CN104262400A - Multilevel pore path MIL-101 material with large pore volume as well as preparation method and application thereof - Google Patents
Multilevel pore path MIL-101 material with large pore volume as well as preparation method and application thereof Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 68
- 239000013177 MIL-101 Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000012423 maintenance Methods 0.000 claims description 12
- 230000009514 concussion Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000000967 suction filtration Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 238000001816 cooling Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N H2BDC Natural products OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 239000012922 MOF pore Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013337 mesoporous metal-organic framework Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 2
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001464887 Parvimonas micra Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000013254 iso-reticular metal–organic framework Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28088—Pore-size distribution
- B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
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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
- 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]
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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Abstract
The invention belongs to the field of preparation of metal-organic framework organics, and discloses a multilevel pore path MIL-101 material with a large pore volume as well as a preparation method and application of the multilevel pore path MIL-101 material. The method comprises the following steps of: dissolving Cr(NO3)3.9H2O with water to obtain clear solution; adding 3-aminopropyl trimethoxy silane into the solution; stirring the solution and adding H2BDC into the solution; dropwise adding HF and continuously stirring the solution; transferring the solution into a stainless steel high-pressure reaction kettle for performing temperature programming; cooling the reaction kettle to be room temperature; dropwise adding DMF into reaction solution, and stirring and shaking the reaction kettle; filtering the solution to obtain a product; drying the product in vacuum; soaking the product with ethanol and then soaking the product with NH4F solution; performing suction filtration and rinsing samples with warm water; drying the samples in vacuum to obtain multilevel pore path MIL-101 with a large pore volume. The preparation process of the multilevel pore path MIL-101 material is simple; the obtained material has a micropore-mesoporous-macropore multilevel pore structure, so that the mass transfer efficiency is improved during reaction. In addition, the product has high specific surface area and a large pore volume, and has good application prospect in the fields of gas absorption and the like.
Description
Technical field
The invention belongs to metal-organic framework organism preparation field, particularly a kind of multistage pore canal MIL-101 material with large pore volume and its preparation method and application.
Background technology
Metal-organic framework materials (MOFs) has the features such as high-specific surface area, high porosity, aperture adjustability and topological framework uniqueness, be used widely in multiple field at present, comprising aspects such as sensing, gas delivery, absorption, bio-pharmaceutical carrier, atmosphere storage and catalysis.The aperture of MOFs material, close to zeolite diameter, is mainly distributed in
small portion MOFs is only had to have less meso-hole structure.But along with petrochemical complex and the building site development that becomes more meticulous, the industrial catalysis often having macromole to participate in, absorption, the processes such as separation, little duct seriously hinders mass transfer and diffusion, makes macromole cannot arrive the avtive spot of MOFs micropore inside, thus limits the practical application of MOFs.Mesoporous greatly and macropore are introduced in traditional MOFs structure, can combine mesoporous greatly with the high-ratio surface sum large pore volume that MOFs material itself has with the duct advantage that macropore has, reach the object of mutual supplement with each other's advantages.
Synthesis multistage pore canal MOFs is by extending part or using template two kinds of common methods to realize.Eddaoudi [Eddaoudi M in 2002, Kim J, Rosi N, et al.Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage [J] .Science, 2002,295 (5554): 469-472.] etc. people reports the first mesoporous MOF material Zn
4o (TPDC)
3(DMF) 12 (H
2o)
2(IRMOF-16), this materials'use has captain's part to dicarboxylic acid terphenyl (TPDC) and Zn
2+salt synthesizes.This material has
and
fixing channel diameter.Sheng-Han Lo [Lo S H, Chien C H, Lai Y L, et al.A mesoporous aluminium metal – organic framework with 3 nm open pores [J] .Journal of Materials Chemistry A, 2013,1 (2): 324-329.] Al (III) ion and the H with large-size etc. is selected
2sDC (4,4 ‵-toluylene diacid) (13.7 dust) part has synthesized the Al with meso-hole structure (OH) (SDC) under hydrothermal conditions] (CYCU-3).Extend part method synthesis multistage pore canal MOFs to be reported by many people, this method tool is resultful can material property in advance, facilitates the development of multi-stage porous MOFs simultaneously.But the method may cause removing object solvent back skeleton caves in, basket structure compression or framework are interconnected, and cause pore volume aperture to reduce, and this directly limit the widespread use extending part method.
