CN104557718B - A kind of preparation method and applications of RHO zeolite type 2-ethyl imidazol(e) zinc porous material - Google Patents
A kind of preparation method and applications of RHO zeolite type 2-ethyl imidazol(e) zinc porous material Download PDFInfo
- Publication number
- CN104557718B CN104557718B CN201410595736.8A CN201410595736A CN104557718B CN 104557718 B CN104557718 B CN 104557718B CN 201410595736 A CN201410595736 A CN 201410595736A CN 104557718 B CN104557718 B CN 104557718B
- Authority
- CN
- China
- Prior art keywords
- maf
- porous material
- ethyl imidazol
- preparation
- zeolite type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/62—In a cartridge
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J2220/86—Sorbents applied to inner surfaces of columns or capillaries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation method of a kind of RHO zeolite type 2 ethyl imidazol(e) zinc porous material and the application in gas chromatogram thereof.The Porous coordination polymer that the present invention relates to, its structural formula is RHO [Zn (eim)2] (code name MAF 6), wherein eim‑Representing the anion after organic ligand 2 ethyl imidazol(e) (Heim) sloughs proton, RHO representation compound has the topological structure of RHO zeolite.Present invention improves over traditional quickly mixing acid-base neutralization reaction, by optimizing the parameters such as reactant concentration, template consumption and response time, particularly change feeding sequence, reactant concentration ratios different when i.e. reaction system starts, finally prepared relatively large high-quality MAF 6, and gained sample has good heat stability and chemical stability, hole ratio is 55.4%, and Langmuir specific surface is more than 1650 m2 g‑1.Described porous material MAF 6 can be prepared as capillary column, has good gas chromatogram separating power and repeatability, and preferably heat/chemical stability, can be used for the organic compound of separation detection boiling point or adjoining dimensions.
Description
Technical field
The present invention relates to coordination compound field of porous materials and gas chromatogram field, more particularly, to a kind of RHO zeolite
The preparation method and applications of type 2-ethyl imidazol(e) zinc porous material.
Background technology
Porous coordination polymer is a kind of crystalline material being made up of metal ion and organic ligand, has specific surface area
Greatly, density is low, aperture size can be in harmonious proportion the advantages such as channel surfaces modifiability is strong, can be widely used for gas absorption and storage, point
From with the fields such as catalysis.And in terms of analytical chemistry, such as field investigation and sampling, Solid-Phase Extraction, high performance liquid chromatography and gas chromatogram
Deng the concern also receiving researcher.
Such as analysis speed is fast and separation efficiency is high owing to having for gas chromatogram (Gas Chromatography is called for short GC)
Feature, be the most widely used in scientific research and commercial production as a kind of common method for separating and analyzing.Wherein, GC
Separating power depend on chromatographic column, especially fix the selection of phase.The fixing porous material needing gram level mutually as packed column
Material, makes and spends greatly, and as the fixing thin film of surface coating within it that has only to mutually of capillary column, extremely saves use
Amount, and can significantly mention post effect.But, prepare the granule of this type of fixing phase it is generally required to nanometer or other of submicron order
Grain is to guarantee uniformity and the high post effect of thin film.
2-three kinds of supramolecular isomers of ethyl imidazol(e) zinc (II) crystallizable one-tenth, are respectively provided with ANA (MAF-5), RHO
And qtz (MAF-32) topological structure (MAF-6).There is 2-ethyl imidazol(e) zinc (II) (code name MAF-6) tool of RHO topological structure
There are loose structure, hydrophobic hole surface and the potential separating property of excellence.If MAF-6 consolidating as capillary column can be utilized
The fixed gas chromatogram realizing compound mutually separates, and it may show good separating effect.But, there is presently no document report
The synthetic method of the road pure phase of this material.MAF-6 is found as by-product when MAF-5 solution diffusion method synthesizes the earliest
(Angew. Chem. Int. Ed., 2006,45:1557).Although Friscic seminar finds by ball-milling method ZnO and
Heim can react and obtain MAF-5 and MAF-6, but product impure (containing ZnO) and the most easily changing into
Closs packing isomer MAF-32(Angew. Chem. Int. Ed., 2010,49,9640).It addition, do not have the most yet
There is the case of the actual application of this porous material.
