体吸附分离、发光、探测与传感等领域具有广阔的应用前景。目前报道的合成稀土有机框架材料的方法基本都是原位自组装的一步合成法。由于稀土离子配位数可调、配位模式多样、多种溶剂均可参与配位,此方法合成的稀土有机框架材料大部分是无孔的层状结构,大大限制了金属有机框架材料多孔性的优势;此外,这种方法合成的稀土有机框架材料结构可设计性和可预知性较差,生长同构的稀土有机框架材料困难,产物可能存在多种晶相、纯度较低。
本发明采用两步合成的策略,即先采用结构导向剂与稀土离子制备得到六核稀土氧簇配合物,然后再将六核稀土氧簇配合物与有机配体进行反应,得到以六核稀土氧簇为结点的稀土有机框架材料。此方法可对合成产物进行预知和控制,易于合成同构的稀土有机框架材料。通过有机配体的修饰和选择,可设计合成不同孔径大小的稀土有机框架材料。此方法合成的稀土有机框架材料中六核稀土氧簇与配体之间的连接方式为十二连接,稳定性好,可能潜在应用于气体存储与分离、发光与传感等领域。
发明内容
本发明的目的在于提供一类高度可控和可设计的稳定稀土有机框架材料的分步制备方法及其在苛刻环境中的应用。
为实现上述目的,本发明制备的一类高稳定稀土有机框架材料为有序微孔的晶态材料且孔径可调,该稀土有机框架材料属于立方晶系,空间群为Fm-3m。该类材料中稀土离子形成分立的六核稀土氧簇,六核稀土氧簇再与线性有机配体通过十二连接的方式形成三维稳定的框架结构,其结构通式为[(CH3)2NH2]2[Ln6(μ3-OH)8(L)6(H2O)6]·(G)X,式中Ln为Eu3+、Tb3+、Er3+、Yb3+、Nd3+或Gd3+,配体为直线型二甲酸有机桥联配体H2L,G代表孔道内的溶剂,其中X为非定值,采用不同有机桥联配体制备得到的材料孔隙率不同,X随之不同,可通过热重分析和元素分析确定X的具体数值。
上述的直线型二甲酸有机桥联配体H2L可为2-甲基对苯二甲酸、4,4′-联苯二甲酸、6-(4-羧基苯基)烟酸、[2,2'-联吡啶]-5,5'-二甲酸和[1,1':4',1”-三联苯]-4,4”-二甲酸。
本发明的高稳定稀土有机框架材料的制备方法为分两步制备法,第一步是采用结构导向剂与稀土离子先制备得到六核稀土氧簇的配合物;第二步是将第一步制备得到的六核稀土氧簇配合物与直线型二甲酸有机桥联配体进行反应,得到以六核稀土氧簇为结点的稀土有机框架材料。具体来说包括以下步骤:
第一步:将稀土盐和结构导向剂邻氟苯甲酸按摩尔比为1:8一起溶于有机溶剂中,然后加入一定量的去离子水,其中有机溶剂与去离子水的体积比为4:1;超声均匀后转移到密封容器中,加热到110℃并保持一天;冷却后在室温保持两周,得到六核稀土氧簇配合物;洗涤,过滤并干燥。
第二步:将第一步制备得到的六核稀土氧簇配合物和直线型二甲酸有机桥联配体分散在有机溶剂中,然后加入去离子水和硝酸,其中六核稀土氧簇配合物和直线型二甲酸有机桥联配体的摩尔比为1:6,有机溶剂、去离子水和硝酸的体积比为36.5:6:1;混合均匀后放入密闭容器中,在100℃~120℃反应1~3天,自然冷却到室温,离心分离,清洗,得到高稳定稀土有机框架材料。
本发明中,所述的稀土盐为硝酸铕、硝酸铽、硝酸铒、硝酸钕、硝酸钇、硝酸钆、氯化铕、氯化铽、氯化铒、氯化钇、氯化钕、氯化钆、乙酸铕、乙酸铽、乙酸铒、乙酸钇、乙酸钕或乙酸钆。
本发明中,所述的直线型二甲酸有机桥联配体是结构式为(a)的2-甲基对苯二甲酸,结构式为(b)的4,4′-联苯二甲酸,结构式为(c)6-(4-羧基苯基)烟酸,结构式为(d)的[2,2'-联吡啶]-5,5'-二甲酸或结构式为(e)的[1,1':4',1”-三联苯]-4,4”-二甲酸。
本发明制备过程中,所用的有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基乙酰胺、二甲基亚砜、甲醇、乙醇、乙腈、二氧六环和四氢呋喃中的任意一种或者几种按任意比的混合。
本发明的有益效果在于:
1、本发明提出通过两步合成的策略合成一类新型高稳定稀土有机框架材料的制备方法。第一步是采用结构导向剂制备得到六核稀土氧簇配合物;第二步是将六核稀土氧簇配合物与有机配体进行反应,得到高稳定的稀土有机框架材料。该合成方法工艺简单、条件温和,产率高达51%~65%。两步合成策略相比目前报道的一步合成法具有更高的设计性和预知性。
2、本发明制得的稀土有机框架材料结构新颖,结晶程度高,形状为八面体,尺寸大约为0.35×0.35×0.35mm3。产物属于立方晶系,空间群为Fm-3m,晶胞参数为α=β=γ=90°,晶胞体积为晶体理论密度Dc=0.820g cm-3。该类材料中稀土离子形成分立的六核稀土氧簇,六核稀土氧簇与配体之间采用十二连接方式形成三维孔笼结构。框架中含有两种孔笼,分别是八面体孔笼和四面体孔笼,两种孔笼之间通过三角形的窗口连接,BET面积高达1508.3m2g-1。
3、本发明制得的稀土有机框架材料热稳定性和化学稳定性好,氮气气氛中能稳定到300℃;能在各种常见的有机溶剂(N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基乙酰胺、乙腈、乙醇、甲醇、二甲基亚砜、二氧六环和四氢呋喃)、pH=7.4的磷酸缓冲液和强酸强碱(pH=2~12)等条件下保持结构完整。
4、采用三个含有不同数量氮原子但长度相同的有机配体,制备得到三个同构的高稳定稀土有机框架材料。氮位点的引入以及氮原子数量的不同并没有改变材料的连接模式和孔笼大小,并且可实现功能化应用,例如:1)氮原子与乙炔分子具有较强的相互作用,氮位点的引入可增加乙炔的吸附量,同时增加对乙炔和甲烷、乙炔和二氧化碳的选择性分离效果;2)氮原子与铜离子具有较强的配位能力,多氮原子能提高与铜离子的螯合作用,可用于选择性荧光检测工业废水、饮用水中的痕量铜离子。
5、采用不同长度的有机配体与六核稀土氧簇配合物反应,制备得到相同拓扑结构的高稳定稀土有机框架材料。随着配体长度的增加,制得的稀土有机框架材料孔笼随着增大,四面体孔笼的直径由一个苯环时的增加到两个苯环时的再增加到三个苯环时的八面体孔笼的直径则由一个苯环时的增加到两个苯环时的再增加到三个苯环时的实际应用中可根据需要选取合适长度的配体制备所需大小的孔笼材料。
6、本发明制得的高稳定稀土有机框架材料均为阴离子型框架结构,孔道中含有大量用于平衡电荷的二甲胺正离子。通过离子交换的方式,能快速吸附和移除水溶液中阳离子污染物和重金属离子,可用于废水中阳离子污染物的去除。
附图说明
图1是本发明的铽六核稀土氧簇配合物的粉末X射线衍射图;
图2是本发明制备的高稳定稀土有机框架材料TbCNA的晶体结构示意图;
具体实施方式
实例1:
(1)将22.6mg的六水合硝酸铽和56.4mg的邻氟苯甲酸溶解于2mL的N,N-二甲基甲酰胺和0.5mL的水的混合溶液中,搅拌均匀后放入密闭的5mL的反应釜中,在105℃恒温烘箱中反应24个小时,随炉冷却到室温并保持两个星期有大量白色固体沉淀析出,离心分离固液体,固体用N,N-二甲基甲酰胺清洗三次得到铽的六核稀土氧簇配合物,产率为75%。通过Oxford Xcalibur Gemini Ultra单晶衍射仪确定其结构式,测试结果表明:该材料的分子式为C80H59F11N2O37Tb6,属于正方晶系,空间群为I4/m,晶胞参数为 α=β=γ=90°,晶胞体积为Z=2,晶体密度Dc=2.008g cm-3。如图1所示,制得的铽六核稀土氧簇配合物的粉末X-射线衍射图与通过单晶模拟的X-射线衍射图吻合,表明该铽六核稀土氧簇配合物成功制备得到。
(2)将步骤(1)中得到的4.7mg的铽六核稀土氧簇配合物和3.52mg的有机配体6-(4-羧基苯基)烟酸(H2CNA)分散在N,N-二甲基甲酰胺(0.73mL)、去离子水(0.02mL)和硝酸(0.04mL)的混合溶液中,混合均匀后放入密闭容器中,在100℃~120℃反应1~3天,自然冷却到室温,离心分离,清洗,得到铽的高稳定稀土有机框架材料TbCNA。
通过Oxford Xcalibur Gemini Ultra单晶衍射仪确定其结构式,测试结果表明:该材料的结构式为[(CH3)2NH2]2[Tb6(μ3-OH)8(CNA)6(H2O)6]·(DMF)8(H2O)2.5,属于立方晶系,空间群为Fm-3m,晶胞参数为α=β=γ=90°,晶胞体积为Z=8,晶体密度Dc=0.820g cm-3。制备的高稳定稀土有机框架材料TbCNA的单晶结构图如图2所示,该材料是由六个铽离子组成的六核氧簇[Tb6(μ3-OH)8(O2C-)12]和有机桥联配体6-(4-羧基苯基)烟酸形成的三维无限网络结构。每个Tb3+离子与周围的九个氧原子配位,临近的Tb3+离子通过μ3-OH基团和去质子化的羧酸基团连接而形成六核稀土氧簇的次级构建单元[Tb6(μ3-OH)8(O2C-)12],每个次级构建单元与十二个有机配体6-(4-羧基苯基)烟酸连接形成三维孔笼结构。该结构为微孔有序结构,含有两种孔笼,分别是八面体孔笼和四面体孔笼。其中八面体孔笼由十二个有机配体和六个次级构建单元围绕而成,直径为四面体孔笼由六个有机配体和四个次级构建单元组成,直径为
获得的高稳定稀土有机框架材料TbCNA为无色透明晶体,形状为八面体。该材料能在各种有机溶剂(N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二乙基乙酰胺、乙腈、乙醇、甲醇、二甲基亚砜、二氧六环和四氢呋喃)、pH=7.4的磷酸缓冲液和酸碱(pH=3~11)水溶液等条件下保持结构完整,热重分析表明该稀土有机框架材料能稳定到300℃。紫外光激发下,固态的该晶体发射明显的铽离子特征荧光,配体的发射峰完全消失,量子效率为43.4%。水溶液中的发光特性与固态时类似,量子效率为13.99%。
该稳定稀土有机框架材料TbCNA能快速吸附和移除溶剂中的阳离子染料甲基蓝。把TbCNA浸泡在甲基蓝的N,N-二甲基甲酰胺的溶液中,一天以后吸附量达到99%,TbCNA的晶体颜色由无色变为蓝色。甲基蓝吸附饱和的TbCNA浸泡在氯化钠的饱和溶液中,钠离子能再次把阳离子染料甲基蓝交换出来,浸泡三天以后,甲基蓝基本被完全交换,表明该材料能重复使用,潜在应用于污水中阳离子染料的吸附与移除。
实例2:
本例实施步骤(1)与实施例1中实施步骤(1)相同。
(2)将步骤(1)中得到的4.7mg的铽六核稀土氧簇配合物和3.51mg的有机配体4,4′-联苯二甲酸(H2BPDC)分散在N,N-二甲基甲酰胺(0.73mL)、去离子水(0.04mL)和硝酸(0.02mL)的混合溶液中,混合均匀后放入密闭容器中,在100℃~120℃反应1~3天,自然冷却到室温,离心分离,清洗,得到铽的高稳定稀土有机框架材料TbBPDC。
(3)将步骤(1)中得到的4.7mg的铽六核稀土氧簇配合物和3.54mg的有机配体[2,2'-联吡啶]-5,5'-二甲酸(H2BPDDC)分散在N,N-二甲基甲酰胺(0.73mL)、去离子水(0.02mL)和硝酸(0.04mL)的混合溶液中,混合均匀后放入密闭容器中,在100℃~120℃反应1~3天,自然冷却到室温,离心分离,清洗,得到铽的高稳定稀土有机框架材料TbBPDDC。
本例所得的两个高稳定稀土有机框架材料TbBPDC与TbBPDDC具有明显的铽离子特征荧光。由粉末X-射线衍射图可知,该两种材料的粉末X-射线衍射图与实例1中TbCNA通过单晶模拟的X-射线衍射图完全吻合,说明此三种材料是完全同构的。进而表明本发明公开的两步合成策略具有很好的指导性,本方法可对合成的稀土有机框架材料结构进行预判,易于合成同构型稀土有机框架材料。
TbBPDDC相对于TbBPDC和TbCNA具有更多的功能识别氮位点,氮原子与铜离子具有较强的配位能力,因此TbBPDDC可用于废水溶液、强酸强碱溶液中的铜离子选择性荧光检测。铜离子与框架中的氮原子相互作用,导致TbBPDDC 荧光强度的淬灭,铜离子浓度越高,淬灭效果越明显。TbBPDDC中两个识别氮原子的相对位置有利于与铜离子的螯合配位,因而加强了对铜离子的检测性能,检出限位0.47μmol/L,荧光线性响应范围为0~1×10-3mol/L。
实例3:
本例实施步骤(1)与实施例1中实施步骤(1)相同。
(2)将步骤(1)中得到的4.7mg的铽六核稀土氧簇配合物和2.61mg的有机配体2-甲基对苯二甲酸(H2BDC-CH3)分散在N,N-二甲基甲酰胺(0.73mL)、去离子水(0.08mL)和硝酸(0.04mL)的混合溶液中,混合均匀后放入密闭容器中,在100℃~120℃反应1~3天,自然冷却到室温,离心分离,清洗,得到铽的高稳定稀土有机框架材料TbBDC-CH3。
通过Oxford Xcalibur Gemini Ultra单晶衍射仪确定其结构式,测试结果表明:该材料的结构式为[(CH3)2NH2]2[Tb6(μ3-OH)8(BDC-CH3)6(H2O)6]·(DMF)6(H2O),属于立方晶系,空间群为Fm-3m,晶胞参数为α=β=γ=90°,晶胞体积为Z=8,晶体密度Dc=1.481g cm-3。由制备的高稳定稀土有机框架材料TbBDC-CH3的单晶结构图可知,该材料是由六个铽离子组成的六核氧簇[Tb6(μ3-OH)8(O2C-)12]和有机桥联配体2-甲基对苯二甲酸形成的三维无限网络结构。该结构中同样含有八面体孔笼和四面体孔笼,孔笼尺寸相对实例1中的TbCNA整体减小,其中八面体孔笼的直径为四面体孔笼的直径为
(3)将步骤(1)中得到的4.7mg的铽六核稀土氧簇配合物和4.62mg的有机配体[1,1':4',1”-三联苯]-4,4”-二甲酸(H2TPDC)分散在N,N-二甲基甲酰胺(1.46mL)、去离子水(0.09mL)和硝酸(0.13mL)的混合溶液中,混合均匀后放入密闭容器中,在100℃~120℃反应1~3天,自然冷却到室温,离心分离,清洗,得到铽的高稳定稀土有机框架材料TbTPDC。该结构中同样含有八面体孔笼和四面体孔笼,孔笼尺寸相对实例1中的TbCNA整体增大,其中八面体孔笼的直径为四面体孔笼的直径为
本例所得的两个高稳定稀土有机框架材料TbBDC-CH3与TbTPDC同样具有明显的铽离子特征荧光。单晶X射线衍射分析表明该两种稀土有机框架材料与实例1中的TbCNA具有相同的拓扑结构,六核稀土氧簇与配体之间的连接方式相同,都为十二连接。框架中都具有两种孔笼,分别是八面体孔笼和四面体孔笼。随着配体的增长,孔笼的尺寸也随着增加。四面体孔笼的直径由一个苯环时的增加到两个苯环时的再增加到三个苯环时的八面体孔笼的直径则由一个苯环时的增加到两个苯环时的再增加到三个苯环时的实际应用中可根据所需孔笼尺寸选择相应长度的配体获得同样拓扑结构的稀土有机框架材料。
上述具体实施方式用来解释说明本发明,但本发明不应该局限于该实施例和附图所公开的内容。所以凡是不脱离本发明公开的精神下完成的等效或修改,都落入本发明保护范围。
Claims (3)
1.一种高稳定稀土有机框架材料的制备方法,其特征在于:所述的高稳定稀土有机框架材料为有序微孔的晶态材料,该材料中稀土离子形成分立的六核稀土氧簇,六核稀土氧簇与配体之间的连接方式为十二连接,该稀土有机框架材料的结构通式为[(CH3)2NH2]2[Ln6(μ3-OH)8(L)6(H2O)6]·(G)X,式中Ln为Eu3+、Tb3+、Er3+、Yb3+、Nd3+或Gd3+,所述的配体为直线型二甲酸有机桥联配体H2L,G代表孔道内的溶剂;
其制备方法为两步制备法,具体包括以下步骤:
第一步:将稀土盐和结构导向剂邻氟苯甲酸按摩尔比为1:8一起溶于有机溶剂中,然后加入一定量的去离子水,其中有机溶剂与去离子水的体积比为4:1;超声均匀后转移到密封容器中,加热到110℃并保持一天;冷却后在室温保持两周,得到六核稀土氧簇配合物;洗涤,过滤并干燥;
第二步:将第一步制备得到的六核稀土氧簇配合物和直线型二甲酸有机桥联配体分散在有机溶剂中,然后加入去离子水和硝酸,其中六核稀土氧簇配合物和直线型二甲酸有机桥联配体的摩尔比为1:6,有机溶剂、去离子水和硝酸的体积比为36.5:1:2;混合均匀后放入密闭容器中,在100℃~120℃反应1~3天,自然冷却到室温,离心分离,清洗,得到高稳定稀土有机框架材料;
其中,所述的有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的任意一种或者两种按任意比的混合。
2.根据权利要求1所述的高稳定稀土有机框架材料的制备方法,其特征在于所用的稀土盐为硝酸铕、硝酸铽、硝酸铒、硝酸钕、硝酸钇、硝酸钆、氯化铕、氯化铽、氯化铒、氯化钇、氯化钕、氯化钆、乙酸铕、乙酸铽、乙酸铒、乙酸钇、乙酸钕或乙酸钆。
3.根据权利要求1所述的高稳定稀土有机框架材料的制备方法,其特征在于所用的直线型二甲酸有机桥联配体是结构式为(a)的2-甲基对苯二甲酸,结构式为(b)的4,4′-联苯二甲酸,结构式为(c)6-(4-羧基苯基)烟酸,结构式为(d)的[2,2'-联吡啶]-5,5'-二甲酸或结构式为(e)的[1,1':4',1”-三联苯]-4,4”-二甲酸,
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