CN109535437B - Method for synthesizing MIL-100Cr with high specific surface area under extremely concentrated system by taking hydrochloric acid as regulator - Google Patents
Method for synthesizing MIL-100Cr with high specific surface area under extremely concentrated system by taking hydrochloric acid as regulator Download PDFInfo
- Publication number
- CN109535437B CN109535437B CN201811648231.8A CN201811648231A CN109535437B CN 109535437 B CN109535437 B CN 109535437B CN 201811648231 A CN201811648231 A CN 201811648231A CN 109535437 B CN109535437 B CN 109535437B
- Authority
- CN
- China
- Prior art keywords
- mil
- hydrochloric acid
- surface area
- specific surface
- product
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
The invention relates to the field of preparation of metal organic framework material MIL-100Cr, in particular to a method for synthesizing MIL-100Cr with a high specific surface area under a very concentrated system by taking hydrochloric acid as a regulator. The method comprises the following steps: CrCl with the molar ratio of 2:1:0.18:143·6H2Mixing and stirring O, trimesic acid, hydrochloric acid and deionized water, then carrying out constant-temperature crystallization reaction for 24 hours at the temperature of 220 ℃ in a sealed container, naturally cooling the sealed container to room temperature, carrying out centrifugal filtration to obtain a product, then sequentially soaking the product in deionized water and ethanol, filtering and drying to obtain the MIL-100 Cr. The preparation method has the advantages of high specific surface area of the selected product, precise and accurate data, and overcomes the defects of long reaction time of dilute solution and difficult mixing of raw materials in a solid phase method.
Description
Technical Field
The invention relates to the field of preparation of metal organic framework material MIL-100Cr, in particular to a method for synthesizing MIL-100Cr with a high specific surface area under a very concentrated system by taking hydrochloric acid as a regulator.
Background
Among many studied Metal Organic Frameworks (MOFs) materials, the MOFs material having unsaturated metal sites has been a hot point of research, and due to the strong interaction between the unsaturated metal sites and guest molecules, the MOFs material often has a good high selective adsorption capacity for specific gas molecules. The MIL-100Cr is a three-dimensional space structure formed by stacking two pore cages with different sizes, the opening size of each pore cage is 0.52-0.88nm, high-vacuum and high-temperature treatment is carried out on the MIL-100Cr material, water molecules participating in coordination of a metal center are removed, and about 1.1-2.6 mmol/g is generated-1Is not fullAnd vacancies of metallic Cr, the exposure of the partially unsaturated metal sites being beneficial for improving the N of the material2And CO2Thereby effectively separating the mixed gas N2/CH4And CO2/CH4。
In 2004, Ferey et al firstly reported a method for thermally synthesizing MIL-100Cr by using a solvent, wherein Cr powder and trimesic acid are used as raw materials, HF acid is used as a regulator, water is used as a solvent, and crystallization is required at a high temperature of 220 ℃ for 96 hours. Ying Mao et al in 2018 with CrCl3·6H2O and trimesic acid are used as raw materials, and the MIL-100Cr crystal is successfully obtained by a solid phase method at 220 ℃ for 15h through an early-stage manual grinding method, so that the synthesis time is greatly reduced, but the method extremely depends on the early-stage grinding and mixing uniformity and the content of crystal water in the raw materials, and is difficult to realize large-scale synthesis.
Disclosure of Invention
The invention aims to provide an environment-friendly MOFs method suitable for scale-up production to obtain MIL-100 Cr.
The most commonly used method for synthesizing MOFs materials at present is a solvothermal method, which realizes the synthesis of crystals by using different solvents, adjusting the PH of a solution, reaction temperature, reaction time, and the like. The synthesis of MIL-100Cr is only carried out in a laboratory at present, researchers often use dilute solution synthesis in order to obtain a crystal form with better growth, and the method is more suitable for crystal growth but not suitable for scale-up production due to longer reaction time and lower yield. Researchers also utilize solid phase synthesis to obtain MIL-100Cr crystals in a relatively short time, but the method depends on the prior grinding and mixing uniformity and the content of crystal water in raw materials and is not easy to control.
