CN110105581A - A method of multi-stage porous UiO-66 material is prepared by template of dodecyl sodium sulfate - Google Patents
A method of multi-stage porous UiO-66 material is prepared by template of dodecyl sodium sulfate Download PDFInfo
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- CN110105581A CN110105581A CN201910336136.2A CN201910336136A CN110105581A CN 110105581 A CN110105581 A CN 110105581A CN 201910336136 A CN201910336136 A CN 201910336136A CN 110105581 A CN110105581 A CN 110105581A
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- sodium sulfate
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- dodecyl sodium
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000013207 UiO-66 Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 21
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 title claims abstract description 19
- 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
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 210000003850 cellular structure Anatomy 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- 229910007926 ZrCl Inorganic materials 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 239000013149 UiO-66 type metal-organic framework Substances 0.000 description 1
- 239000013208 UiO-67 Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HMKKIXGYKWDQSV-KAMYIIQDSA-N alpha-Amylcinnamaldehyde Chemical compound CCCCC\C(C=O)=C\C1=CC=CC=C1 HMKKIXGYKWDQSV-KAMYIIQDSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011469 building brick Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- -1 hydrone Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000013337 mesoporous metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 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
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods for preparing multi-stage porous UiO-66 material as template using dodecyl sodium sulfate.The synthetic method includes the following steps: ZrCl respectively4It is dissolved in DMF, stirs with terephthalic acid (TPA)；Template dodecyl sodium sulfate is added in terephthalic acid (TPA)-DMF solution, after stirring, two kinds of resulting mixed liquors of solution mixing is placed in autoclave and carry out hydro-thermal reaction；After products therefrom is purified, suction filtration, it is put into drying in vacuum oven, obtains the multi-stage porous UiO-66 material with well-crystallized pattern.The present invention is not only environmentally protective, easy to operate by dodecyl sodium sulfate being added as template, but also mild condition.In addition, product has good crystallization shape and cellular structure abundant, while there is micropore, mesoporous, three kinds of ducts of macropore, not only has high specific surface area, stable structure also has preferable application prospect in terms of the absorption of macromolecular and catalysis.
Description
Technical field
The invention belongs to the preparation fields of multi-stage porous metal organic framework, and in particular to a kind of to be with dodecyl sodium sulfate
The method that template prepares multi-stage porous UiO-66 material.
Background technique
In past ten years, metal ion or cluster are had with the metal-that organic ligand assembles by coordinate bond
Machine skeleton (MOFs) is always the emphasis of people's research.It is because of the different secondary building unit of design and use and one pack system or more
Component organic linking agent produces the MOFs different more than 20000 kinds.And by feat of well define hole geometry, high ratio
The advantage of surface area, adjustable porosity and various topological structure, MOFs, which will become, to be stored and separates, be catalyzed, medicine in gas
The forward position material in the fields such as object delivering and electronics.
Although the researcher of many difference interest in research and utilizes MOFs material, UiO series (including UiO-
66, UiO-67 and UiO-68) it is to be widely studied most one of materials, they are by Zr4+The three-dimensional constituted with dicarboxylic acids
Porous material.2008, Cavka et al. [Cavka J H, Jakobsen S, Olsbye U, et al.A new
zirconiuminorganic building brick forming metal organic frameworks with
exceptional stability[J].Journal of the American Chemical Society,2008,130
(42): 13850-13851. it] reports for the first time using Zr as metal center and terephthalic acid (TPA) (H2BDC) pass through for organic ligand strong
The MOF, i.e. UiO-66 of coordinate bond self assembly building.It is being permitted because of bigger serface, excellent thermal stability and chemical stability
Great interest and the rapid development of people, absorption and regeneration especially at high temperature, asymmetry catalysis are mostly caused in application
Etc..Xiao and its partner [Zhang X, Yang Y, Song L, et al.Enhanced adsorption
performance of gaseous toluene on defective UiO-66metal organic framework:
Equilibrium and kinetic studies[J].Journal of hazardous materials,2019,365:
597-605.] primary study UiO-66 and its modified material be to the Adsorption and desorption performance and corresponding dynamics of toluene vapor.