The group water solution utilizing slaine and glyoxaline ligand directly mix add the mode of alkali liquor again can be the most a large amount of
Synthesizing methyl zinc imidazolate (code name MAF-4) (CN 103635463 A), but the method can not synthesize pure phase MAF-6；Take fast
Speed mixing soda acid neutralisation, alcoholic solution and the zinc ammonia solution of part are simply mixed stirring, distinguish successfully synthesis MAF-5 with
MAF-32(ZL201010169244.4).But directly utilize this traditional method, the MAF-6 of pure phase cannot be obtained the most all the time,
It is relatively big that this is likely due to its hole, the most sensitive to reaction condition.Accordingly, during we improve general quickly mixing soda acid
And method, it being able to a large amount of MAF-6 of Fast back-projection algorithm, the method productivity is high, and gained sample purity is the highest, and shows the porous of excellence
Energy, good heat/chemical stability.It addition, the MAF-6 synthesized in this way is as the fixing gas phase color preparing superior performance mutually
Spectrum capillary column.
Summary of the invention
The technical problem to be solved is to provide the preparation of a kind of RHO zeolite type 2-ethyl imidazol(e) zinc porous material
Method.
It is a further object to provide the gas-phase chromatographic capillary column of above-mentioned 2-ethyl imidazol(e) zinc porous material
Preparation and application.
The technical problem to be solved is achieved by the following technical programs:
The preparation method of a kind of RHO zeolite type 2-ethyl imidazol(e) zinc porous material, comprises the steps:
(1) being dissolved in the middle of organic solvent by organic ligand 2-ethyl imidazol(e), stir formation mixed liquor A,
(2) stir after then template being added mixed liquor A formation mixed liquid B, wherein, described template with mix
The volume ratio of liquid A is 6:90 ~ 120；
(3) being added to solvent by zinc hydroxide, stir formation mixed liquor C；
(4) mixed liquor C is at the uniform velocity added in 20-40min react to mixed liquid B, after reaction, product is carried out
Filter, wash, be dried, obtain described RHO zeolite type 2-ethyl imidazol(e) zinc porous material.
Further, the concentration of described mixed liquor A is 0.08-0.13 mol/L.
Further, the concentration of described mixed liquor C is 0.03-0.06 mol/L.
Further, organic solvent in step (1) is at least one of methanol or ethanol.
Further, described template is at least one in benzene, hexamethylene or dimethylbenzene.
Further, the solvent in described step (2) is aqueous ammonia solvent.
It is further preferred that the concentration of described aqueous ammonia solvent is 22%-28%.
Wherein, the nanometer 2-ethyl imidazol(e) zinc porous material of preparation method gained of the present invention has RHO topological structure (code name
For MAF-6), its chemical formula is [Zn (C5H7N2) 2], and wherein C5H7N2 represents organic ligand 2-ethyl imidazol(e) (Heim) and sloughs matter
Anion after son.And, traditional quickly mixing soda acid neutralisation, is by the simplest to alcoholic solution and the zinc ammonia solution of part
Mix and blend is to prepare target compound, but experiment confirms that this method cannot obtain pure phase MAF-6(and see comparative example 1-3).This
Bright based on the general principle quickly mixing soda acid neutralisation, during by optimizing reactant concentration, template consumption and reaction
Between etc. parameter, particularly change feeding sequence, reactant concentration ratios different when i.e. reaction system starts, finally closed
Become out the MAF-6 of relatively large pure phase.
By the nanometer 2-ethyl imidazol(e) zinc porous material of above-mentioned preparation method gained as fixing in gas chromatograph
Application.
The preparation method of above-mentioned fixing phase comprises the steps:
(1) nanometer 2-ethyl imidazol(e) zinc porous material is scattered in solvent and is respectively formed suspension C；
(2) by suspension C by being coated on capillary inner surface in noble gas press-in capillary column；
(3) described fixing phase is obtained after carrying out burin-in process under an inert atmosphere.
Solvent in the preparation method of fixing phase selects, burin-in process mode is the known technology of the art,
The present invention is not described in detail.