Researchers have realized the synthesis of MIL-100Cr by using both a dilute solution system and a solid phase system, but for the scale-up synthesis, the dilute solution system has good crystallization but longer reaction time, while the solid phase method has short reaction time but is difficult to uniformly mix the raw materials at the early stage, so that it is not an intermediate concentrated solution system, and can effectively overcome the problems of the dilute solution system and the solid phase system and further realize the scale-up production of MIL-100 Cr? Based on the above ideaThe inventors carried out a series of experiments. Firstly, CrCl is added in a certain proportion3·6H2Adding a small amount of water into O and trimesic acid, uniformly mixing the O and the trimesic acid by stirring, and crystallizing the mixture at 220 ℃ for a certain time, wherein the MIL-100Cr with good crystallinity cannot be obtained under the condition. On the basis, the inventor adds a certain amount of hydrochloric acid into a concentrated solution system for regulation, and successfully obtains MIL-100Cr with good crystallinity.
The invention is realized by the following technical scheme: a method for synthesizing MIL-100Cr with high specific surface area by using hydrochloric acid as a regulator under a very concentrated system comprises the following steps:
CrCl with the molar ratio of 2:1:0.18:143·6H2Mixing and stirring O, trimesic acid, hydrochloric acid and deionized water, then carrying out constant-temperature crystallization reaction for 24 hours at the temperature of 220 ℃ in a sealed container, naturally cooling the sealed container to room temperature, carrying out centrifugal filtration to obtain a product, then sequentially soaking the product in deionized water and ethanol, filtering and drying to obtain the MIL-100 Cr.
As a further improvement of the technical scheme of the invention, the soaking temperature of the product in deionized water is 85 ℃, and the soaking temperature of the product in ethanol is 60 ℃.
As a further improvement of the technical scheme of the invention, the soaking time of the product in deionized water and ethanol is 5 hours respectively.
In the present invention, the very concentrated system refers to CrCl3·6H2The concentration of O in the reaction system is higher relative to the prior art. In addition, hydrochloric acid plays a role in adjusting the pH of a reaction system in the invention, and Cl ions can coordinate with Cr in the growth process of the MIL-100Cr to promote the growth of MIL-100Cr crystals.
Further, the surface area of MIL-100Cr prepared in example 1 was calculated according to the present invention, and the detailed data thereof are shown in table 1.
TABLE 1
| SL(m2/g) | SBET(m2/g) |
| 3447.3342 | 2140.0091 |
In table SLLangmuir surface area; sBETSpecific surface area.
In addition, the inventor aims at CrCl3·6H2The different molar ratios of O and trimesic acid were studied for 24h (except for the different amounts of trimesic acid added, the other conditions were the same as in example 1), and the synthesis was carried out according to the parameters in Table 2, the synthesis results are shown in FIG. 4, and the BET characterization of the samples is shown in FIG. 5.
TABLE 2
Further, the inventor aims at CrCl3·6H2When the molar ratio of O to trimesic acid is 2:1, different amounts of hydrochloric acid were investigated (except for the amount of hydrochloric acid, the conditions were the same as in example 1), and the synthesis was carried out according to the parameters in Table 3, the synthesis results are shown in FIG. 6, and the BET characteristics of the samples are shown in FIG. 7.
TABLE 3
Meanwhile, the detailed data of the surface area of MIL-100Cr synthesized according to each parameter of Table 3 are shown in Table 4.
TABLE 4
| Serial number | SL(m2/g) | SBET(m2/g) |
| 1 | 2326.3238 | 1323.3706 |
| 2 | 2981.2424 | 1789.2371 |
| 3 | 3447.3342 | 2140.0091 |
| 4 | 2676.8004 | 1644.7910 |
Further, the inventors also aimed at CrCl3·6H2When the molar ratio of O, the powdered trimesic acid, the hydrochloric acid and the deionized water is 2:1:0.18, different reaction times are studied, the synthesis is respectively carried out according to the parameters in the table 5, the synthesis result is shown in figure 8, and the BET representation of the sample is shown in figure 9.