Huang et al. [Huang Y, Qin W, Li Z, et al.Enhanced stability and CO2 affinity of a
UiO-66type metal–organic framework decorated with dimethyl groups[J].Dalton
Transactions, 2012,41 (31): 9283-9285.] CO under the conditions of 0 and 20 DEG C (0.1 MPa) is had studied for the first time2Not
With the absorption behavior on the UiO-66-X of ligand function.Vermoortele research group [Vermoortele F, Ameloot
R,Vimont A,et al.An amino-modified Zr-terephthalate metal–organic framework
as an acid–base catalyst for cross-aldol condensation[J].Chemical
Communications, 2011,47 (5): 1521-1523.] with UiO-66 and UiO-66-NH2For acid catalyst, it is right to study its
The catalytic action of benzaldehyde and enanthaldehyde reaction synthesis jasminal.However, the MOF limit of most of list microcellular structures (< 2nm)
Diffusion and mass transfer of the guest molecule in duct are made.In addition, biggish aperture permission is a large amount of organic in hole wall surface grafting
Group, to improve absorption, the catalytic performance of MOFs.Therefore, being dedicated to design has the more of mesoporous (2nm < aperture < 50nm) structure
Grade hole MOFs is essential for the application (gas absorption separation is catalyzed, the sustained release of drug) of macromolecular.
It is to prepare the important channel of multi-stage porous MOFs using surfactant as the template of structure directing agent, it not only can be with
The composite material with significant ordered structure is obtained, and easily operated.Xiao et al. [Zhang X, Yang Y, Lv X, et
al.Adsorption/desorption kinetics and breakthrough of gaseous toluene for
modified microporous-mesoporous UiO-66metal organic framework[J].Journal of
Hazardous materials, 2019,366:140-150.] with P123 (EO20PO70EO20) it is structure directing agent, using simple
Solvent-thermal method is successfully prepared the UiO-66 with meso-hole structure.The result shows that micro- mesoporous UiO-66 crystal toluene adsorption capacity is
2.6 times of original UiO-66.Wherein, biggish hole increases the diffusion rate of molecule, reduces the resistance of mass transfer, i.e., micro- mesoporous
Structure has positive-effect to toluene molecule capture.Ke et al. [Li K, Lin S, Li Y, et al.Aqueous-Phase
Synthesis of Mesoporous Zr-Based MOFs Templated by Amphoteric Surfactants[J]
.Angewandte Chemie, 2018,130 (13): 3497-3501.] by utilizing amphoteric surfactant, i.e. alkylamide
Glycine betaine (CAPB) or oleic acid amidopropyl betaine (OAPB) construct in aqueous based systems with even mesoporous as template
With the mesoporous MOFs of Zr base of crystalline microporous skeleton.In addition, changing the long alkyl chains of surfactant, adjust with can be convenient
The size in hole aperture.Although templated synthesis strategy is great to have application value for obtaining desired, ordered structure MOFs
Approach, moreover it is possible to due to avoiding extending ligand method because using between the internal crystal structure that occurs interpenetrate it is unstable with cellular structure
Property the problem of, but the formation of template occasional interference MOF crystal, the part that this may result in mesoporous framework is non-homogeneous
Change, and Zr base MOFs of the preparation with good crystallinity is more difficult from DMF solution.On the other hand, synthesis path
Variation may bring the different coordinations of zirconium position, influence stability and activity of the UiO-66 material in the application such as catalysis.Cause
This, the MOFs material that preparation crystallinity is high, metal center is evenly distributed, hole is orderly is still a stern challenge.It is based on
These merits and demerits, this invention address that a kind of reasonable surfactant self assembly strategy is developed, to retain template method
The advantages of, while avoiding the problem that the unstable pore structure of MOFs may collapse when removing template agent removing.The present invention is with ten
Dialkyl sulfonates directly cooperate with self assembly as template, by metal ion, ligand and template, using one-step synthesis method
A kind of multi-stage porous metal-organic framework materials of regular appearance.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for synthesizing multi-stage porous UiO-66 material, it is intended to quickly and easily synthesize
Regular appearance and there is micropore, mesoporous, three kinds of cellular structures of macropore multi-stage porous UiO-66 material simultaneously.
Raw material of the present invention is ZrCl4, terephthalic acid (TPA), template dodecyl sodium sulfate (being purchased from lark prestige), DMF, only
Surfactant sodium dodecyl base sodium sulfonate is used as structure directing agent, can prepare out a kind of regular appearance and rich in a variety of
The UiO-66 material of cellular structure.
The purpose of the invention is achieved by the following technical solution.
A kind of method of rapid synthesis multi-stage porous UiO-66 material, includes the following steps:
(1) at room temperature, by ZrCl4It is dissolved in DMF, stirs, obtain solution A；
(2) at room temperature, terephthalic acid (TPA) is dissolved in DMF, stirs, obtains solution B；
(3) solution B is added in template dodecyl sodium sulfate, stirring obtains solution C；
(4) solution A and solution C are mixed, stirring obtains mixed solution；
(5) step (4) resulting mixed solution is sealed in the stainless steel autoclave with polytetrafluoroethyllining lining, and
It is placed in baking oven and handles certain time；
(6) reaction solution after step (5) hydro-thermal reaction is cooled to room temperature, resulting product is after DMF is washed, certain
At a temperature of immerse methanol；
(7) the resulting product of step (6) is filtered, is put into vacuum oven dry, obtained multi-stage porous UiO-66 material.
Preferably, step (1), step (2) described stirring time be 10-15 minutes.
Preferably, the time of step (3) described stirring is 5-10 minutes.
Preferably, the time of step (4) described stirring is 1-5 minutes.
Preferably, the temperature of step (5) described baking oven be 110~120 DEG C, processing the time be 20~for 24 hours.
Preferably, after step (6) described hydro-thermal reaction, after step (6) described hydro-thermal reaction, by reaction solution with 5-8 DEG C/
The rate of min is cooled to room temperature；Methanol impregnates 2~4 days by a definite date, and required temperature is 50-60 DEG C
Preferably, in step (6), a methanol is replaced daily.
Preferably, the temperature of step (7) described drying is 130-150 DEG C, and the dry time is 10-12h.
Preferably, the ZrCl4, terephthalic acid (TPA), dodecyl sodium sulfate molar ratio be 1:(0.8-1.2): (0.5-
1.5), further preferably 1:(0.95-1.05): (0.9-1.1.
Compared with the existing technology, the invention has the advantages that and effect:
(1) preparation method of the invention is simple, can prepare multi-stage porous UiO-66 material using one-step method.
(2) material possesses micropore-mesopore abundant-macropore cellular structure, and material structure is stablized, and specific surface area is high,
The absorption of macromolecular and catalysis aspect also have preferable application prospect.
(3) dodecyl sodium sulfate belongs to anionic surfactant, environmentally protective, no pollution to the environment.
Detailed description of the invention
Fig. 1 is the conventional microporous UiO-66 material synthesized using conventional hydrothermal method and UiO- prepared by the embodiment of the present invention 1
The Wide angle X-ray diffraction figure of 66 materials.
Fig. 2 is the stereoscan photograph of multi-stage porous UiO-66 material prepared by the embodiment of the present invention 1.
Fig. 3 is the hot weight curve of multi-stage porous UiO-66 material prepared by the embodiment of the present invention 1,3,5.
Fig. 4 is the N of multi-stage porous UiO-66 material prepared by embodiment 1,3,52Adsorption-desorption isothermal figure.
Fig. 5 is that the complete opening pore-size distribution that multi-stage porous UiO-66 material prepared by embodiment 1,3,5 is calculated according to DFT model is bent
Line chart.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the range of embodiment statement.
Embodiment 1
By 0.233g ZrCl4It is dissolved in 20ml DMF, obtains solution A within stirring 10 minutes；0.133g terephthalic acid (TPA) is dissolved in
In 20ml DMF, stirring obtains solution B in 10 minutes；0.144g dodecyl sodium sulfate is added in solution B, 5 points of stirring is continued
Clock obtains solution C；Solution A and solution C, which are mixed, is placed on progress hydro-thermal reaction (110 DEG C, 20h), institute in autoclave for 1 minute
It obtains product to be cooled to room temperature with the rate of 5 DEG C/min, then after methanol purifies 2 days (50 DEG C), filters, is put into 130 DEG C of vacuum
Dry 10h, is made the multi-stage porous UiO-66 material with well-crystallized pattern in drying box, is labeled as sample 1.
Embodiment 2
By 0.233g ZrCl4It is dissolved in 20ml DMF, obtains solution A within stirring 10 minutes；0.158g terephthalic acid (TPA) is dissolved in
In 20ml DMF, stirring obtains solution B in 12 minutes；0.260g dodecyl sodium sulfate is added in solution B, 7 points of stirring is continued
Clock obtains solution C；Solution A and solution C, which are mixed, is placed on progress hydro-thermal reaction (110 DEG C, 20h), institute in autoclave for 2 minutes
It obtains product to be cooled to room temperature with the rate of 5 DEG C/min, then after methanol purifies 3 days (55 DEG C), filters, is put into 140 DEG C of vacuum
Dry 11h, is made the multi-stage porous UiO-66 material with well-crystallized pattern in drying box, is labeled as sample 2.