There is advantages that
(1) used by the present invention, synthetic method raw material and solvent are cheap and easily-available, and the response time is short, and productivity is high；
(2) the inventive method can be directly synthesized a large amount of MAF-6 nanoscale powder crystal, size uniformity, and synthesized MAF-6 is pure
Spend the highest, Heat stability is good, 400 oC can be stabilized to；Solvent stability is also fine, refluxes and at least stablize 7 in benzene and methanol
My god, saturated vapor can being stablized two weeks, 3 days can also be stablized even if being completely sunk in the water；
(3) MAF-6 synthesized by the present invention has the biggest hole ratio and specific surface area, the specific surface of this material and hole
Rate is to utilize low temperature nitrogen absorption and use Langmuir and Dubinin-Raduskhvich Equation for Calculating to obtain respectively, its
Langmuir specific surface area is 1695 m2 g-1, and pore volume is 0.61 cm3 g-1；
(4) MAF-6 synthesized by the present invention has hydrophobic hole surface, to common solvents (benzene, ethanol, first alcohol and water)
Absorption start pressure and become positive correlation with the polarity of this solvent；
(5) the nanoscale MAF-6 that gas-phase chromatographic capillary column coating is uniform particle sizes that prepared by the present invention, and be distributed relatively
Uniformly；
(6) (linear paraffin and the hexane of normal hexane-n-decane are different to alkane for gas-phase chromatographic capillary column prepared by the present invention
Structure body) and substituted benzene (xylene isomer；Styrene and ethylbenzene；Benzene, cyclohexene and hexamethylene) show high dividing
From degree and selectivity factor and good repeatability.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction figure of MAF-6 of the present invention.
Fig. 2 is the thermogravimetric curve figure of MAF-6 of the present invention.
Fig. 3 is MAF-6 of the present invention nitrogen adsorption isotherm when 77 K.
Fig. 4 is MAF-6 ambient solvent vapor sorption isothermal line of the present invention.
Fig. 5 is the scanning electron microscope (SEM) photograph that MAF-6 of the present invention fixes the MAF-6 of phase as gas-phase chromatographic capillary column.
Fig. 6 is the gas chromatogram that on gas-phase chromatographic capillary column prepared by the present invention, linear paraffin separates.
Fig. 7 is the gas chromatogram that on gas-phase chromatographic capillary column prepared by the present invention, isomeric hexane body separates.
Fig. 8 is the gas chromatogram of separation of Xylene Isomer on gas-phase chromatographic capillary column prepared by the present invention.
Fig. 9 is the gas chromatogram that on gas-phase chromatographic capillary column prepared by the present invention, benzene, cyclohexene and hexamethylene separate.
Figure 10 is the gas chromatogram that on gas-phase chromatographic capillary column prepared by the present invention, styrene separates with ethylbenzene.
Figure 11 is traditional PXRD pattern quickly mixing soda acid neutralisation gained sample.
Figure 12 is to improve reactant mixing velocity and the PXRD pattern of template concentration gained sample.
Figure 13 is the PXRD pattern by changing reactant concentration gained sample.
Detailed description of the invention
The present invention is further described below in conjunction with the accompanying drawings with specific embodiment.Unless stated otherwise, the present invention uses
Reagent, equipment and method be the art conventional commercial reagent, equipment and conventional use of method.
The preparation of embodiment 1 Porous coordination polymer MAF-6
By 2-ethyl imidazol(e) (4.0 mmol, 0.384 g) is dissolved in methanol solution (30 mL) and obtains colorless cleared solution,
Add 5 mL hexamethylene.At ambient temperature, Zn (OH) at the uniform velocity it is added dropwise in 40 min2(2.0 mmol, 0.198 g) dense
Ammonia (25%, 40 mL) solution, is then stirred for 1 h, is filtered by the white precipitate obtained, washs with water and methanol and be dried,
Obtain 0.40 g sample (productivity 78%).Gained powder under nitrogen atmosphere 120oC heats 30 min and removes guest molecule, i.e.
The MAF-6 of the pure phase without object can be obtained.The X-ray diffractogram of product is shown in Fig. 1.
The heat stability of embodiment 2 embodiment 1 gained MAF-6 characterizes
The heat stability of the MAF-6 of embodiment 1 gained is obtained by thermogravimetry.Thermogravimetric curve figure is shown in Fig. 2.