TABLE 5
Compared with the prior art, the invention has the following beneficial effects: the invention can mix the raw materials evenly in the concentrated solution system by simple stirring, and the MIL-100Cr sample can be obtained successfully by crystallization in a short time, centrifugation, washing and drying.
Drawings
FIG. 1 is a schematic diagram of the preparation of a very concentrated system solution, with numbers 1, 2, 3 and 4 representing CrCl respectively3·6H2O, trimesic acid, deionized water and a reaction system (mixture of raw materials). The specific process is that a certain mass of raw material CrCl is added3·6H2O and trimesic acid were added to deionized water and stirred uniformly, and it can be seen from the figure that the resulting early mixture was a very concentrated solution in a dark green color.
FIG. 2 is a schematic diagram showing the comparison of XRD (as synthesized) and simulated XRD (simulated) patterns of the MIL-100Cr prepared by the present invention by using an x-ray diffractometer for crystal phase analysis. The main peak positions of XRD diffraction peaks of the two materials can be aligned, which indicates that the material prepared by the invention is MIL-100 Cr.
FIG. 3 is a graph comparing MIL-100Cr nitrogen adsorption prepared by the present invention with MIL-100Cr product nitrogen adsorption prepared by dilute solution system and solid phase method. The graph shows that the MIL-100Cr surface area prepared by the present invention is much larger than the products prepared by the other two methods. Wherein the numbers 1, 2 and 3 represent the nitrogen adsorption curves of the product obtained by the solid phase method and the traditional dilute solution method respectively.
FIG. 4 is an XRD (as synthesized) spectrum of crystal phase analysis of MIL-100Cr prepared according to Table 2 by an x-ray diffractometer. The diagram shows the CrCl according to the differences3·6H2The mol ratio of O and trimesic acid can be reacted for 24 hours under certain acidic condition to obtain MIL-100Cr crystal.
FIG. 5 is a graphical representation of the nitrogen adsorption characterization of MIL-100Cr prepared according to Table 2. The figure shows that when CrCl is used3·6H2When the molar ratio of O to trimesic acid is 2:1, the synthesized MIL-100Cr has the largest specific surface area.
FIG. 6 is an XRD pattern of crystal phase analysis of MIL-100Cr prepared according to Table 3 using an x-ray diffractometer(as synthesized). It can be seen from the figure that when CrCl is used3·6H2When the molar ratio of O to trimesic acid is 2:1, MIL-100Cr crystals are successfully obtained under different addition amounts of hydrochloric acid.
FIG. 7 is a graphical representation of the nitrogen adsorption characterization of MIL-100Cr prepared according to Table 3. The figure shows that when CrCl is used3·6H2When the molar ratio of O to trimesic acid is 2:1 and the addition of hydrochloric acid is 0.0036mol, the synthesized MIL-100Cr has the largest specific surface area.
FIG. 8 is an XRD (as synthesized) spectrum of crystal phase analysis by an x-ray diffractometer on MIL-100Cr prepared as in Table 5. It can be seen from the figure that when CrCl is used3·6H2When the molar ratio of O, trimesic acid, hydrochloric acid and deionized water is 2:1:0.18:14, MIL-100Cr crystals are successfully obtained in different crystallization time.
FIG. 9 is a graphical representation of the nitrogen adsorption characterization of MIL-100Cr prepared according to Table 5. When CrCl is present3·6H2When the molar ratio of O, trimesic acid, hydrochloric acid and deionized water is 2:1:0.18:14, the specific surface area of the synthesized MIL-100Cr is the largest within 24 hours of crystallization time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The technical solution of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
Chemical substance material: CrCl3·6H2O, deionized water, trimesic acid and concentrated hydrochloric acid (36.5 wt% aqueous solution), and the preparation amounts of the combination are as follows: taking g and ml as measurement unit
Preparation of MIL-100Cr
The method comprises the following specific steps:
a method for synthesizing MIL-100Cr with high specific surface area by using hydrochloric acid as a regulator under a very concentrated system comprises the following steps:
(1) preparation of MIL-100Cr
The synthesis of MIL-100Cr is carried out in a closed reaction kettle and is completed in the processes of heating, standing and crystallizing:
firstly, weighing 10.50g of chromium trichloride hexahydrate, 4.20g of trimesic acid, 0.30mL of concentrated hydrochloric acid (water in the concentrated hydrochloric acid is neglected in calculation due to low molar weight of the water), 5.00mL of deionized water, adding the deionized water into a 20mL beaker, and violently stirring the mixture for 20min at normal temperature to obtain a mixed reaction solution.
