CN105384762B - A kind of synthetic method of metal-organic framework materials MIL 53 (Al) - Google Patents
A kind of synthetic method of metal-organic framework materials MIL 53 (Al) Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- 238000010189 synthetic method Methods 0.000 title claims abstract description 21
- 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 100
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 23
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 18
- 230000004913 activation Effects 0.000 claims abstract description 12
- 239000013206 MIL-53 Substances 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 34
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000012043 crude product Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 14
- 235000019253 formic acid Nutrition 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052710 silicon Inorganic materials 0.000 abstract description 9
- 239000010703 silicon Substances 0.000 abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 abstract description 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000003205 fragrance Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 238000001994 activation Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910002702 AlO4(OH)2 Inorganic materials 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 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
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QMKYBPDZANOJGF-UHFFFAOYSA-N trimesic acid Natural products OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the preparing technical field of metal-organic framework materials, and in particular to (structural formula is Al (OH) [O to a kind of metal-organic framework materials-MIL 53 (Al) of fragrance organic carboxyl acid and aluminium coordination2C‑C6H4‑CO2]) synthetic method, for this method using aluminium hydroxide and terephthalic acid (TPA) as raw material, acid is auxiliary agent, prepares MIL 53 (Al) using hydro-thermal method, high-temperature activation obtains metal organic framework-MIL 53 (Al) with open duct.The method of the present invention as presoma and is used cooperatively acid assistant using water-insoluble metal silicon source, more existing synthetic method has the advantages that cost of material is low, condition is relatively gentle and energy conservation and environmental protection, solve the problems, such as that present in current MIL 53 (Al) building-up process, there is potential industrial production prospect.
Description
Technical field
The present invention relates to the preparing technical field of metal-organic framework materials, more particularly, to a kind of metal organic framework material
Expect the synthetic method of MIL-53 (Al).
Background technology
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) are a kind of inorganic-organic hybrid materials
Material, it forms the static porous material with periodic network structure by metal ion and organic ligand by self assembly behavior.
Due to combining the opening structure of periodic network and the property of organic material skeleton, the characteristics of MOFs materials are maximum is exactly to have
The porosity of superelevation and huge inner ratio surface area.In recent years, the synthesis of porous material and application field are more and more extensive, MOFs
Material is enriched in hydrogen storage, drug delivery because it has the characteristics that tuneable duct shape, size and its duct skeleton composition, urged
Change and Selective Separation etc. have huge contribution.
MIL-53 (Al) is by AlO4(OH)2The octahedra carboxyl with terephthalic acid (TPA) is self-assembly of with one-dimensional diamond shape
The three dimensional skeletal structure in duct, was proposed by Ferey in 2004 earliest.This material can be autonomous when adsorbing some polar molecules
Adjustment hole road shape and size, namely so-called " skeleton breathing " effect, the macropore (large after removing guest molecule
Pore, lp) form is changed into narrowed aperture (narrow pore, np) form, and with the increase of coverage, and can be from np forms
It is changed into lp forms, original skeleton structure is not destroyed in transition process.MIL-53 (Al) is due to the higher ratio of its skeleton
The special respiration of surface area and hole has huge potentiality in terms of Molecular Adsorption and separation.Finsy et.al were once reported
CO is selectively adsorbing and separating using MIL-53 (Al)2And CH4Mixed gas (Separation of CO2/CH4mixtures
With the MIL-53 (Al) metal-organic framework, Microporous and Mesoporous
Materials)；Jie Li et al remove the micro amount of arsenic in water using MIL-53 (Al), and removal effect is fine
(Characteristics of arsenate removal from water by metal-organic frameworks
(MOFs), Water Science and technology)；Tan Haiyan etc. is used with MIL-53 (Al) for carrier loaded Co catalysts
In the catalytic oxidation of CO, it was demonstrated that the stability and high-specific surface area (gold having had with the catalyst that MIL-53 (Al) is carrier
Belong to the CO catalytic oxidation performances of organic framework material MIL-53 (Al) load cobalt catalyst, Acta PhySico-Chimica Sinica).