The porous of embodiment 3 embodiment 2 gained MAF-6 characterizes
Put in hyaloid QC, then at ASAP 2020M adsorption instrument after the MAF-6 of embodiment 1 gained is removed object
Its nitrogen adsorption isotherm is measured under the conditions of 77 K.N2Adsorption isotherm is the absorption of I type, and Langmuir specific surface area is 1695
m2 g-1, BET specific surface area is 1343 m2 g-1, its adsorption isotherm line chart is shown in Fig. 3.
Put in hyaloid QC after the MAF-6 of embodiment 1 gained is removed object, then adsorb at BELSORP-max
Benzene, ethanol, the vapor sorption isothermal line of first alcohol and water is measured under instrument room temperature condition.The saturated extent of adsorption of benzene, ethanol and methanol (P/P 0=0.83 value) it is respectively 6.3 mmol g-1、9.2 mmol g-1With 13.2 mmol g-1, water base is not adsorbed,
Adsorption isotherm line chart is shown in Fig. 4.
The preparation of the embodiment 4 capillary column with MAF-6 as coating
The MAF-6 of embodiment 1 gained is carried out ultrasonic disperse process, after standing 12 h, the soliquid on upper strata is centrifuged
Collect, at the air drying of 120 ° of C.Before coating MAF-6, vitreous silica capillary tube is the most respectively with NaOH solution, hydrochloric acid
And milli-Q water, then 120oN is used at a temperature of C2Purge 3 h to dry.The methanol suspension of MAF-6 is passed through N2Press-in hair
In capillary column, at N2Temperature programming is used to activate after air-flow stands 1 h: 60 ° of C constant temperature 30 minutes, then 5 ° of C min-1It is warmed up to 150 ° of C constant temperature 60 min, then 5 ° of C min-1It is warmed up to 250 ° of C constant temperature 60 min.Temperature program(me) repeats
3 times.The scanning electron microscopic picture of capillary column is shown in Fig. 5.
Alkane is separated by the capillary column of embodiment 5 embodiment 4 gained with the gas chromatogram of substituted benzene
5 μ L analytes of decile are injected into and have been filled with N225 mL hermetic glass bottle in, and 100oC heats
3 minutes, then extract a certain amount of and N2Analyte (xylol isomer, benzene/cyclohexene/hexamethylene, the benzene second of mixing
Alkene/ethylbenzene is 20 L；C6 Alkane isomer is 4L；Normal hexane-n-decane linear paraffin is 6 L) at Agilent 7890 be
Test on system.Taking hand sampling, the inlet temperature of gas chromatograph and the temperature of thermal conductivity detector (TCD) are set as 250oC,
N2As carrier gas, qualitative by chromatographic peak retention time, use peak area quantification.The gas chromatogram of each analyte component see Fig. 6-
10。
The sample quickly mixing soda acid neutralisation gained that comparative example 1 is traditional
Use traditional quickly mixing soda acid neutralisation, by methanol (or ethanol) solution and the Zn (OH) of Heim2Strong aqua ammonia
(25%) solution is plus finite concentration hydrophobicity template (benzene or hexamethylene) directly mix and blend, obtains the MAF-5 of high yield.
But, if this mixture to be continued stirring reaction 3 days, product will appear from MAF-32.Template concentration is increased under the conditions of this
Also cannot obtain target product MAF-6(and see Figure 11).
Comparative example 2 changes reactant mixing velocity and the sample of template concentration gained
On the basis of traditional quickly mixing soda acid neutralisation, we change reactant mixing velocity, will the first of Heim
Alcoholic solution is slowly added drop-wise to be pre-mixed the Zn (OH) of the hydrophobicity template (benzene or hexamethylene) of variable concentrations2Strong aqua ammonia is molten
In liquid, stirring obtains the White microcrystalline product of high yield.When without template, product is MAF-32.But add a small amount of
During template (2.50%,v/v), product is the mixture of MAF-32 and MAF-5.When the concentration of template increases to 3.25%(v/v), pure MAF-5 product may only be obtained.When template concentrations increases to 5.00%(v/v), product is MAF-6, MAF-5 and MAF-32
Mixture, but further increase template concentration (12.5%,v/v), product is the most still MAF-6, MAF-5 and MAF-
The mixture (see Figure 12) of 32.Result shows, benzene or hexamethylene can be used as synthesizing the template of MAF-5 and MAF-6, and template
Agent concentration is the highest, is more conducive to the generation of MAF-6, but such synthetic method is also not enough to obtain pure MAF-6 product.
