CN106748731A - The preparation method of complex nanometer rods of the one kind with MIL 88B (Fe) structure - Google Patents
The preparation method of complex nanometer rods of the one kind with MIL 88B (Fe) structure Download PDFInfo
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- CN106748731A CN106748731A CN201611096223.8A CN201611096223A CN106748731A CN 106748731 A CN106748731 A CN 106748731A CN 201611096223 A CN201611096223 A CN 201611096223A CN 106748731 A CN106748731 A CN 106748731A
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- terephthalic acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000013215 MIL-88B Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000243 solution Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000000640 hydroxylating effect Effects 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000003911 water pollution Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000008187 granular material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002372 labelling Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 206010009691 Clubbing Diseases 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BULOCEWDRJUMEL-UHFFFAOYSA-N benzene formaldehyde Chemical group C=O.C1=CC=CC=C1.C=O BULOCEWDRJUMEL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229960002163 hydrogen peroxide Drugs 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- 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
- B01J2531/0213—Complexes 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
- 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
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of bar-shaped metal organic hybrid complex MIL 88B (Fe) and preparation method thereof, belong to novel nano catalysis material preparation field.Synthetic method used of the invention is solwution method.Comprise the following steps that：Anhydrous ferric chloride and terephthalic acid (TPA) (tp) are dissolved into ethylene glycol (EG) and the NaOH aqueous solution respectively first, then above two solution are mixed and is heated in oil bath and is reacted.The nano catalytic material is by dark red powder solid is obtained after products therefrom centrifugation, washing, drying.Preparation method is simple of the present invention is easy; the catalytic nanometer strong mechanical property of synthesis, experiment condition environmental protection is adapted to large-scale production; and the material has good catalytic performance to the hydroxylating of toluene, there is applications well prospect in the field such as environmental protection and water pollution control.
Description
Technical field
The present invention relates to a kind of bar-shaped metal organic hybrid complex MIL-88B (Fe) and preparation method thereof, belong to new
Type technical field of function materials.
Background technology
Metal organic frame (Metal-Organic Frameworks, MOFs) complex is by ion cluster or gold
A category class novel inorganic-organic Hybrid Materials for being formed under the connection of various organic ligands of ion, with specific surface area greatly, hole
The good characteristics such as gap rate is high, stable performance, density are small, in recent years gas storage with separate, be catalyzed, the aspect such as sense and show
Come excellent properties and receive much concern.But traditional MOFs researchs are concentrated mainly on block crystalline state or pulverulence field, one
Determine to be limited in degree the range of application of MOFs.For example in order to carry out drug delivery using MOFs, it is necessary to be contracted to receive
Meter ruler cun.Thus, in order to meet wider application demand, people need to prepare the MOFs cooperations of miniaturization to micro/nano-scale
Thing.Meanwhile, with size reduction to nm regime, its " nano effect " will make MOFs complexs in optics, electricity, catalysis etc.
Aspect shows more excellent performance.Such as, compared with traditional catalyst material, the MOFs complexs of micro/nano-scale can be with
Easily it is evenly dispersed in the reaction mediums such as water, it is fully contacted with reaction substrate homogeneous so as to play simulation
The effect of catalysis.On the other hand, for homogeneous catalyst, the MOFs complexs of micro/nano-scale can be by the side such as centrifugation
Formula is easier separated and recovered from recycling from reaction system.This feature of the MOFs complexs of micro/nano-scale can be effective
Simplify the separating-purifying process of catalysate, so that lowering apparatus device requirement and production cost.Additionally, with loose structure
MOFs complexs can also be as carrier material carried noble metal nanocatalyst, so as to reduce noble metal catalyst be catalyzed
There is the probability for inactivating of reuniting in journey.
The content of the invention
Metal organic complex based on MOFs synthesis micro-nano sizes is for expanding the range of application of MOFs materials, improving it
Application value is significant, and preparation method and the performance study of such material are the study hotspots of current field of coordinative chemistry
One of.It is an object of the invention to provide a kind of preparation of the metallic organic frame complex MIL-88B (Fe) with club shaped structure
Method, and its performance applications as catalyst in terms of toluene hydroxylating.
The purpose of the present invention is achieved through the following technical solutions, a kind of with good catalysis toluene hydroxylating performance
Prepared by the solwution method of bar-shaped MIL-88B (Fe) metallic organic frame complex, comprise the following steps：
1）Anhydrous ferric chloride is weighed respectively by certain mol proportion in round bottom beaker, terephthalic acid (TPA) (tp) [or 2- ammonia is weighed
Base terephthalic acid (TPA) (atp), or 2,6- naphthalene diacid (nda)] solid is in beaker；
2）To step 1）The NaOH aqueous solution, and ultrasound is added in beaker used to promote terephthalic acid (TPA) (tp) [or 2- amino
Terephthalic acid (TPA) (atp), or 2,6- naphthalene diacid (nda)] dissolving；
3）To step 1）Ethylene glycol is added in round-bottomed flask（EG）And rock so that anhydrous ferric chloride dissolves；
4）By step 2）Resulting solution is added to step 3）In resulting solution, and rocking round-bottomed flask is well mixed the two；
5）By step 4）Round-bottomed flask used is put into 100oHeating response 30 minutes in C oil bath pans；
6）By step 5）Resulting solution centrifugation, and washed with deionized water and ethanol, and 60oC is obtained most after drying
End-product.
First can be in the reaction catalyzed using bar-shaped MIL-88B (Fe) complex prepared by above-mentioned steps as catalyst
The hydroxylating of benzene.
Beneficial effects of the present invention：
（1）Product prepared by the present invention is MIL-88B (Fe) complex nanometer rods, and its preparation method is simple, and controllability is strong；
（2）Novel clubbed MIL-88B (Fe) complex prepared by the present invention is small-sized, big compared to block complex specific surface area
And be easily uniformly dispersed, have a wide range of application；
（3）MIL-88B (Fe) complexs prepared by the present invention have good catalytic performance to the hydroxylating of toluene；
（4）Preparation of the invention only needs the conventional conventional equipment in laboratory, is not required to special equipment, and technical process is simple to operation；
（5）The present invention is raw materials used cheap and easy to get, can effectively reduce the synthesis cost of material, is adapted to a large amount of productions to meet work
Industry application demand.
Brief description of the drawings
Fig. 1 is that bar-shaped MIL-88B (Fe) complexs prepared by the inventive method transmit electricity with JEOL JEOL-1400
Multiple transmission electron microscopes shot after the micro- sem observation of son（TEM）One of in photo；Wherein, Fig. 1 a are MIL-88B (Fe) cooperations
Composition granule low power TEM image, Fig. 1 b are that MIL-88B (Fe) coordinates composition granule high power TEM image；
Fig. 2 is the X-ray diffraction of MIL-88B (Fe) the cooperation composition granules prepared by the inventive method（XRD）Figure, it is (wherein organic
Part is Fetp for the Product Labeling of terephthalic acid (TPA)；Organic ligand is Featp for the Product Labeling of 2- amino terephthalic acid (TPA)s；
Organic ligand is that the Product Labeling of 2,6- naphthalene diacid is Fenda), as can be seen from the figure experiment three parts of spectrograms of sample of gained and
Diffraction maximum position and peak shape are coincide good in analogue spectrums, it was demonstrated that the theoretical mould of sample structure and MIL-88B (Fe) complex
Intend structure consistent, and prepared sample purity is good；
MIL-88B (Fe) complex-catalyzed toluene conversion prepared by Fig. 3 the inventive method is the product gas phase color of cresols
Spectrum separates spectrogram；
Specific embodiment
Present disclosure is described in further detail below by specific implementation example with reference, but these embodiments
It is not intended to limit protection scope of the present invention.
Embodiment 1
Anhydrous ferric chloride 0.64mmol is weighed first to be dissolved into 8 milliliters of EG, is weighed terephthalic acid (TPA) 0.36mmol and is dissolved into 8 millis
Rise in NaOH solution, ultrasound mixes the two after promoting dissolving, is then placed in 50 oCReacted 1 hour in oil bath pan, be then centrifuged for
Separate, 60 after being cleaned with deionized water and EtOH Sonicate respectivelyoDried under C, MIL-88B (Fe) is obtained and coordinates composition granule.
Embodiment 2
Anhydrous ferric chloride 0.64mmol is weighed first to be dissolved into 8 milliliters of EG, is weighed terephthalic acid (TPA) 0.36mmol and is dissolved into 4 millis
Rise NaOH solution in, ultrasound after the two is mixed, after be put into 100 oCReacted 15 minutes in oil bath pan, be then centrifuged for separating, respectively
60 after being cleaned with deionized water and EtOH SonicateoDried under C, MIL-88B (Fe) is obtained and coordinates composition granule.
Embodiment 3
Anhydrous ferric chloride 0.64mmol is weighed first to be dissolved into 8 milliliters of EG, weighs 0.36mmol 2- amino terephthalic acid (TPA)s
（2-atp）Be dissolved into 8 milliliters of NaOH solutions, the two mixed, after be put into 100 oCReacted 15 minutes in oil bath pan, Ran Houli
The heart is separated, 60 after being cleaned with deionized water and EtOH Sonicate respectivelyoDried under C, MIL-88B (Fe) is obtained and coordinates composition granule.
Embodiment 4
Iron chloride 0.64mmol is weighed first to be dissolved into 8 milliliters of EG, weighs 0.36mmol NDAs (nda) dissolving
To in 8 milliliters of NaOH solutions, the two is mixed, after be put into 100 oCReacted 15 minutes in oil bath pan, be then centrifuged for separating, respectively
60 after being cleaned with deionized water and EtOH SonicateoDried under C, MIL-88B (Fe) is obtained and coordinates composition granule.
Embodiment 5
MIL-88B (Fe) hydroxylated catalytic performance test of complex-catalyzed toluene prepared by the inventive method.
The catalytic performance of MIL-88B (Fe) complex prepared by the inventive method is separated in fact by doing gas-chromatography
Test, probe into the product characteristicses obtained after catalysis toluene solution, evaluated using sample conversion data.Specific steps are such as
Under：
Coordinate composition granule, Ran Houjia toward addition water, toluene solution and proper catalyst MIL-88B (Fe) in round-bottomed flask first
Enter hydrogenperoxide steam generator, finally gas-chromatography separating experiment is done in the h of stirring reaction 5 samplings under the conditions of 70 DEG C, probes into product
Matter.Experimental product is analyzed further with gas-chromatography separating experiment, turning for toluene is drawn by meteorological separation chromatography map analysis
Rate is 43%, and product is respectively benzaldehyde, orthoresol and paracresol, by chromatogram it was additionally observed that selectivity of product is benzene
Formaldehyde:Orthoresol:Paracresol=4:34:62.
Accompanying drawing 3 is the product gas-chromatography discrete spectrum in the prepared sample catalysis toluene hydroxylating of the present invention
Figure.
Claims (5)
1. a kind of preparation method of bar-shaped MIL-88B (Fe) complex, it is characterised in that as follows the step of preparation method：
1）Weigh the anhydrous ferric chloride of certain mol proportion, terephthalic acid (TPA) (or 2- amino terephthalic acid (TPA)s, or 2,6- naphthalene
Diacid) and be dissolved into respectively in EG the and NaOH aqueous solution；
2）By above-mentioned steps 1）Gained mixed solution is transferred in round-bottomed flask, is reacted in oil bath pan；
3）It is centrifuged and washs after drying and obtains dark red powder product；
Anhydrous ferric chloride and terephthalic acid (TPA)（Or 2- amino terephthalic acid (TPA)s, or 2,6- naphthalene diacid）Amount ratio be：
0.64mmol：0.36mmol.
2. the preparation method of bar-shaped MIL-88B (Fe) complex according to claim 1, it is characterised in that source of iron used
It is anhydrous ferric chloride.
3. the preparation method of bar-shaped MIL-88B (Fe) complex according to claim 1, it is characterised in that used organic
Part can be terephthalic acid (TPA), or 2- amino terephthalic acid (TPA)s, or 2,6- naphthalene diacid.
4. the preparation method of bar-shaped MIL-88B (Fe) complex according to claim 1, it is characterised in that solvent for use
It is ethylene glycol (EG) and the NaOH aqueous solution.
5. the preparation method of bar-shaped MIL-88B (Fe) complex according to claim 1, it is characterised in that step 3）Institute
State oil bath reaction temperature interval for 50-100oC, the reaction time is 15 to 60 minutes.
Priority Applications (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112934271A (en) * | 2021-01-29 | 2021-06-11 | 广东工业大学 | Porous nanowire with metal-organic framework and preparation method and application thereof |
| CN115353452A (en) * | 2022-09-14 | 2022-11-18 | 巢湖学院 | Iron benzoate complex and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103657596A (en) * | 2013-12-13 | 2014-03-26 | 天津工业大学 | Synthesis method of magnetic metal organic framework composite material |
| CN104857933A (en) * | 2015-05-18 | 2015-08-26 | 苏州汇通色谱分离纯化有限公司 | Preparation and application of core-shell type magnetic metal organic framework nano-particles |
| CN104998688A (en) * | 2015-06-17 | 2015-10-28 | 北京科技大学 | Magnetic composite metal organic framework material of multi-stage structure and manufacturing method thereof |
| CN105032486A (en) * | 2015-06-17 | 2015-11-11 | 济南大学 | Preparation method of spindle-shaped metal organic framework compound grains |
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| CN103657596A (en) * | 2013-12-13 | 2014-03-26 | 天津工业大学 | Synthesis method of magnetic metal organic framework composite material |
| CN104857933A (en) * | 2015-05-18 | 2015-08-26 | 苏州汇通色谱分离纯化有限公司 | Preparation and application of core-shell type magnetic metal organic framework nano-particles |
| CN104998688A (en) * | 2015-06-17 | 2015-10-28 | 北京科技大学 | Magnetic composite metal organic framework material of multi-stage structure and manufacturing method thereof |
| CN105032486A (en) * | 2015-06-17 | 2015-11-11 | 济南大学 | Preparation method of spindle-shaped metal organic framework compound grains |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112934271A (en) * | 2021-01-29 | 2021-06-11 | 广东工业大学 | Porous nanowire with metal-organic framework and preparation method and application thereof |
| CN112934271B (en) * | 2021-01-29 | 2022-10-28 | 广东工业大学 | Porous nanowire with metal-organic framework and preparation method and application thereof |
| CN115353452A (en) * | 2022-09-14 | 2022-11-18 | 巢湖学院 | Iron benzoate complex and preparation method and application thereof |
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