At present, use template to introduce mesoporous or macropore and obtain extensive concern.Lin-Bing Sun [Sun L B, Li J R, Park J, et al.Cooperative template-directed assembly of mesoporous metal – organic frameworks [J] .Journal of the American Chemical Society, 2011,134 (1): 126-129.] etc. people uses CTAB as template, and CA (citric acid) connects CTAB and Cu (II) as sequestrant, synthesizes Cu
3(BTC)
2(HKUST-1).The mesoporous HKUST-1 synthesized in this way has that larger mesoporous (as mol ratio CTAB/CA=2.3, mesoporous pore size is 19.6nm, and BET specific surface area is 1162m
2.g
-1).Tian-Yi Ma [Ma T Y, Li H, Deng Q F, et al.Ordered Mesoporous Metal – Organic Frameworks Consisting of Metal Disulfonates [J] .Chemistry of Materials, 2012, 24 (12): 2253-2255.] etc. people uses different disulfonic acid and metal nitrate or metal chlorination salt respectively as part and inorganic precursor, F127 is as template, with crown ether 1, 10-diaza 18-is preced with-6 (NC) control metal ion release as blender, final synthesis has the MOFs material that hexagonal mesoporous and mesoporous wall is crystalline texture.Yueju Zhao [Zhao Y, Zhang J, Han B, et al.Metal – Organic Framework Nanospheres with Well ?Ordered Mesopores Synthesized in an Ionic Liquid/CO
2/ Surfactant System [J] .Angewandte Chemie International Edition, 2011,50 (3): 636-639.] etc. people is at supercritical CO
2synthesize MOFs nanometer ball in/ionic liquid/N-EtFOSA template emulsion system, contain order mesoporous in this nanometer ball simultaneously, and mesoporous wall is micropore.Mesoporous pore size is 3.6nm, and nanosphere size is about 80nm.Although use template successfully can synthesize multi-stage porous MOFs material, and the method has very strong Modulatory character, still less for the synthesis of the Template Types of multi-stage porous MOFs at present.
Summary of the invention
In order to solve the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method with the multistage pore canal MIL-101 material of large pore volume.The method is intended to use a kind of new template, and new mesoporous and macropore is introduced on basis, MIL-101 original duct, expands the pore volume of MOFs material simultaneously, keeps its bigger serface.
Another object of the present invention is to provide a kind of multistage pore canal MIL-101 material with large pore volume prepared by aforesaid method.This material contains the multistage pore canal of micropore, mesoporous and macropore.
Another object of the present invention is to provide a kind of above-mentioned application with the multistage pore canal MIL-101 material of large pore volume.
The object of the invention is achieved through the following technical solutions:
A preparation method for the multistage pore canal MIL-101 material of large pore volume, is characterized in that: this preparation method comprises following operation steps:
(1) by Cr (NO
3)
3.9H
2o is soluble in water, stirs and obtains settled solution; Wherein Cr (NO
3)
3.9H
2the mol ratio of O and water is 1:(260 ~ 270);
(2) in step (1) gained settled solution, add 3-aminopropyl trimethoxysilane, stir under room temperature condition; 3-aminopropyl trimethoxysilane and the described Cr (NO of step (1)
3)
3.9H
2the mol ratio of O is 1:(0.09 ~ 0.10);
(3) terephthalic acid (H is added
2bDC), and drip hydrofluoric acid (HF) solution, continue to stir, obtain mixed solution; Phthalic acid, hydrofluoric acid and the described Cr (NO of step (1)
3)
3.9H
2the mol ratio of O is (0.98 ~ 1.1): (0.90 ~ 1.12): 1;
(4) step (3) gained mixed solution is loaded in stainless steel autoclave, carry out temperature programming; At 220 DEG C, keep 8h, 160 DEG C of maintenance 3h, 90 DEG C of maintenance 3h successively, in 6h, be down to 30 DEG C;
(5) drip dimethyl formamide (DMF) under agitation, concussion, filter, vacuum-drying; The consumption of described dimethyl formamide is with the described Cr (NO of every 4g step (1)
3)
3.9H
2o correspondence uses 15 ~ 20ml dimethyl formamide;
(6) dry for step (5) gained thing is loaded in stainless steel autoclave, add alcohol immersion 3 ~ 5 times, Neutral ammonium fluoride (NH
4f) solution embathes 1 ~ 2 time;
(7) filter, with warm water washing, vacuum-drying, the multistage pore canal MIL-101 material of obtained large pore volume.
The temperature of step (1) described stirring is 20 ~ 30 DEG C, and the time of stirring is 10 ~ 20min.
The temperature of step (2) described stirring is 20 ~ 30 DEG C, and the time of stirring is 1 ~ 2h.
The temperature of step (3) described stirring is 20 ~ 30 DEG C, and the time of stirring is 30 ~ 60min; The mass percent concentration of described hydrofluoric acid solution is 40%.
The described concussion temperature of step (5) is 35 ~ 45 DEG C, and the concussion time is 40min ~ 1h; Described vacuum-drying temperature is 120 ~ 150 DEG C, and time of drying is 10 ~ 15h.
The temperature that step (6) described ethanol embathes 100 ~ 150 DEG C, embathes time 8 ~ 14h at every turn; The concentration of described ammonium fluoride solution is 30 ~ 40mmol/L, and embathing temperature is 50 ~ 60 DEG C, embathes time 8 ~ 14h.
The described vacuum drying temperature of step (7) is 120 ~ 150 DEG C, and time of drying is 10 ~ 15h, and warm water temperature is 60 ~ 70 DEG C.
A kind of multistage pore canal MIL-101 material of the large pore volume prepared by above-mentioned preparation method.
The application of multistage pore canal MIL-101 material in water absorption and organic steam adsorbing domain of above-mentioned large pore volume.
The present invention adopts 3-aminopropyl trimethoxysilane tensio-active agent as template, synthesizes and has micropore, the mesoporous multi-stage porous MIL-101 with macroporous structure simultaneously, be conducive to being applied to catalyzed reaction.Synthetic sample has 2.27cm simultaneously
3the large pore volume of/g, makes it have broad application prospects in gas adsorption field.
The present invention adopts hydrothermal synthesis method, using 3-aminopropyl trimethoxysilane tensio-active agent as template, with H
2bDC and Cr (NO
3)
3.9H
2o is respectively as organic ligand and source metal, and the order adjustment added by reactant, obtains having micropore, multistage pore canal MIL-101 that is mesoporous and macropore and large pore volume after crystallization certain hour.
Compared with prior art, the present invention has following beneficial effect:
(1) the multi-stage porous MIL-101 material that prepared by the present invention has micropore, mesoporous and macroporous structure simultaneously, and the multi-stage porous MIL-101 prepared is made up of regular octahedron;
(2) the multi-stage porous MIL-101 material that prepared by the present invention has larger specific surface area and pore volume, and BET specific surface area can reach 3385m
3/ g, pore volume is 2.27cm
3/ g;
(3) the present invention only using 3 ?a kind of tensio-active agent of aminopropyl trimethoxysilane as template, adopt water heat transfer, its building-up process is easy.
accompanying drawing explanation
Fig. 1 is the N of multi-stage porous MIL-101 material prepared by embodiment 1
2adsorption-desorption isothermal figure.
Fig. 2 is multi-stage porous MIL-101 material aperture scatter chart prepared by embodiment 1.
Fig. 3 is the XRD spectra of multi-stage porous MIL-101 material prepared by embodiment 1.
Fig. 4 is the SEM figure of multi-stage porous MIL-101 material prepared by embodiment 1.
Fig. 5 is the TEM figure of multi-stage porous MIL-101 material prepared by embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
By 4.0g Cr (NO
3)
3.9H
2o is dissolved in H
2in O 48ml, 30 DEG C are stirred 20min and obtain settled solution; Add 0.18g 3-aminopropyl trimethoxysilane, after stirring 1h at 30 DEG C, add 1.64g H
2bDC, dropwise drips the hydrofluoric acid solution of 0.5ml massfraction 40%, continues to stir 30min at dispersed latter 30 DEG C.Reaction solution is moved into the temperature programming of stainless steel autoclave, at 220 DEG C, keep 8h, 160 DEG C of maintenance 3h, 90 DEG C of maintenance 3h.After cooling, at 40 DEG C, drip 15ml DMF stir 30min, concussion, reaction solution obtains filtrate through G1 funnel suction filtration, then obtains filter cake through G4 funnel suction filtration, vacuum-drying 10h at 150 DEG C.Obtain sample ethanol at 150 DEG C and embathe 4 times, each 12h.Again with 30mmol/L NH
4f solution soaks 10h at 60 DEG C, suction filtration with 60 DEG C of warm water washing samples, vacuum-drying 10h at 150 DEG C, the multistage pore canal MIL-101 material sample B1 of obtained large pore volume.
Embodiment 2
By 4.0g Cr (NO
3)
3.9H
2o be dissolved in H
2in O 46ml, 20 DEG C are stirred 10min and obtain settled solution; Add 0.16g 3-aminopropyl trimethoxysilane, after stirring 2h at 30 DEG C, add 1.63g H
2bDC, dropwise drips the hydrofluoric acid solution of 0.4ml massfraction 40%, continues to stir 40min at dispersed latter 30 DEG C.Reaction solution is moved into the temperature programming of stainless steel autoclave, at 220 DEG C, keep 8h, 160 DEG C of maintenance 3h, 90 DEG C of maintenance 3h.After cooling, at 35 DEG C, drip 18ml DMF stir 40min, concussion, reaction solution obtains filtrate through G1 funnel suction filtration, then obtains filter cake through G4 funnel suction filtration, vacuum-drying 15h at 120 DEG C.Obtain sample ethanol at 100 DEG C and embathe 5 times, each 8h.Again with 35mmol/L NH
4f solution soaks 10h at 50 DEG C, and suction filtration also with 70 DEG C of warm water washing samples, by sample vacuum-drying 12h at 140 DEG C, obtains the multistage pore canal MIL-101 material sample B2 of large pore volume.
Embodiment 3
By 4.0g Cr (NO
3)
3.9H
2o be dissolved in H
2in O 49ml, 40 DEG C are stirred 20min and obtain settled solution; Add 0.17g 3-aminopropyl trimethoxysilane, after stirring 1.5h at 20 DEG C, add 1.83g H
2bDC, dropwise drips the hydrofluoric acid solution of 0.4ml massfraction 40%, continues to stir 60min at dispersed latter 20 DEG C.Reaction solution is moved into the temperature programming of stainless steel autoclave, at 220 DEG C, keep 8h, 160 DEG C of maintenance 3h, 90 DEG C of maintenance 3h.After cooling, at 45 DEG C, dropwise drip 20ml DMF and stir 60min, concussion, reaction solution obtains filtrate through G1 funnel suction filtration, then obtains filter cake through G4 funnel suction filtration, vacuum-drying 12h at 140 DEG C.Obtain sample ethanol at 120 DEG C and embathe 3 times, each 14h.Again with 40mmol/L NH
4f solution soaks 14h at 50 DEG C, suction filtration with 65 DEG C of warm water washing samples, vacuum-drying 15h at 120 DEG C, the multistage pore canal MIL-101 material sample B3 of obtained large pore volume.
Embodiment 4
By 4.0g Cr (NO
3)
3.9H
2o and 1.74g H
2bDC is dissolved in H
2in O 49ml, after dispersed, dropwise drip the hydrofluoric acid solution that 0.5ml massfraction is 40%, after stirring 2h at 30 DEG C, add 0.18g 3-aminopropyl trimethoxysilane, continue to stir 60min.Reaction solution is moved into the temperature programming of stainless steel autoclave, at 220 DEG C, keep 8h, 160 DEG C of maintenance 3h, 90 DEG C of maintenance 3h.Drip 20ml DMF after cooling and stir 40min, concussion, reaction solution obtains filtrate through G1 funnel suction filtration, then obtains filter cake through G4 funnel suction filtration, vacuum-drying 12h at 150 DEG C.Obtain sample ethanol at 150 DEG C and embathe 5 times, each 8h.Again with 35mmol/L NH
4f solution soaks 10h at 60 DEG C, suction filtration with 70 DEG C of warm water washing samples, vacuum-drying 10h at 150 DEG C, the multistage pore canal MIL-101 material sample B4 of obtained large pore volume.
With embodiment 1 for representative, analyze multi-stage porous MIL-101 prepared by embodiment 1, other embodiment analytical structures, substantially with embodiment 1, do not provide one by one.
(1) pore structure character
The ASAP-2020 specific surface pore size distribution instrument adopting U.S. Micro company to produce characterizes the pore structure of sample prepared by the present invention, result as table 1, shown in table 2.
The specific surface area parameter of table 1 table 1 multi-stage porous MIL-101 of the present invention
The pore volume of table 2 multi-stage porous MIL-101 of the present invention and aperture parameters
By table 1, table 2 can be found out, the multi-stage porous MIL-101 prepared by the present invention has higher specific surface area and larger pore volume.
Fig. 1 is the N of the embodiment of the present invention 1
2adsorption/desorption curve, can find out, multistage pore canal MIL-101 prepared by the present invention has meso-hole structure, Fig. 2 is the pore size distribution curve of the embodiment of the present invention 1 multi-stage porous MIL-101, can find out, the multistage pore canal MIL-101 prepared by the present invention has pore size distribution in a big way, possess micropore, mesoporous and macropore three kinds of aperture structures simultaneously, be conducive to the widespread use of material at catalytic field, and prepared by other products to the present invention, all show identical characteristics.
(2) crystal structure properties (embodiment 1) of multi-stage porous MIL-101
The crystalline structure of D8-ADVANCE model X-ray diffractometer to the embodiment of the present invention 1 adopting German Bruker company to produce characterizes, and wherein operational condition is: copper target, 40KV, 40mA, step-length 0.02 degree, sweep velocity 17.7 seconds/step.