Comparative example 3 is by changing the sample of reactant concentration gained
By Zn (OH)2Concentrated ammonia solution (25%) joins in the methanol solution of Heim, when ligand concentration is 0.08-0.13
mol L-1Or 0.20 mol L-1Time, product is respectively the mixture of MAF-6 and MAF-5 or pure MAF-5.If reaction is mixed
Compound continues stirring 3 days, and product will be completely transformed into MAF-32, illustrate that MAF-6 is belonging to the most favourable product.These
Test result indicate that, in this reaction system, methanol can also be as the template of MAF-6, but it is also not enough to obtain pure
MAF-6.By the simple concentration changing reactant, the MAF-6 crystallite (see Figure 13) of a large amount of pure phase can not be obtained.
Relatively above comparative example with embodiment 1 it can be seen that utilize and traditional quick mix soda acid neutralisation, in any case
Adjust reactant concentration and the consumption of template, be all the MAF-6 that cannot obtain pure phase.Therefore for the system of this special material
For Bei, the dropping order of reactant and template and the proportioning of drop rate, reactant and template, the most each reactant
The series of parameters such as concentration are the most crucial, and the core technology of the present invention is that and provides a kind of new and effective reaction stream
Journey, for the MAF-6 that processability is superior in large quantities.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained
Art scheme, all should fall within the scope and spirit of the invention.
Claims (7)
1. the preparation method of a RHO zeolite type 2-ethyl imidazol(e) zinc porous material, it is characterised in that comprise the steps:
S1. being dissolved in the middle of organic solvent by organic ligand 2-ethyl imidazol(e), stir formation mixed liquor A,
The most then stir after template being added mixed liquor A formation mixed liquid B, wherein, and described template and mixed liquor A
Volume ratio be 6:90 ~ 120；
S3. being added to solvent by zinc hydroxide, stir formation mixed liquor C；
S4. mixed liquor C is at the uniform velocity added in 20-40min and react to mixed liquid B, after reaction, product was carried out
Filter, wash, be dried, obtain described RHO zeolite type 2-ethyl imidazol(e) zinc porous material；
The concentration of described mixed liquor A is 0.08-0.13 mol/L；
The concentration of described mixed liquor C is 0.03-0.06 mol/L.
The preparation method of a kind of RHO zeolite type 2-ethyl imidazol(e) zinc porous material the most according to claim 1, its feature exists
In, organic solvent in step sl is at least one of methanol or ethanol.
The preparation method of a kind of RHO zeolite type 2-ethyl imidazol(e) zinc porous material the most according to claim 1, its feature exists
In, described template is at least one in benzene, hexamethylene or dimethylbenzene.
The preparation method of a kind of RHO zeolite type 2-ethyl imidazol(e) zinc porous material the most according to claim 1, its feature exists
In, the solvent in described step S3 is aqueous ammonia solvent.
The preparation method of a kind of RHO zeolite type 2-ethyl imidazol(e) zinc porous material the most according to claim 1, its feature exists
In, the concentration of described aqueous ammonia solvent is 22%-28%.
6. the RHO zeolite type 2-ethyl imidazol(e) zinc porous material of a claim 1 preparation method gained as fixing at gas
Application in chromatography.