Transferring the mixed reaction solution into a polytetrafluoroethylene container (23mL), placing the mixed reaction solution into a stainless steel reaction kettle, and sealing the stainless steel reaction kettle;
the reaction kettle is then placed in a heating furnace and sealed.
And thirdly, starting the heating furnace, heating at 220 ℃ for 24 hours, and carrying out crystallization reaction on the mixed reaction solution.
Fourthly, after the crystallization reaction, stopping heating, and cooling the crystallization reaction solution to 25 ℃ along with a heating furnace.
(2) Centrifugation
And (3) placing the crystallization reaction solution after the crystallization reaction into a centrifuge tube, placing the centrifuge tube into a centrifuge at the rotating speed of 9000r/min for 10min, precipitating the product at the bottom layer of the centrifuge tube, and pouring the upper-layer waste liquid.
(3) Washing and centrifuging
Soaking the product in deionized water at 85 deg.C and distilled water at 60 deg.C for 5 hr at a ratio of 1g/250mL, placing the cleaning solution in a centrifuge tube, placing in a centrifuge at 9000r/min for 10min, precipitating the product at the bottom of the centrifuge tube, and discarding the upper waste liquid.
(4) Vacuum drying
And (3) putting the washed product into a quartz container, and then putting the quartz container into a drying oven for drying at the drying temperature of 85 ℃ for 12 h.
(5) Product storage
The MIL-100Cr is stored in a transparent glass container and is sealed for storage.
The color and the chemical and physical properties of the MIL-100Cr prepared by the invention are detected, analyzed and characterized, and the conclusion is that: the MIL-100Cr sample is light green powder, and the specific surface area of the MIL-100Cr sample is larger than that of an MIL-100Cr sample obtained by a dilute solution system and a solid phase method.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (3)
1. A method for synthesizing MIL-100Cr with high specific surface area under a very concentrated system by taking hydrochloric acid as a regulator is characterized by comprising the following steps:
CrCl with the molar ratio of 2:1:0.18:143·6H2Mixing and stirring O, trimesic acid, hydrochloric acid and deionized water, then carrying out constant-temperature crystallization reaction for 24 hours at the temperature of 220 ℃ in a sealed container, naturally cooling the sealed container to room temperature, carrying out centrifugal filtration to obtain a product, then sequentially soaking the product in deionized water and ethanol, filtering and drying to obtain the MIL-100 Cr.
2. The method for synthesizing MIL-100Cr with high specific surface area under the very concentrated system using hydrochloric acid as the regulator according to claim 1, wherein the soaking temperature of the product in deionized water is 85 ℃ and the soaking temperature in ethanol is 60 ℃.