Fig. 3 is the XRD spectra of the embodiment of the present invention 1, as can be seen from Figure 3, the sample prepared in 2 θ=2.84 °, 3.31 °, 5.22 °, 8.45 ° and the 9.10 ° characteristic diffraction peak peaks all occurring MIL-101, illustrate that product has MIL-101 crystalline texture.
(3) the SEM figure of multi-stage porous MIL-101
ZEISS Ultra 55 type field emission scanning electron microscope (Carl Zeiss company, Germany) is adopted to characterize the surface topography of sample.As shown in Figure 4, sample presents the surface topography of relatively homogeneous crystallization to result, by many sizes and the more homogeneous octahedra nanometer small-crystalline of shape pile up and formed.
(4) the TEM figure of multi-stage porous MIL-101
JEM-2100HR type transmission electron microscope (electronics corporation JEOL, Japan) is adopted to characterize product.As shown in Figure 5, multi-stage porous MIL-101 has abundant accumulation hole to result, and aperture is comparatively large, and distribution range is wider.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a preparation method for the multistage pore canal MIL-101 material of large pore volume, is characterized in that: this preparation method comprises following operation steps:
(1) by Cr (NO
3)
3.9H
2o is soluble in water, stirs and obtains settled solution; Wherein Cr (NO
3)
3.9H
2the mol ratio of O and water is 1:(260 ~ 270);
(2) in step (1) gained settled solution, add 3-aminopropyl trimethoxysilane, stir under room temperature condition; 3-aminopropyl trimethoxysilane and the described Cr (NO of step (1)
3)
3.9H
2the mol ratio of O is 1:(0.09 ~ 0.10);
(3) add terephthalic acid, and drip hydrofluoric acid solution, continue to stir, obtain mixed solution; Phthalic acid, hydrofluoric acid and the described Cr (NO of step (1)
3)
3.9H
2the mol ratio of O is (0.98 ~ 1.1): (0.90 ~ 1.12): 1;
(4) step (3) gained mixed solution is loaded in stainless steel autoclave, carry out temperature programming; At 220 DEG C, keep 8h, 160 DEG C of maintenance 3h, 90 DEG C of maintenance 3h successively, in 6h, be down to 30 DEG C;
(5) drip dimethyl formamide under agitation, concussion, filter, vacuum-drying; The consumption of described dimethyl formamide is with the described Cr (NO of every 4g step (1)
3)
3.9H
2o correspondence uses 15 ~ 20ml dimethyl formamide;
(6) loaded in stainless steel autoclave by dry for step (5) gained thing, add alcohol immersion 3 ~ 5 times, ammonium fluoride solution embathes 1 ~ 2 time;
(7) filter, with warm water washing, vacuum-drying, the multistage pore canal MIL-101 material of obtained large pore volume.
2. preparation method according to claim 1, is characterized in that: the temperature of step (1) described stirring is 20 ~ 30 DEG C, and the time of stirring is 10 ~ 20 min.
3. preparation method according to claim 1, is characterized in that: the temperature of step (2) described stirring is 20 ~ 30 DEG C, and the time of stirring is 1 ~ 2 h.
4. preparation method according to claim 1, is characterized in that: the temperature of step (3) described stirring is 20 ~ 30 DEG C, and the time of stirring is 30 ~ 60min; The mass percent concentration of described hydrofluoric acid solution is 40%.
5. preparation method according to claim 1, is characterized in that: the described concussion temperature of step (5) is 35 ~ 45 DEG C, and the concussion time is 40min ~ 1h; Described vacuum-drying temperature is 120 ~ 150 DEG C, and time of drying is 10 ~ 15h.
6. preparation method according to claim 1, is characterized in that: the temperature that step (6) described ethanol embathes 100 ~ 150 DEG C, embathes time 8 ~ 14h at every turn; The concentration of described ammonium fluoride solution is 30 ~ 40mmol/L, and embathing temperature is 50 ~ 60 DEG C, embathes time 8 ~ 14h.
7. preparation method according to claim 1, is characterized in that: the described vacuum drying temperature of step (7) is 120 ~ 150 DEG C, and time of drying is 10 ~ 15h, and warm water temperature is 60 ~ 70 DEG C.
8. the multistage pore canal MIL-101 material of the large pore volume prepared by preparation method described in any one of claim 1 ~ 7.
9. the application of multistage pore canal MIL-101 material in water absorption and organic steam adsorbing domain of large pore volume according to claim 8.
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| CN111389371A (en) * | 2020-04-28 | 2020-07-10 | 宋家豪 | Modified adsorbent based on glass fiber and preparation method thereof |
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