7. the preparation method of the fixing phase in a gas chromatograph, it is characterised in that comprise the steps:
(1) RHO zeolite type 2-ethyl imidazol(e) zinc porous material is scattered in solvent formation suspension C；
(2) by suspension C by being coated on capillary inner surface in noble gas press-in capillary column；
(3) described fixing phase is obtained after carrying out burin-in process under an inert atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410595736.8A CN104557718B (en) | 2014-10-30 | 2014-10-30 | A kind of preparation method and applications of RHO zeolite type 2-ethyl imidazol(e) zinc porous material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410595736.8A CN104557718B (en) | 2014-10-30 | 2014-10-30 | A kind of preparation method and applications of RHO zeolite type 2-ethyl imidazol(e) zinc porous material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104557718A CN104557718A (en) | 2015-04-29 |
| CN104557718B true CN104557718B (en) | 2016-12-07 |
Family
ID=53074894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410595736.8A Expired - Fee Related CN104557718B (en) | 2014-10-30 | 2014-10-30 | A kind of preparation method and applications of RHO zeolite type 2-ethyl imidazol(e) zinc porous material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104557718B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819424A (en) * | 2016-03-21 | 2016-08-03 | 太原理工大学 | Preparation method of porous carbon material |
| CN108744596A (en) * | 2018-05-31 | 2018-11-06 | 南开大学 | A kind of preparation method for detaching the micropore organic network quartz capillary column of hexane isomer |
| CN108587732A (en) * | 2018-06-06 | 2018-09-28 | 太原理工大学 | A kind of solid additive and its application |
| CN111617743B (en) * | 2020-06-08 | 2023-01-06 | 太原理工大学 | Zeolite imidazolate framework material ANA- [ Co (eIm) 2 ]Preparation method and application of |
-
2014
- 2014-10-30 CN CN201410595736.8A patent/CN104557718B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104557718A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107362785B (en) | Hydrazone bond connection type chiral covalent organic framework bonded silica gel stationary phase and application thereof | |
| CN104557718B (en) | A kind of preparation method and applications of RHO zeolite type 2-ethyl imidazol(e) zinc porous material | |
| CN108014752B (en) | A kind of separation method of metal-organic framework material and ethylene-ethane for separating ethane and ethylene | |
| CN110292910B (en) | Chiral MOFs functional material and preparation method and application thereof | |
| Li et al. | A novel dispersive solid-phase extraction method using metal-organic framework MIL-101 as the adsorbent for the analysis of benzophenones in toner | |
| CN114130374B (en) | Application of magnetic carboxylated covalent organic framework material as magnetic solid-phase extraction adsorbent | |
| Qian et al. | Immobilized chiral tropine ionic liquid on silica gel as adsorbent for separation of metal ions and racemic amino acids | |
| CN110327886B (en) | Zeolite imidazate framework material and preparation method and application thereof | |
| WO2015192387A1 (en) | Aqueous phase metal organic framework molecular imprinting material of enriched trace metolcarb | |
| CN112473625B (en) | Preparation method of ultra-microporous metal organic framework material for separating acetylene and ethylene | |
| CN109261141A (en) | A kind of ZIF-8 is nanocrystalline and its preparation method and application | |
| CN106674118A (en) | Preparation of ZIF-8 adsorption material and application of ZIF-8 adsorption material to de-coloring of malachite green water solution | |
| CN104722284A (en) | Microporous material loaded ion liquid composite material or film, and preparation thereof | |
| CN102775430B (en) | Coordination polymer porous material MAF-X8 and preparing method and application thereof | |
| CN110575817A (en) | Magnetic different-pore covalent nano material and preparation method and application thereof | |
| Jiang et al. | One-step fabrication of hydrophilic MIL-68 (Al)/Chitosan-coated melamine sponge for vortex-assisted solid-phase extraction of parabens in water samples | |
| CN110833818A (en) | Preparation method of hierarchical porous metal-organic framework gas chromatography stationary phase material | |
| CN108727607A (en) | A kind of separation method for detaching the metal-organic framework material and xenon Krypton of xenon and Krypton | |
| Dowlatshah et al. | A silica-based three-dimensional molecularly imprinted coating for the selective solid-phase microextraction of difenoconazole from wheat and fruits samples | |
| CN104083904B (en) | Functionalization porous zinc sulfide nano microballoon solid-phase extraction column and preparation method thereof | |
| Yohannes et al. | Preconcentration of tropane alkaloids by a metal organic framework (MOF)-immobilized ionic liquid with the same nucleus for their quantitation in Huashanshen tablets | |
| CN108993417A (en) | A kind of metal-organic framework material and its preparation and application for xenon and Krypton adsorbing separation | |
| CN105080517A (en) | Hybrid mesoporous silica gel matrix coated type polysaccharide chiral stationary phase and preparation method therefor | |
| CN114713196A (en) | Preparation and application of metal organic framework derived bimetallic oxide magnetic carbon material | |
| Lee et al. | Adsorption isotherms of caffeine and theophylline on metal-organic frameworks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161207 Termination date: 20171030 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |