CN104262400B - 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 59
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000013177 MIL-101 Substances 0.000 title abstract 5
- 238000003756 stirring Methods 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 230000009514 concussion Effects 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 239000002253 acid Substances 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- 238000007654 immersion Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000001914 filtration Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 5
- 239000012621 metal-organic framework Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000012546 transfer Methods 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
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract 1
- 229910001220 stainless steel Inorganic materials 0.000 abstract 1
- 239000010935 stainless steel Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 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
- 239000002077 nanosphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001027 hydrothermal synthesis 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
- 150000003839 salts Chemical class 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YASAKCUCGLMORW-UHFFFAOYSA-N Rosiglitazone Chemical compound C=1C=CC=NC=1N(C)CCOC(C=C1)=CC=C1CC1SC(=O)NC1=O YASAKCUCGLMORW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 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
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 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
- 239000010949 copper Substances 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
- -1 dimethyl methyl Chemical group 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
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction 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
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013589 supplement 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
-
- 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
- B01J20/28069—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
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
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 Organic substance preparation field, particularly to a kind of multi-stage porous with big pore volume
Road mil-101 material and its preparation method and application.
Background technology
It is only that metal-organic framework materials (mofs) have high-specific surface area, high porosity, aperture adjustability and topological structure
Top grade feature, is used widely in multiple fields at present, and including sensing, gas separates, adsorbs, bio-pharmaceutical carries
The aspects such as body, gas storage and catalysis.The aperture of mofs material, close to zeolite diameter, is mainly distributed onOnly
Fraction mofs has less meso-hole structure.However as petrochemical industry and the building site development that becomes more meticulous, industrial often have big point
The catalysis that son participates in, absorption, the process such as separation, little duct seriously hinders mass transfer with diffusion so that macromole cannot reach
Avtive spot within mofs micropore, thus limit the practical application of mofs.Mesoporous greatly and macropore are introduced traditional mofs
In structure, the high-specific surface area mesoporous greatly duct advantage having with macropore being had with mofs material itself and macropore
Appearance combines, and reaches the purpose of mutual supplement with each other's advantages.
Synthesis multistage pore canal mofs by extending part or can use two kinds of common methods of template to realize.2002
eddaoudi[eddaoudi m,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.] et al. report the first mesoporous mof material zn4o(tpdc)3·
(dmf)12(h2o)2(irmof-16), this materials'use has captain's part to dicarboxylic acids terphenyl (tpdc) and zn2+Salt synthesizes.
This material hasAndFixing channel diameter.sheng-han lo[lo s h,chien c h,lai y
l,et al.a mesoporous aluminium metal–organic framework with 3nm open pores
[j] .journal of materials chemistry a, 2013,1 (2): 324-329.] etc. al (iii) ion and tool are selected
There is the h of large-size2Sdc (4,4-stilbene diacid) (13.7 angstroms) part has synthesized under hydrothermal conditions and has had mesoporous knot
The al (oh) (sdc) of structure] (cycu-3).Extend part method synthesis multistage pore canal mofs to be reported by many people, this method
Tool is resultful to be anticipated that property, has simultaneously facilitated the development of multi-stage porous mofs.But the method may lead to remove object solvent
Back skeleton caves in, and basket structure compression or framework are connected with each other, and lead to pore volume aperture to reduce, and this directly limit and extends part method
Extensively apply.
At present, introduce mesoporous or macropore using template 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.] et al. ctab is used as template, ca (citric acid) connects ctab and cu (ii) as chelating agen, synthesizes cu3
(btc)2(hkust-1).The mesoporous hkust-1 synthesizing in this way have larger mesoporous (when mol ratio ctab/ca=2.3
When, mesoporous pore size is 19.6nm, and bet specific surface area is 1162m2.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.] et al. using different
Disulfonic acid and metal nitrate or metal chlorination salt respectively as part and inorganic precursor, f127 as template, with crown ether
1,10- diaza 18- crown- 6 (nc) controls the release of metal ion as blender, and final synthesis has hexagonal mesoporous and mesoporous
Hole wall is the mofs material of 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/co2/surfactant system[j].angewandte chemie international edition,2011,
50 (3): 636-639.] et al. in supercritical co2In/ionic liquid/n-etfosa template emulsion system, synthesis mofs receives
Rice ball, comprises order mesoporous simultaneously in this nanosphere, and mesoporous wall is micropore.Mesoporous pore size is 3.6nm, nanosphere size
About 80nm.Although can successfully synthesizing multi-stage porous mofs material using template, and the method having very strong Modulatory character,
Template Types currently used for synthesis multi-stage porous mofs are still less.