Current published MIL-53 (Al) synthetic method mainly has following three kinds：
Method one：Using nine water aluminum nitrates as silicon source, terephthalic acid (TPA) is organic ligand, the confined reaction under 220 DEG C of high temperature
72h, the high-temperature calcination 72h being placed in 300 DEG C, finally obtain MIL-53 (Al) product.But this method is in the synthesis process
A large amount of nitric acid accessory substances are produced, system is acid after reaction and oxidisability is extremely strong.Since reaction temperature is higher, cause in reaction system
Pressure is larger (for example, in the case of solvent volume accounts for reaction vessel 60%, internal pressure can be of about 12atm).Therefore, prepared by this method
Resistance to pressure and corrosion resistance requirement stringent (Hydrogen of MIL-53 (Al) the process condition harshnesses to synthesis device
Adsorption in the nanoporous metal-benzenedicarboxylate, Chemical
Communication).United States Patent (USP) US8,658,562 discloses a kind of series multiwell aluminium coordinating metal organic framework materials
Synthetic method, using nine water aluminum nitrates as silicon source, is matched somebody with somebody with 1,3,5- trimesic acid and 1,2,4,5- benzene tetracarboxylic acids to be organic respectively
Body is prepared for MIL-100 (Al), MIL-120 (Al) and three kinds of metal-organic framework materials of MIL-121 (Al).Disclosed in the patent
Reaction temperature is 210 DEG C in synthesis condition.
Method two：Primary synthetic methods and method one are similar, the difference is that later stage activation process slightly produces MIL-53 (Al)
Thing 150 DEG C of multiple activation in N,N-dimethylformamide finally obtain MIL-53 (Al) product (Metal-organic
framework membranes fabricated via reactive seeding；A European Journal).The party
Although method changes the work method method of MIL-53 (Al) crude product, replace high-temperature activation with organic solvent activation, reduce activation
Temperature, but synthesis condition is still identical with method one.And need largely to use organic solvent N, N- dimethyl formyl in activation process
Amine.N,N-Dimethylformamide is a kind of with all harmful organic solvent of irritation, suction or skin contact, cost
It is higher.
Method three：Zehua Li et et al. research is successfully closed with aluminium oxide, aluminium hydroxide and boehmite for alternative silicon source
MIL-53 (Al) products (The is finally obtained into MIL-53 (Al) crude product, and with n,N-Dimethylformamide activation
Metal–Organic Framework MIL-53(Al)Constructed from Multiple Metal Sources
Alumina Aluminum Hydroxide and Boehmite；A European Journal) replaced with water-insoluble silicon source
ANN aluminium nitrate nonahydrate, avoids the generation of oxidisability strong acidic by-products, reduces consersion unit to corrosion-resistant to a certain extent
The requirement of property.But its synthesis temperature and crude product activation method (220 DEG C and organic solvent work still identical with method one and method two
Change method), the harsh reaction condition of high temperature and pressure and high cost crude product activation method remain unchanged and constrain the big rule of MIL-53 (Al)
Mould commercial synthesis.
However, MIL-53 (Al) synthetic methods disclosed above consider to be not suitable for work from production equipment requirement and cost angle
Industry metaplasia is produced.Therefore, research cost is low, gently energy-saving and environment-friendly metal-organic framework material optimization preparation method is synthesis condition
Promote a kind of needs of related new function material industrialized production and application.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of technique is simple, cost
The synthetic method of moderate, synthesis temperature and the relatively low metal-organic framework material MIL-53 (Al) of reaction pressure.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), comprises the following steps：
(1) aluminium hydroxide, terephthalic acid (TPA) and water are mixed and stirred for making aluminium hydroxide and terephthalic acid (TPA) dispersed
Yu Shuizhong；
(2) acid assistant is added in step (1) obtained reaction system and stirred evenly；
(3) reaction system for obtaining step (2) reacted under 100~150 DEG C of hydrothermal condition 48~96 it is small when, then
It is cooled to room temperature, the solid obtained after separation of solid and liquid is MIL-53 (Al) crude product；
(4) MIL-53 (Al) crude product for obtaining step (3) is dried, and is then forged in 300~350 DEG C of air atmosphere
Burn, be cooled to room temperature to obtain MIL-53 (Al) product；
The aluminium hydroxide, terephthalic acid (TPA), the molar ratio of acid assistant and water are (0.5~1.5):1:(0.5~
1.5):(150~200).
When the time of calcining in the step (4) is 36~96 small.
In the step (4), MIL-53 (Al) crude product that step (3) is obtained is first in 140~160 DEG C of hydrothermal conditions
It is lower activation 12~48 it is small when, then dry, calcined in 300~350 DEG C of air atmosphere, be cooled to room temperature to obtain MIL-53 (Al)
Product.It can so reduce and calcine the time used at high temperature, save the energy.At this time, when the time of calcining is 24 small.High temperature
The purpose of calcining is to burn unreacted terephthalic acid (TPA), terephthalic acid (TPA) slightly soluble under 140~160 DEG C of temperature environment
Yu Shui, and the dissolution rate higher of terephthalic acid (TPA) in water under High Voltage in a kettle so that MIL-53 (Al) crude product
In free terephthalic acid (TPA) be dissolved in water, so as to reduce the terephthalic acid (TPA) in crude product, so as to reduce calcination time.
The acid assistant includes the one or more in formic acid, acetic acid or hydrochloric acid.
Drying in the step (4) is dry in 70~90 DEG C of baking oven.
The synthetic method for the metal-organic framework materials MIL-53 (Al) that the present invention uses, using water-insoluble aluminium hydroxide as
Silicon source, adds a certain proportion of acid assistant in building-up process, higher yield, hydro-thermal is kept in the case where reducing reaction temperature
Under the conditions of, acid assistant is acted on aluminium hydroxide, is improved the dissolubility of aluminium hydroxide in the reaction system, is improved the anti-of silicon source
Should activity, so as to accelerate combining to form MIL-53 (Al) and improving for silicon source and terephthalic acid (TPA) at a lower temperature
Reaction yield, and reduce reaction pressure (dropping to 3 atmospheric pressure from about 12 atmospheric pressure)；The pH of reaction solution is improved, is not had
There is powerful corrosivity；Reaction solution is subsequently repeatable to be utilized；It is organic molten that later stage activation process substitutes DMF in the form of calcining
Agent activates, and reducing the reaction condition of MIL-53 (Al) makes it possible that its industry is combined to.
Compared with prior art, the present invention has following significant beneficial effect：
(1) substitute aluminum nitrate using aluminium hydroxide makes do not have strong acid severe corrosive by-product produce in building-up process for silicon source
It is raw, improve the service life of industrialization building-up process Instrumental；
(2) synthesis reaction temperature is reduced by the addition of acid assistant in the case where not reducing yield；
(3) aqueous solvent in building-up process, which repeats to utilize, improves utilization rate；
(4) activation replacement DMF activation is carried out by way of calcining makes the more greenization of whole reaction process, makes green work
Industry is combined to be possibly realized；
(5) MIL-53 (Al) prepared by the present invention is compared with the material of conventional synthesis, the table such as its XRD, nitrogen adsorption curve
Sign is all similar, shows that material prepared by the present invention does not have very big difference with its performance of comparing of conventional synthesis.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction of the metal-organic framework materials of MIL-53 (Al) prepared by the embodiment of the present invention 1
(XRD) standard spectrogram of spectrogram and MIL-53 (Al)；
Fig. 2 is the thermogravimetric curve of the metal-organic framework materials of MIL-53 (Al) prepared by the embodiment of the present invention 1.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.But it should explanation, implements below
Example is merely illustrative of the technical solution of the present invention and unrestricted, and technical scheme is appropriately modified or is equally replaced
Change, without departing from the spirit and scope of technical solution of the present invention, it should all cover in scope of the presently claimed invention.
Embodiment 1
The molar ratio of aluminium hydroxide, terephthalic acid (TPA), formic acid and water that the present embodiment is used is 1:1:1:160.
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), this method comprises the following steps：
(1) mixing to be sufficiently stirred by aluminium hydroxide, terephthalic acid (TPA) and water makes aluminum contained compound and organic carboxyl acid uniformly divide
Dissipate in pure water；Formic acid is added in above-mentioned reactant solution and moves into stainless steel cauldron progress hydro-thermal after stirring
Synthesis, 150 DEG C, reaction time 72h of reaction temperature, it is thick production to stop heating being cooled to room temperature the solid that rear separation of solid and liquid obtains
Thing, is positioned in 80 DEG C of baking oven dry；
(2) crude product that step (1) obtains is put into high temperature furnace and is calcined in air atmosphere, 330 DEG C of calcining heat, calcining
Time 72h, obtains MIL-53 (Al) product after being cooled to room temperature.
This method technique is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Fig. 1 is X-ray powder diffraction (XRD) spectrogram and MIL- of the MOFs materials of MIL-53 manufactured in the present embodiment (Al)
The standard spectrogram of 53 (Al)；It can be seen from the figure that the product that the present embodiment obtains is consistent with the standard spectrogram of MIL-53 (Al).
Fig. 2 be the embodiment of the present invention 1 prepare MIL-53 (Al) metal-organic framework materials thermogravimetric curve, this thermogravimetric curve be
Obtained under air atmosphere, this curve matches with the thermogravimetric curve of the standard substance of MIL-53 (Al).
Embodiment 2
The molar ratio of aluminium hydroxide, terephthalic acid (TPA), formic acid and water that the present embodiment is used is 1:1:1:160.
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), this method comprises the following steps：
(1) mixing to be sufficiently stirred by aluminium hydroxide, terephthalic acid (TPA) and water makes aluminum contained compound and organic carboxyl acid uniformly divide
Dissipate in pure water；Formic acid is added in above-mentioned reactant solution and moves into stainless steel cauldron progress hydro-thermal after stirring
Synthesis, 150 DEG C, reaction time 72h of reaction temperature, is cooled to room temperature rear separation of solid and liquid and obtains crude product；Obtained crude product exists
24h centrifugations are activated under 150 DEG C of hydrothermal conditions after dry in 80 DEG C of baking oven；
(2) product that step (1) obtains is put into high temperature furnace and is calcined in air atmosphere, 330 DEG C of calcining heat, during calcining
Between 24h, obtained after being cooled to room temperature with MIL-53 (Al) product.
This method technique is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Embodiment 3
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), substantially identical with embodiment 1, difference exists
The molar ratio of aluminium hydroxide, terephthalic acid (TPA), formic acid and the water used in the present embodiment is 0.5:1:0.5:150.This method work
Skill is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Embodiment 4
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), substantially identical with embodiment 1, difference exists
The molar ratio of aluminium hydroxide, terephthalic acid (TPA), formic acid and the water used in the present embodiment is 1.5:1:1.5:200.This method work
Skill is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Embodiment 5
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), substantially identical with embodiment 1, difference exists
In formic acid is replaced with hydrochloric acid.This method technique is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Embodiment 6
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), substantially identical with embodiment 1, difference exists
In formic acid is replaced with acetic acid.This method technique is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Embodiment 7
The molar ratio of aluminium hydroxide, terephthalic acid (TPA), formic acid and water that the present embodiment is used is 1:1:1:160.
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), this method comprises the following steps：
(1) mixing to be sufficiently stirred by aluminium hydroxide, terephthalic acid (TPA) and water makes aluminum contained compound and organic carboxyl acid uniformly divide
Dissipate in pure water；Formic acid is added in above-mentioned reactant solution and moves into stainless steel cauldron progress hydro-thermal after stirring
Synthesis, 100 DEG C, reaction time 96h of reaction temperature, it is thick production to stop heating being cooled to room temperature the solid that rear separation of solid and liquid obtains
Thing, is positioned in 70 DEG C of baking oven dry；
(2) crude product that step (1) obtains is put into high temperature furnace and is calcined in air atmosphere, 300 DEG C of calcining heat, calcining
Time 96h, obtains MIL-53 (Al) product after being cooled to room temperature.
This method technique is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Embodiment 8
The molar ratio of aluminium hydroxide, terephthalic acid (TPA), formic acid and water that the present embodiment is used is 1:1:1:160.
A kind of synthetic method of metal-organic framework materials MIL-53 (Al), this method comprises the following steps：
(1) mixing to be sufficiently stirred by aluminium hydroxide, terephthalic acid (TPA) and water makes aluminum contained compound and organic carboxyl acid uniformly divide
Dissipate in pure water；Formic acid is added in above-mentioned reactant solution and moves into stainless steel cauldron progress hydro-thermal after stirring
Synthesis, 150 DEG C, reaction time 48h of reaction temperature, it is thick production to stop heating being cooled to room temperature the solid that rear separation of solid and liquid obtains
Thing, is positioned in 90 DEG C of baking oven dry；
(2) crude product that step (1) obtains is put into high temperature furnace and is calcined in air atmosphere, 350 DEG C of calcining heat, calcining
Time 72h, obtains MIL-53 (Al) product after being cooled to room temperature.
This method technique is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Embodiment 9
The present embodiment is substantially the same manner as Example 2, and difference is crude product in step (1) in 140 DEG C of hydro-thermals
Under the conditions of activate 36h centrifugations after dry in 80 DEG C of baking oven.
This method technique is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Embodiment 10
The present embodiment is substantially the same manner as Example 2, and difference is crude product in step (1) in 160 DEG C of hydro-thermals
Under the conditions of activate 12h centrifugations after dry in 80 DEG C of baking oven.
This method technique is simple, moderate cost, synthesis temperature and reaction pressure are relatively low.
Claims (1)
1. a kind of synthetic method of metal-organic framework materials MIL-53 (Al), it is characterised in that comprise the following steps：
(1) aluminium hydroxide, terephthalic acid (TPA) and water are mixed and stirred for making aluminium hydroxide and terephthalic acid (TPA) be dispersed in water
In；
(2) acid assistant is added in step (1) obtained reaction system and stirred evenly；
(3) reaction system for obtaining step (2) reacted under 100~150 DEG C of hydrothermal condition 48~96 it is small when, then cool down
To room temperature, the solid obtained after separation of solid and liquid is MIL-53 (Al) crude product；
(4) MIL-53 (Al) crude product obtained step (3) is when first activation 12~36 is small under 140~160 DEG C of hydrothermal conditions,
Then dry, calcined in 300~350 DEG C of air atmosphere, be cooled to room temperature to obtain MIL-53 (Al) product；
The aluminium hydroxide, terephthalic acid (TPA), the molar ratio of acid assistant and water are (0.5~1.5):1:(0.5~1.5):
(150~200)；
One or more of the acid assistant in formic acid or acetic acid；
When the time of calcining in the step (4) is 24 small.
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| CN111318294A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
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| CN110412105B (en) * | 2019-07-30 | 2022-03-25 | 陕西科技大学 | Application of electrochemical sensor of MIL-53 derived cementite in detection of chromate ions |
| CN114106344B (en) * | 2020-08-28 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of aluminum metal organic framework material Al-MIL-53 |
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| "Turning Redundant Ligands into Treasure: A New Strategy for Constructing MIL-53(Al)@Nanoscale TiO2 Layers";Yifan Gu et al.;《Chem. Eur. J.》;20151014;第21卷(第48期);第17485-17490页 * |
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