Embodiment 3
By 0.233g ZrCl4It is dissolved in 20ml DMF, obtains solution A within stirring 12 minutes；0.166g terephthalic acid (TPA) is dissolved in
In 20ml DMF, stirring obtains solution B in 12 minutes；0.288g dodecyl sodium sulfate is added in solution B, 7 points of stirring is continued
Clock obtains solution C；Solution A and solution C, which are mixed, is placed on progress hydro-thermal reaction (115 DEG C, 22h), institute in autoclave for 2 minutes
It obtains product to be cooled to room temperature with the rate of 6 DEG C/min, then after methanol purifies 3 days (55 DEG C), filters, is put into 140 DEG C of vacuum
Dry 11h, is made the multi-stage porous UiO-66 material with well-crystallized pattern in drying box, is labeled as sample 3.
Embodiment 4
By 0.233g ZrCl4It is dissolved in 20ml DMF, obtains solution A within stirring 15 minutes；0.174g terephthalic acid (TPA) is dissolved in
In 20ml DMF, stirring obtains solution B in 15 minutes；0.317g dodecyl sodium sulfate is added in solution B, 10 points of stirring is continued
Clock obtains solution C；Solution A and solution C mixing are placed in progress hydro-thermal reaction (120 DEG C, for 24 hours), institute in autoclave after five minutes
It obtains product to be cooled to room temperature with the rate of 8 DEG C/min, then after methanol purifies 3 days (60 DEG C), filters, is put into 150 DEG C of vacuum
Dry 12h, is made the multi-stage porous UiO-66 material with well-crystallized pattern in drying box, is labeled as sample 4.
Embodiment 5
By 0.233g ZrCl4It is dissolved in 20ml DMF, obtains solution A within stirring 15 minutes；0.200g terephthalic acid (TPA) is dissolved in
In 20ml DMF, stirring obtains solution B in 15 minutes；0.432g dodecyl sodium sulfate is added in solution B, 10 points of stirring is continued
Clock obtains solution C；Solution A and solution C mixing are placed in progress hydro-thermal reaction (120 DEG C, for 24 hours), institute in autoclave after five minutes
It obtains product to be cooled to room temperature with the rate of 8 DEG C/min, then after methanol purifies 4 days (60 DEG C), filters, is put into 150 DEG C of vacuum
Dry 12h, is made the multi-stage porous UiO-66 material with well-crystallized pattern in drying box, is labeled as sample 5.
It is analyzed according to multi-stage porous UiO-66 material prepared by embodiment, analysis result is as shown in the picture.
(1) crystal structure properties of the multi-stage porous UiO-66 of hydro-thermal method synthesis
Using the D8-ADVANCE model X-ray diffractometer of German Bruker company production to the crystalline substance of the embodiment of the present invention 1
Body structure is characterized.
Fig. 1 uses the UiO-66 material (preparation method:, difference similar with 1 step of embodiment of conventional hydrothermal method synthesis
Be to be added without template neopelex, remaining step is the same) and the embodiment of the present invention 1 prepare UiO-66 material
Wide angle X-ray diffraction figure.From figure 1 it appears that embodiment 1 is made compared with the UiO-66 material of conventional hydrothermal method synthesis
There is the characteristic diffraction peak of stronger UiO-66 metal organic framework in standby sample 1 out, illustrates that there are high-crystallinities in product
UiO-66 component.But the part diffraction maximum of multi-stage porous UiO-66 weakens even disappearance, due to matter crystal internal defect is deposited
, and defect part is hierarchical porous structure.
(2) the SEM figure of rapid synthesis multi-stage porous UiO-66 material
The sample carry out table that embodiment 1 is prepared using JSM-6330F type scanning electron microscope (electronics corporation JEOL, Japan)
Sign.Fig. 2 shows representative SEM image (sample 1), crystalline material by the little particle accumulation between 50-150nm and
At this matches with result reported in the literature, shows the addition of template (dodecyl sodium sulfate) and has not been changed UiO-66 crystalline substance
The pattern and structure of body material.In addition, there is the mesoporous and macropore duct of random distribution between particle, show that hole is abundant, with X-ray
Diffraction patterns are consistent.
(3) thermogravimetric analysis of bimetal salt room temperature rapid synthesis UiO-66 material is utilized
Sample prepared by embodiment 1,3,5 is characterized to examine using 209 thermogravimetric analyzer of TG (Netzsch)
Survey its thermal stability.As shown in figure 3, the sample of all synthesis all had good thermal stability before temperature reaches 500 DEG C.
Two kinds of main weightlessness can be observed in we from curve, and the first time mass loss before 300 DEG C is attributable to material
The removal of the residual solvents such as hydrone, DMF and methanol in duct, and mass loss next time be between 400~600 DEG C due to
Presoma decomposes, caused by material structure collapse.Hereafter curve gradually tends to be horizontal, illustrates that structure collapse is complete at this time.
(4) pore properties
Using the ASAP2460 specific surface pore-size distribution instrument of Micro company, U.S. production to 1,3,5 institute of the embodiment of the present invention
The pore structure for preparing sample is characterized, and the results are shown in Table 1.As can be seen from Table 1, the BET specific surface area of material prepared
Respectively 1171,927,799m2.g-1.Wherein, the S of sample 1/3/5meso/SmicroValue is respectively 0.75,1.41 and 0.77.Sample
3 obtain maximum Smeso/SmicroValue, shows there is more meso-hole structures.In addition, multi-stage porous UiO-66 prepared by the present invention
Material mesoporous Kong Rong with higher, up to 0.98cm3.g-1。
Table 1
Fig. 4 is the N of multi-stage porous UiO-66 material prepared by the embodiment of the present invention 1,3,52Adsorption-desorption isothermal figure,
P/P0I type adsorption isotherm is shown as under < 0.01 pressure, adsorbance steeply rises.Precipitous N is presented under low relative pressure2It inhales
It receives, this is usually related with micro-porosity, shows that sample has microcellular structure.In relative pressure P/P0There is IV type in ≈ 0.8 or so
Adsorption hysteresis ring, this is mesoporous material in N2Characteristic feature in adsorption desorption curve, shows containing mesoporous material.
The DFT full aperture distribution map of Fig. 5 shows that multi-stage porous UiO-66 material prepared by embodiment 1,3,5 is big in addition to possessing
The mesoporous and bigger macropore duct measured the micropore canals of 1.5nm or so, while possessing a large amount of 25nm or so, these results are into one
Step, which confirms, is provided simultaneously with micropore and mesoporous in UiO-66.
Above-described embodiment is the comparatively ideal embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination, letter
Change, should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method for preparing multi-stage porous UiO-66 material as template using dodecyl sodium sulfate, which is characterized in that including
Following steps:
(1) by ZrCl4It is dissolved in DMF, stirs, obtain solution A；
(2) terephthalic acid (TPA) is dissolved in DMF, stirs, obtains solution B；
(3) template dodecyl sodium sulfate is added in B solution, stirring obtains solution C；
(4) solution A and solution C are mixed, stirring；
(5) step (4) resulting mixed solution is sealed in the stainless steel autoclave with polytetrafluoroethyllining lining, is placed in
It is reacted in baking oven；
(6) reaction solution after step (5) hydro-thermal reaction is cooled to room temperature, resulting product immerses methanol after DMF is washed
In；
(7) the resulting product of step (6) is filtered, is put into vacuum oven dry, obtained multi-stage porous UiO-66 material.
2. according to the method described in claim 1, it is characterized by: the time of step (1), step (2) described stirring is 10-
15 minutes.
3. according to the method described in claim 4, it is characterized by: the time of step (3) described stirring is 5-10 minutes.
4. according to the method described in claim 1, it is characterized by: the time of step (4) described stirring is 1-5 minutes.
5. according to the method described in claim 1, it is characterized by: the temperature of step (5) described baking oven is 110 ~ 120 DEG C.
6. according to the method described in claim 1, it is characterized by: the time of step (5) described reaction be 20 ~ for 24 hours.
7. according to the method described in claim 1, it is characterized by: after step (6) described hydro-thermal reaction, by reaction solution with 5-8
DEG C/rate of min is cooled to room temperature, methanol impregnates 2 ~ 4 days by a definite date, and required temperature is 50-60 DEG C.
8. according to the method described in claim 1, it is characterized by: replacing a methanol daily in step (6).
9. according to the method described in claim 1, it is characterized by: the temperature of step (7) described drying be 130-150 DEG C, do
The dry time is 10-12h.
10. according to the method described in claim 1, it is characterized by: the ZrCl4, terephthalic acid (TPA), dodecyl sodium sulfate
Molar ratio be 1:(0.8-1.2): (0.5-1.5).
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| CN115025818A (en) * | 2022-06-20 | 2022-09-09 | 常州大学 | adenine/SDBS/UiO-66 composite catalyst and preparation method and application thereof |
| CN115216052A (en) * | 2021-04-21 | 2022-10-21 | 北京化工大学 | Preparation method of hierarchical porous MOFs material with complete framework |
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