Content of the invention
In place of solving the shortcoming and defect of prior art, the primary and foremost purpose of the present invention is to provide one kind to have macropore
The preparation method of the multistage pore canal mil-101 material holding.The method is intended to using a kind of new template, original in mil-101
Introduce new mesoporous and macropore on the basis of duct, expand the pore volume of mofs material simultaneously, keep its bigger serface.
Another object of the present invention is to providing a kind of multistage pore canal with big pore volume being prepared by said method
Mil-101 material.This material contains the multistage pore canal of micropore, mesoporous and macropore.
It is still another object of the present invention to provide a kind of above-mentioned multistage pore canal mil-101 material with big pore volume should
With.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of the multistage pore canal mil-101 material of big pore volume it is characterised in that: this preparation method include with
Lower operating procedure:
(1) by cr (no3)3.9h2O is soluble in water, and stirring obtains settled solution；Wherein cr (no3)3.9h2O and water mole
Than for 1:(260～270)；
(2) add 3- aminopropyl trimethoxysilane in step (1) gained settled solution, stirred under room temperature condition
Mix；3- aminopropyl trimethoxysilane and the described cr (no of step (1)3)3.9h2The mol ratio of o is 1:(0.09～0.10)；
(3) add p-phthalic acid (h2Bdc), and Deca Fluohydric acid. (hf) solution, continue stirring, obtain mixed liquor；Benzene
Dioctyl phthalate, Fluohydric acid. and the described cr (no of step (1)3)3.9h2The mol ratio of o is (0.98～1.1): (0.90～1.12): 1；
(4) step (3) gained mixed liquor is loaded in rustless steel autoclave, carry out temperature programming；Successively at 220 DEG C
Lower holding 8h, 160 DEG C of holding 3h, 90 DEG C of holding 3h, are down to 30 DEG C in 6h；
(5) Deca dimethylformamide (dmf), concussion under agitation, filters, vacuum drying；Described dimethyl methyl
The consumption of amide is with the described cr (no of every 4g step (1)3)3.9h2O is corresponding to use 15～20ml dimethylformamide；
(6) step (5) gained dried object is loaded in rustless steel autoclave, add ethanol to soak 3～5 times, fluorination
Ammonium (nh4F) solution embathes 1～2 time；
(7) filter, with warm water washing, vacuum drying, the multistage pore canal mil-101 material of big pore volume is obtained.
The temperature of the described stirring of step (1) is 20～30 DEG C, and the time of stirring is 10～20min.
The temperature of the described stirring of step (2) is 20～30 DEG C, and the time of stirring is 1～2h.
The temperature of the described stirring of step (3) is 20～30 DEG C, and the time of stirring is 30～60min；Described hydrofluoric acid solution
Mass percent concentration be 40%.
Step (5) described concussion temperature is 35～45 DEG C, and the concussion time is 40min～1h；Described vacuum drying temperature is
120～150 DEG C, drying time is 10～15h.
100～150 DEG C of the temperature that the described ethanol of step (6) embathes, embathes time 8～14h every time；Described ammonium fluoride solution
Concentration be 30～40mmol/l, embathe temperature be 50～60 DEG C, embathe time 8～14h.
The described vacuum drying temperature of step (7) is 120～150 DEG C, and drying time is 10～15h, and warm water temperature is 60
～70 DEG C.
A kind of multistage pore canal mil-101 material of the big pore volume being prepared by above-mentioned preparation method.
Application in water absorption and organic steam adsorbing domain for the multistage pore canal mil-101 material of above-mentioned big pore volume.
The present invention adopt 3- aminopropyl trimethoxysilane surfactant as template, synthesize have simultaneously micro-
Hole, the mesoporous multi-stage porous mil-101 with macroporous structure, are conducive to being applied to catalytic reaction.Simultaneously synthesizing sample has
2.27cm3The big pore volume of/g is so as to have broad application prospects in gas absorption field.
The present invention adopts hydrothermal synthesis method, using 3- aminopropyl trimethoxysilane surfactant as template, with
h2Bdc and cr (no3)3.9h2O, respectively as organic ligand and source metal, is adjusted by the order that reactant adds, crystallization is certain
Obtain after time that there is micropore, the multistage pore canal mil-101 of mesoporous and macropore and big pore volume.
Compared with prior art, the method have the advantages that
(1) the multi-stage porous mil-101 material of present invention preparation has micropore, mesoporous and macroporous structure simultaneously, prepares
Multi-stage porous mil-101 is made up of regular octahedron；
(2) the multi-stage porous mil-101 material of present invention preparation has larger specific surface area and pore volume, bet specific surface area
Up to 3385m3/ g, pore volume is 2.27cm3/g；
(3) present invention is only using a kind of surfactant of 3 aminopropyl trimethoxysilane as template, using hydro-thermal method
Synthesis, its building-up process is easy.
Figure of description
Fig. 1 is the n of the multi-stage porous mil-101 material of embodiment 1 preparation2Adsorption-desorption isothermal figure.
Fig. 2 is the multi-stage porous mil-101 material pore size distribution curve figure of embodiment 1 preparation.
Fig. 3 is the xrd spectrogram of the multi-stage porous mil-101 material of embodiment 1 preparation.
Fig. 4 is the sem figure of the multi-stage porous mil-101 material of embodiment 1 preparation.
Fig. 5 is the tem figure of the multi-stage porous mil-101 material of embodiment 1 preparation.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
By 4.0g cr (no3)3.9h2O is dissolved in h2In o 48ml, 30 DEG C of stirring 20min obtain settled solution；Add 0.18g
3- aminopropyl trimethoxysilane, adds 1.64g h after stirring 1h at 30 DEG C2Bdc, dropwise Deca 0.5ml mass fraction 40%
Hydrofluoric acid solution, at dispersed latter 30 DEG C continue stirring 30min.Reactant liquor is moved into rustless steel autoclave program liter
Temperature, keeps 8h, 160 DEG C of holding 3h, 90 DEG C of holding 3h at 220 DEG C.After cooling, Deca 15ml dmf stirring 30min at 40 DEG C,
Concussion, reactant liquor obtains filtrate through g1 funnel sucking filtration, then obtains filter cake through g4 funnel sucking filtration, is vacuum dried 10h at 150 DEG C.Obtain sample
Product ethanol at 150 DEG C embathes 4 times, each 12h.Again with 30mmol/l nh4F solution soaks 10h at 60 DEG C, sucking filtration and with
60 DEG C of warm water washing samples, are vacuum dried 10h, the multistage pore canal mil-101 material sample b1 of big pore volume are obtained at 150 DEG C.
Embodiment 2
By 4.0g cr (no3)3.9h2O be dissolved in h2In o 46ml, 20 DEG C of stirring 10min obtain settled solution；Add
0.16g 3- aminopropyl trimethoxysilane, adds 1.63g h after stirring 2h at 30 DEG C2Bdc, dropwise Deca 0.4ml mass divide
The hydrofluoric acid solution of number 40%, continues stirring 40min at dispersed latter 30 DEG C.Reactant liquor is moved into rustless steel autoclave
Temperature programming, keeps 8h, 160 DEG C of holding 3h, 90 DEG C of holding 3h at 220 DEG C.After cooling, Deca 18ml dmf stirring at 35 DEG C
40min, concussion, reactant liquor obtains filtrate through g1 funnel sucking filtration, then obtains filter cake through g4 funnel sucking filtration, is vacuum dried 15h at 120 DEG C.
Obtain sample ethanol at 100 DEG C to embathe 5 times, each 8h.Again with 35mmol/l nh4F solution soaks 10h, sucking filtration at 50 DEG C
And with 70 DEG C of warm water washing samples, sample is vacuum dried at 140 DEG C 12h, the multistage pore canal mil-101 material of big pore volume is obtained
Material sample b2.
Embodiment 3
By 4.0g cr (no3)3.9h2O be dissolved in h2In o 49ml, 40 DEG C of stirring 20min obtain settled solution；Add
0.17g 3- aminopropyl trimethoxysilane, adds 1.83g h after stirring 1.5h at 20 DEG C2Bdc, dropwise Deca 0.4ml mass
The hydrofluoric acid solution of fraction 40%, continues stirring 60min at dispersed latter 20 DEG C.Reactant liquor is moved into rustless steel reaction under high pressure
Kettle temperature programming, keeps 8h, 160 DEG C of holding 3h, 90 DEG C of holding 3h at 220 DEG C.After cooling, at 45 DEG C, dropwise Deca 20ml
Dmf stirs 60min, concussion, and reactant liquor obtains filtrate through g1 funnel sucking filtration, then obtains filter cake through g4 funnel sucking filtration, and at 140 DEG C, vacuum is done
Dry 12h.Obtain sample ethanol at 120 DEG C to embathe 3 times, each 14h.Again with 40mmol/l nh4F solution soaks at 50 DEG C
14h, sucking filtration with 65 DEG C of warm water washing samples, it is vacuum dried 15h at 120 DEG C, the multistage pore canal mil-101 material of big pore volume is obtained
Material sample b3.
Embodiment 4
By 4.0g cr (no3)3.9h2O and 1.74g h2Bdc is dissolved in h2In o 49ml, dispersed after dropwise Deca 0.5ml
Mass fraction is 40% hydrofluoric acid solution, adds 0.18g 3- aminopropyl trimethoxysilane, continue at 30 DEG C after stirring 2h
Stirring 60min.By reactant liquor move into rustless steel autoclave temperature programming, at 220 DEG C keep 8h, 160 DEG C keep 3h, 90 DEG C
Keep 3h.Deca 20ml dmf stirring 40min, concussion after cooling, reactant liquor obtains filtrate through g1 funnel sucking filtration, then takes out through g4 funnel
Filter to obtain filter cake, at 150 DEG C, be vacuum dried 12h.Obtain sample ethanol at 150 DEG C to embathe 5 times, each 8h.Again with 35mmol/l
nh4F solution soaks 10h at 60 DEG C, sucking filtration with 70 DEG C of warm water washing samples, is vacuum dried 10h, prepared macropore at 150 DEG C
The multistage pore canal mil-101 material sample b4 holding.
With embodiment 1 as representative, the multi-stage porous mil-101 of embodiment 1 preparation is analyzed, other embodiment analysis knot
Structure with embodiment 1, does not provide substantially one by one.
(1) pore structure property
The asap-2020 specific surface pore-size distribution instrument being produced using micro company of the U.S. is to sample prepared by the present invention
Pore structure is characterized, and result such 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 is as can be seen that 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 12Adsorption/desorption curve is it can be seen that multistage pore canal prepared by the present invention
Mil-101 has meso-hole structure, Fig. 2 be the embodiment of the present invention 1 multi-stage porous mil-101 pore size distribution curve it can be seen that this
The prepared multistage pore canal mil-101 of invention has large range of pore-size distribution, is provided simultaneously with micropore, mesoporous and three kinds of holes of macropore
Gauge structure, is conducive to material in the extensive application of catalytic field, and prepared by the present invention with other products, all show identical spy
Property.
(2) crystal structure properties (embodiment 1) of multi-stage porous mil-101
The crystalline substance to the embodiment of the present invention 1 for the d8-advance model x-ray diffraction instrument being produced using German bruker company
Body structure is characterized, and wherein operating condition is: copper target, 40kv, 40ma, 0.02 degree of step-length, 17.7 seconds/step of scanning speed.
Fig. 3 be the embodiment of the present invention 1 xrd spectrogram, from figure 3, it can be seen that the sample prepared 2 θ=2.84 °,
All the characteristic diffraction peak peak of mil-101 in 3.31 °, 5.22 °, 8.45 ° and 9.10 °, illustrate that product has mil-101 crystallization knot
Structure.
(3) the sem figure of multi-stage porous mil-101
Using zeiss ultra 55 type field emission scanning electron microscope (carl zeiss company, Germany) to sample
Surface topography is characterized.Result as shown in figure 4, sample presents the surface topography of relatively uniform crystallization, by many sizes and
The more uniform octahedra nanometer small crystalss of shape are piled up and are formed.
(4) the tem figure of multi-stage porous mil-101
Using jem-2100hr type transmission electron microscope (electronics corporation jeol, Japan), product is characterized.Result
As shown in figure 5, multi-stage porous mil-101 has abundant accumulation hole, and aperture is larger, and distribution is wider.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.
Claims (7)
1. a kind of multistage pore canal mil-101 material of big pore volume preparation method it is characterised in that: this preparation method includes following
Operating procedure:
(1) by cr (no3)3·9h2O is soluble in water, and stirring obtains settled solution；Wherein cr (no3)3·9h2O and the mol ratio of water
For 1:260～1:270；
(2) add 3- aminopropyl trimethoxysilane in step (1) gained settled solution, be stirred under room temperature condition；3-
Aminopropyl trimethoxysilane and the described cr (no of step (1)3)3·9h2The mol ratio of o is 1:0.09～1:0.10；
(3) add p-phthalic acid, and Deca hydrofluoric acid solution, continue stirring, obtain mixed liquor；Phthalic acid, Fluohydric acid. and
Described cr (the no of step (1)3)3·9h2The mol ratio of o is (0.98～1.1): (0.90～1.12): 1；
(4) step (3) gained mixed liquor is loaded in rustless steel autoclave, carry out temperature programming；Protect at 220 DEG C successively
Hold 8h, 160 DEG C of holding 3h, 90 DEG C of holding 3h, be down to 30 DEG C in 6h；
(5) Deca dimethylformamide, concussion under agitation, filters, vacuum drying；The consumption of described dimethylformamide
With the described cr (no of every 4g step (1)3)3·9h2O is corresponding to use 15～20ml dimethylformamide；
(6) step (5) gained dried object is loaded in rustless steel autoclave, add ethanol to soak 3～5 times, ammonium fluoride is molten
Immersion washes 1～2 time；
(7) filter, with warm water washing, vacuum drying, the multistage pore canal mil-101 material of big pore volume is obtained.
2. preparation method according to claim 1 it is characterised in that: the temperature of the described stirring of step (1) be 20～30 DEG C,
The time of stirring is 10～20min.
3. preparation method according to claim 1 it is characterised in that: the temperature of the described stirring of step (2) be 20～30 DEG C,
The time of stirring is 1～2h.
4. preparation method according to claim 1 it is characterised in that: the temperature of the described stirring of step (3) be 20～30 DEG C,
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 it is characterised in that: step (5) described concussion temperature be 35～45 DEG C, shake
Time of swinging is 40min～1h；Described vacuum drying temperature is 120～150 DEG C, and drying time is 10～15h.
6. preparation method according to claim 1 it is characterised in that: temperature that the described ethanol of step (6) embathes 100～
150 DEG C, embathe time 8～14h every time；The concentration of described ammonium fluoride solution is 30～40mmol/l, and embathing temperature is 50～60
DEG C, embathe time 8～14h.
7. preparation method according to claim 1 it is characterised in that: the described vacuum drying temperature of step (7) be 120～
150 DEG C, drying time is 10～15h, and warm water temperature is 60～70 DEG C.
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| CN107362830B (en) * | 2017-06-27 | 2020-01-10 | 哈尔滨理工大学 | Preparation method of MIL-101(Cr) loaded CdS hydrogen production photocatalyst |
| CN107088401B (en) * | 2017-06-29 | 2020-02-21 | 华中科技大学 | Rapid CO production using ionic liquid additives2Method for producing adsorbent |
| CN108404871A (en) * | 2018-04-20 | 2018-08-17 | 万玉梅 | A kind of preparation method of high adsorption metal-organic framework materials |
| CN110961080B (en) * | 2018-09-29 | 2022-06-28 | 中国石油化工股份有限公司 | Adsorption separation C8Adsorbent for aromatic hydrocarbon and preparation method thereof |
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