CN105330681A - Microporous rare earth cluster metal organic anion framework and preparation method and application thereof - Google Patents
Microporous rare earth cluster metal organic anion framework and preparation method and application thereof Download PDFInfo
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- CN105330681A CN105330681A CN201510705960.2A CN201510705960A CN105330681A CN 105330681 A CN105330681 A CN 105330681A CN 201510705960 A CN201510705960 A CN 201510705960A CN 105330681 A CN105330681 A CN 105330681A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 42
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 42
- 150000002891 organic anions Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 claims abstract description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical group C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 35
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000012621 metal-organic framework Substances 0.000 description 9
- 150000002500 ions Chemical group 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 241000405217 Viola <butterfly> Species 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 description 4
- 150000002892 organic cations Chemical class 0.000 description 4
- 229940073450 sudan red Drugs 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- MECHNRXZTMCUDQ-RKHKHRCZSA-N vitamin D2 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)/C=C/[C@H](C)C(C)C)=C\C=C1\C[C@@H](O)CCC1=C MECHNRXZTMCUDQ-RKHKHRCZSA-N 0.000 description 4
- 235000001892 vitamin D2 Nutrition 0.000 description 4
- 239000011653 vitamin D2 Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
-
- 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]
-
- 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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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention relates to a microporous rare earth cluster metal organic anion framework and a preparation method and application thereof. According to the technical scheme, the preparation method comprises the steps that RE(NO<3>)<3>/4, 4'-diphenyldicarboxylic acid, o-fluorobenzoic acid, N, N-dimethyl formamide and ethanol are added into a container and stirred at the normal temperature; the container is sealed and then placed into a drying oven, and the container is maintained for 1-2 days at the temperature of 300-400 K; the mixture is cooled slowly to the room temperature and left standing for 20-30 hours, and crystals are obtained; N, N-dimethyl formamide is used for washing the mixture, filtration and drying are conducted, and a target product is obtained. The microporous rare earth cluster metal organic anion framework prepared through the preparation method can serve as an adsorption base material for adsorbing cation type organic dyestuff, and the cation organic dyestuff is separated in an efficient and selective mode.
Description
Technical field
The present invention relates to a kind of metal organic anion skeleton and its preparation method and application, specifically, relate to a kind of bunch metal organic anion skeleton of the rare earth based on micropore with cationic exchange function and preparation method thereof, and to the absorption of organic dye and be separated application.
Background technology
In host-guest chemistry field, metallic organic framework (MOFs) is as a kind of novel molecular functional materials, and the research about it spans multiple ambits such as inorganic chemistry, organic chemistry, physical chemistry, materials chemistry, crystal engineering, topology, supramolecular chemistry and coordination chemistry.As the product that multidisciplinary field intersects, the design and synthesis of metal organic framework compound and performance study have developed into one of field that Recent study enlivens very much.Recently, charged MOFs more and more can cause the interest of investigator by electric charge inducing ion exchange process, this makes rear synthetic modification process simple and easy and controlled.In these MOFs, the MOFs of anionic produces in the process of be everlasting neutral organic ligand and metal ion structure skeleton, therefore, needs the positively charged ion beyond skeleton to play the effect of charge balance.Counter cation occupies in the hole of skeleton usually, with metal ion not coordination or there is weak coordination.This material is build to provide a unique chance based on the cation receptor of cationic exchange.On the other hand, inorganic-organic hybridization MOFs has diversified inner microenvironment, and can be used for identifying and being separated cationic system as outstanding material of main part, this process will depend on the size in MOFs hole, geometric shape and binding ability.Compared with neutral backbone, the MOFs research of anionic is very limited.
China has been now global maximum DYE PRODUCTION state, and annual dyestuff output reaches 150000 tons, and environmental pollution phenomenon is very serious, increasingly sophisticated along with dye structure, the development of dyeing, performance is more and more stable, and the process of these waste water from dyestuff is more complicated.Utilizing the different different types of waste water from dyestuff of sewage disposal technology process, realize sewage qualified discharge or recycling, is current problem in the urgent need to address.
Summary of the invention
The object of the invention is to utilize six core Eu bunches as metal node, utilize 4,4 '-biphenyl dicarboxylic acid, as organic ligand, at a certain temperature, utilizes the method for solvent thermal to synthesize a kind of rare earth bunch metal organic anion skeleton of micropore.
The technical solution used in the present invention is: a kind of rare earth bunch metal organic anion skeleton of micropore, comprises the following steps:
1) by RE (NO
3)
3, 4,4 '-biphenyl dicarboxylic acid, o-fluorobenzoic acid, DMF and ethanol add in container, under normal temperature, stir; Wherein, RE is rare earth metal.Preferably, RE (NO
3)
3for Eu (NO
3)
3.In molar ratio, Eu (NO
3)
3: 4,4 '-biphenyl dicarboxylic acid: o-fluorobenzoic acid=1:1-1.5:3-3.5.
2) put into baking oven by after container sealing, under 300-400K, keep 1-2 days; Preferably, temperature rise rate is 2-8 DEG C of min
-1.
3) progressively cool to room temperature, leave standstill 20-30h, obtain crystal; Preferably, the rate of temperature fall progressively cooling to room temperature is 2-8 DEG C of h
-1, and at room temperature leave standstill at least 24 hours.
4) crystal DMF is washed, filter, dry, obtain target product.
The invention has the beneficial effects as follows: the rare earth bunch metal organic anion skeleton of the micropore prepared by the present invention can be used as the rear synthesis field that material of main part is applied to host-guest chemistry.A rare earth bunch metal organic anion skeleton for prepared micropore can adsorb cationic organic dye as adsorbing base, and efficient selective is separated Cationic organic dyes.The rare earth bunch metal organic anion skeleton preparation method of micropore of the present invention is simple, has great application prospect.
Accompanying drawing explanation
Fig. 1 is the synthesis schematic diagram of the rare earth bunch metal organic anion skeleton of micropore of the present invention.
Fig. 2 is the XRD figure of the rare earth bunch metal organic anion skeleton of micropore of the present invention.
Fig. 3 a be micropore of the present invention a kind of cage of rare earth bunch metal organic anion skeleton (
) schematic diagram.
Fig. 3 b be micropore of the present invention a kind of cage of rare earth bunch metal organic anion skeleton (
) schematic diagram.
Fig. 3 c be micropore of the present invention rare earth bunch metal organic anion skeleton duct (
) schematic diagram.
Fig. 4 is the cage skeleton structure schematic diagram of the rare earth bunch metal organic anion skeleton of micropore of the present invention.
Fig. 5 is the rare earth bunch metal organic anion skeleton selective separation tropeolin-D of micropore of the present invention and the ultraviolet-visible spectrogram of methylene blue organic dye.
Fig. 6 the present invention is based on the rare earth bunch metal organic anion skeleton selective separation Sudan red of micropore and the ultraviolet-visible spectrogram of methylene blue organic dye.
Fig. 7 the present invention is based on the rare earth bunch metal organic anion skeleton selective separation Viola crystallina of micropore and the ultraviolet-visible spectrogram of methylene blue organic dye.
Embodiment
The rare earth bunch metal organic anion skeleton of embodiment 1 micropore
By the Eu (NO of 0.0225mmol
3)
3, 4 of 0.0225mmol, 4 '-biphenyl dicarboxylic acid, the o-fluorobenzoic acid of 0.0675mmol, the DMF (DMF) of 2ml, it is in the vial of 5ml that the ethanol of 0.5ml adds volume, under normal temperature, stirs 30 minutes.Vial good seal is put into baking oven.Heating makes the temperature of baking oven reach 378K from room temperature, and temperature rise rate is 5 DEG C of min
-1, be incubated 36 hours at this temperature.With 5 DEG C of h
-1rate of temperature fall progressively cool to room temperature, obtain faint yellow cubic type crystal; With N, N '-dimethyl methane amide (DMF) solution washing, filtration are also dry in atmosphere, and be the rare earth bunch metal organic anion skeleton of target product micropore, productive rate is 68%.
As shown in figs 2-4, this crystalline structure belongs to isometric system to the structure of the rare earth bunch metal organic anion skeleton of the micropore of the present invention's synthesis, and spacer is Fm-3m.Molecular formula is: [(CH
3)
2nH
2]
2[Eu
6(μ
3-OH)
8(BPDC)
6(H
2o)
6] 32DMF.This compound is by six core [Eu
6(μ
3-OH)
8(O
2c –)
6] as node, by the three-dimensional structure of dicarboxylates bridging.Positively charged ion [(CH
3)
2nH
2]
+the duct of this MOF is arranged in as counter ion.Each 4,4 '-biphenyl dicarboxylic acid part and four Eu
3+ion coordination, six Eu
3+ion and six come from 4, the oxygen on the carboxyl of 4 '-biphenyl dicarboxylic acid and six μ
3-OH coordination.Along b-direction of principal axis, this structure has two kinds of different cage structures, and cage is of a size of
and there is a duct
The rare earth bunch metal organic anion skeleton selective adsorption organic dye of embodiment 2 one kinds of micropores
Method: adsorb as adsorbing base being mixed with organic dye using a rare earth bunch metal organic anion skeleton for the micropore of embodiment 1 preparation.
1) get OAD tropeolin-D and organic cation dye methylene blue is dissolved in DMF solution, the concentration obtaining tropeolin-D and methylene blue is respectively 5 × 10
-5the mixed dye solution of M.
Get mixed dye solution 5ml, add the rare earth bunch metal organic anion skeleton crystal 20mg of micropore, soak under room temperature.The change of dye strength in mixed dye solution is detected with uv-vis spectra.As shown in Figure 5, in figure, peak value is followed successively by 0min to result from top to bottom, 10min, 30min, 1h, 2h, 3h, 4h, 6h, 24h.As seen from Figure 5, in mixed dye solution, methylene blue reduces gradually in the characteristic peak intensity of 650nm, and tropeolin-D is constant in the characteristic peak intensity of 420nm.This illustrates that the crystalline structure of the rare earth bunch metal organic anion skeleton of a kind of micropore of the present invention has good selective adsorption to methylene blue.
The rare earth bunch metal organic anion skeleton of micropore of the present invention is when 6h, and reach 75% to the adsorption rate of methylene blue, when 24h, adsorption rate reaches 98%.
2) get organic zeroth order dyestuff Sudan red and organic cation dye methylene blue is dissolved in DMF solution, the concentration obtaining Sudan red and methylene blue is respectively 5 × 10
-5the mixed dye solution of M.
Get mixed dye solution 5ml, add the rare earth bunch metal organic anion skeleton crystal 20mg of micropore, soak under room temperature.The change of dye strength in mixed dye solution is detected with uv-vis spectra.As shown in Figure 6, in Fig. 6, peak value is followed successively by 0min to result from top to bottom, 10min, 30min, 1h, 2h, 3h, 4h, 5h, 7h, 24h.As seen from Figure 6, in mixed dye solution, methylene blue reduces gradually in the characteristic peak intensity of 650nm, and Sudan red is constant in the characteristic peak intensity of 480nm.This illustrates that the crystalline structure of the rare earth bunch metal organic anion skeleton of micropore of the present invention has good selective adsorption to methylene blue.
3) get organic cation dye Viola crystallina and organic cation dye methylene blue is dissolved in DMF solution, the concentration obtaining Viola crystallina and methylene blue is respectively 5 × 10
-5the mixed dye solution of M.
Get mixed dye solution 5ml, add the rare earth bunch metal organic anion skeleton crystal 20mg of micropore, soak under room temperature.The change of dye strength in mixed dye solution is detected with uv-vis spectra.As shown in Figure 7, in Fig. 7, peak value is followed successively by 0min to result from top to bottom, 10min, 30min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 24h.As seen from Figure 7, in mixed dye solution, methylene blue reduces gradually in the characteristic peak intensity of 650nm, and Viola crystallina is constant in the characteristic peak intensity of 600nm.This illustrates that the crystalline structure of the rare earth bunch metal organic anion skeleton of micropore of the present invention has good selective adsorption to methylene blue.
Claims (9)
1. a rare earth bunch metal organic anion skeleton for micropore, is characterized in that: preparation method comprises the steps:
1) by RE (NO
3)
3, 4,4 '-biphenyl dicarboxylic acid, o-fluorobenzoic acid, DMF and ethanol add in container, under normal temperature, stir; Wherein, RE is rare earth metal;
2) put into baking oven by after container sealing, under 300-400K, keep 1-2 days;
3) progressively cool to room temperature, leave standstill 24-30h, filter, obtain crystal;
4) crystal DMF washs, and filters, dry, obtains target product.
2. the rare earth bunch metal organic anion skeleton of a kind of micropore according to claim 1, is characterized in that: the rare earth bunch metal organic anion skeleton of described micropore, its crystal belongs to isometric system, and spacer is Fm-3m.
3. the rare earth bunch metal organic anion skeleton of a kind of micropore according to claim 1, is characterized in that: described RE (NO
3)
3for Eu (NO
3)
3.
4. the rare earth bunch metal organic anion skeleton of a kind of micropore according to claim 1, is characterized in that: in molar ratio, Eu (NO
3)
3: 4,4 '-biphenyl dicarboxylic acid: o-fluorobenzoic acid=1:1-1.5:3-3.5.
5. the rare earth bunch metal organic anion skeleton of a kind of micropore according to claim 1,2,3 or 4, is characterized in that: step 2) in, put into baking oven by after container sealing, temperature rise rate is 2-8 DEG C of min
-1.
6. the rare earth bunch metal organic anion skeleton of a kind of micropore according to claim 1,2,3 or 4, is characterized in that: step 3) in, the described rate of temperature fall progressively cooling to room temperature is 2-8 DEG C of h
-1.
7. the rare earth bunch metal organic anion skeleton of micropore according to claim 1 is as the application of adsorbing base in Liquidity limit type organic dye.
8. application according to claim 7, is characterized in that, method is as follows: in the DMF solution containing cationic organic dye, adds the rare earth bunch metal organic anion skeleton of micropore according to claim 1, soaks, adsorbs.
9. the application according to claim 7 or 8, is characterized in that: described cationic organic dye is methylene blue.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753891A (en) * | 2016-03-23 | 2016-07-13 | 浙江大学 | Rare earth organic framework material for fluorescence detection of trace water and preparation method of rare earth organic framework material |
| CN106397467A (en) * | 2016-08-31 | 2017-02-15 | 北京化工大学 | Metal-organic skeleton functionalized fluorescent material, preparation method and application thereof |
| CN106632433A (en) * | 2016-11-18 | 2017-05-10 | 大连理工大学 | Luminous metal organic framework material for uranyl ion detection in water and preparation method thereof |
| CN106699783A (en) * | 2016-11-23 | 2017-05-24 | 浙江大学 | High-connection rare earth organic framework material for fluorescence detection of alcoholic strength and preparation method of high-connection rare earth organic framework material |
| CN106905534A (en) * | 2017-01-17 | 2017-06-30 | 浙江大学 | A kind of substep preparation method and application of high stable rare earth organic framework materials |
| CN107245149A (en) * | 2017-06-21 | 2017-10-13 | 辽宁大学 | The six core rare earth cluster metal-organic framework materials of one kind based on Eu (III) and its preparation method and application |
| CN107497402A (en) * | 2017-09-25 | 2017-12-22 | 江苏大学 | A kind of water stabilizing dye adsorbent and preparation method |
| CN109821575A (en) * | 2019-02-18 | 2019-05-31 | 河海大学 | A kind of terbium Base Metal organic framework material Tb-MOF and preparation method thereof, methylene blue dye photocatalytic degradation method |
| CN109821576A (en) * | 2019-02-18 | 2019-05-31 | 河海大学 | A kind of dysprosium Base Metal organic framework material Dy-MOF and preparation method thereof, methylene blue dye photocatalytic degradation method |
| CN109821574A (en) * | 2019-02-18 | 2019-05-31 | 河海大学 | A kind of europium Base Metal organic framework material Eu-MOF and preparation method thereof, congo red photocatalytic degradation method |
| CN110560004A (en) * | 2019-09-19 | 2019-12-13 | 西北师范大学 | Eu-MOF complex, synthesis thereof and application of Eu-MOF complex in adsorption of organic dye in wastewater |
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| CN105753891A (en) * | 2016-03-23 | 2016-07-13 | 浙江大学 | Rare earth organic framework material for fluorescence detection of trace water and preparation method of rare earth organic framework material |
| CN105753891B (en) * | 2016-03-23 | 2018-04-20 | 浙江大学 | A kind of rare earth organic framework materials for trace water fluoroscopic examination and preparation method thereof |
| CN106397467A (en) * | 2016-08-31 | 2017-02-15 | 北京化工大学 | Metal-organic skeleton functionalized fluorescent material, preparation method and application thereof |
| CN106397467B (en) * | 2016-08-31 | 2018-07-06 | 北京化工大学 | A kind of metal-organic framework functional fluorescence material, preparation method and applications |
| CN106632433A (en) * | 2016-11-18 | 2017-05-10 | 大连理工大学 | Luminous metal organic framework material for uranyl ion detection in water and preparation method thereof |
| CN106632433B (en) * | 2016-11-18 | 2018-09-04 | 大连理工大学 | A kind of luminescent metal organic framework material and preparation method thereof detected for uranyl ion in water |
| CN106699783B (en) * | 2016-11-23 | 2018-12-14 | 浙江大学 | A kind of high connection rare earth organic framework materials and preparation method thereof for alcoholic strength fluorescence detection |
| CN106699783A (en) * | 2016-11-23 | 2017-05-24 | 浙江大学 | High-connection rare earth organic framework material for fluorescence detection of alcoholic strength and preparation method of high-connection rare earth organic framework material |
| CN106905534A (en) * | 2017-01-17 | 2017-06-30 | 浙江大学 | A kind of substep preparation method and application of high stable rare earth organic framework materials |
| CN106905534B (en) * | 2017-01-17 | 2019-08-13 | 浙江大学 | A kind of substep preparation method and application of high stable rare earth organic framework materials |
| CN107245149A (en) * | 2017-06-21 | 2017-10-13 | 辽宁大学 | The six core rare earth cluster metal-organic framework materials of one kind based on Eu (III) and its preparation method and application |
| CN107497402A (en) * | 2017-09-25 | 2017-12-22 | 江苏大学 | A kind of water stabilizing dye adsorbent and preparation method |
| CN107497402B (en) * | 2017-09-25 | 2019-12-31 | 江苏大学 | Water-stable dye adsorbent and preparation method thereof |
| CN109821575A (en) * | 2019-02-18 | 2019-05-31 | 河海大学 | A kind of terbium Base Metal organic framework material Tb-MOF and preparation method thereof, methylene blue dye photocatalytic degradation method |
| CN109821576A (en) * | 2019-02-18 | 2019-05-31 | 河海大学 | A kind of dysprosium Base Metal organic framework material Dy-MOF and preparation method thereof, methylene blue dye photocatalytic degradation method |
| CN109821574A (en) * | 2019-02-18 | 2019-05-31 | 河海大学 | A kind of europium Base Metal organic framework material Eu-MOF and preparation method thereof, congo red photocatalytic degradation method |
| CN109821576B (en) * | 2019-02-18 | 2021-07-27 | 河海大学 | Dysprosium-based metal organic framework material Dy-MOF, preparation method thereof and methylene blue dye photocatalytic degradation method |
| CN109821574B (en) * | 2019-02-18 | 2021-07-30 | 河海大学 | Europium-based metal organic framework material Eu-MOF, preparation method thereof and Congo red dye photocatalytic degradation method |
| CN109821575B (en) * | 2019-02-18 | 2021-07-30 | 河海大学 | Terbium-based metal organic framework material Tb-MOF, preparation method thereof and methylene blue dye photocatalytic degradation method |
| CN110560004A (en) * | 2019-09-19 | 2019-12-13 | 西北师范大学 | Eu-MOF complex, synthesis thereof and application of Eu-MOF complex in adsorption of organic dye in wastewater |
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