3. The method for synthesizing MIL-100Cr with high specific surface area by using hydrochloric acid as a very concentrated system as a regulator according to claim 2, wherein the soaking time of the product in deionized water and ethanol is 5 hours respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811648231.8A CN109535437B (en) | 2018-12-30 | 2018-12-30 | Method for synthesizing MIL-100Cr with high specific surface area under extremely concentrated system by taking hydrochloric acid as regulator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811648231.8A CN109535437B (en) | 2018-12-30 | 2018-12-30 | Method for synthesizing MIL-100Cr with high specific surface area under extremely concentrated system by taking hydrochloric acid as regulator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109535437A CN109535437A (en) | 2019-03-29 |
| CN109535437B true CN109535437B (en) | 2021-09-07 |
Family
ID=65831735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811648231.8A Active CN109535437B (en) | 2018-12-30 | 2018-12-30 | Method for synthesizing MIL-100Cr with high specific surface area under extremely concentrated system by taking hydrochloric acid as regulator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109535437B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110605097B (en) * | 2019-09-19 | 2022-03-15 | 太原理工大学 | Binder-free MIL-100Cr forming method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002057210A1 (en) * | 2001-01-19 | 2002-07-25 | Simafex | Stabilised o-iodoxybenzoic acid compositions and preparation method |
| CN104525122A (en) * | 2014-12-05 | 2015-04-22 | 昆明理工大学 | Preparation method and application of metal-organic framework material |
| CN105061482A (en) * | 2015-08-17 | 2015-11-18 | 太原理工大学 | Method for directly compounding metal-organic framework material MIL-100A1 by using trimesic acid |
| CN105344327A (en) * | 2015-11-26 | 2016-02-24 | 中国科学院生态环境研究中心 | Preparation method of MOFs graphene composite material |
| WO2016106094A2 (en) * | 2014-12-23 | 2016-06-30 | The Regents Of The University Of California | Metal-organic frameworks for the conversion of lignocellulosic derivatives to renewable platform chemicals |
| CN107262046A (en) * | 2017-08-14 | 2017-10-20 | 河南圣玛斯科技有限公司 | A kind of metal organic framework MIL 53 and preparation method thereof |
-
2018
- 2018-12-30 CN CN201811648231.8A patent/CN109535437B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002057210A1 (en) * | 2001-01-19 | 2002-07-25 | Simafex | Stabilised o-iodoxybenzoic acid compositions and preparation method |
| CN104525122A (en) * | 2014-12-05 | 2015-04-22 | 昆明理工大学 | Preparation method and application of metal-organic framework material |
| WO2016106094A2 (en) * | 2014-12-23 | 2016-06-30 | The Regents Of The University Of California | Metal-organic frameworks for the conversion of lignocellulosic derivatives to renewable platform chemicals |
| CN105061482A (en) * | 2015-08-17 | 2015-11-18 | 太原理工大学 | Method for directly compounding metal-organic framework material MIL-100A1 by using trimesic acid |
| CN105344327A (en) * | 2015-11-26 | 2016-02-24 | 中国科学院生态环境研究中心 | Preparation method of MOFs graphene composite material |
| CN107262046A (en) * | 2017-08-14 | 2017-10-20 | 河南圣玛斯科技有限公司 | A kind of metal organic framework MIL 53 and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "A Eu/Tb-mixed MOF for luminescent high-temperature sensing";Huizhen Wang，et al.;《Journal of Solid State Chemistry》;20161206;第246卷;第341-345页 * |
| "Porous structured MIL-101 synthesized with different mineralizers for adsorptive removal of oxytetracycline from aqueous solution";Tianding Hu，et al.;《RSC Adv.》;20160727;第6卷;第73741-73747页 * |
| "金属有机骨架材料的合成条件";章永明，等;《建材世界》;20121231;第33卷(第2期);第1-3页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109535437A (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Synthesis of metal–organic framework MIL-101 in TMAOH-Cr (NO3) 3-H2BDC-H2O and its hydrogen-storage behavior | |
| CN103626655B (en) | A kind of expose the metal-organic framework materials preparation method that crystal face is controlled | |
| CN106215866B (en) | The method that steam assistant metal displacement prepares bimetallic MOFs materials | |
| CN111943227B (en) | Preparation method of low-defect and low-water-content Prussian white analogue | |
| CN107312181B (en) | Method for rapidly preparing Cu-BTC | |
| CN110343259B (en) | Green fluorescent sandwich type zinc coordination polymer and preparation method and application thereof | |
| CN111253586B (en) | Cadmium-based metal-organic framework material and preparation method and application thereof | |
| CN110396006A (en) | A kind of ZIF-8 film cladding SnO2Composite air-sensitive material and its preparation method and application | |
| CN110256706A (en) | A kind of synthetic method of metal-organic framework materials high molecular polymer film | |
| CN109535437B (en) | Method for synthesizing MIL-100Cr with high specific surface area under extremely concentrated system by taking hydrochloric acid as regulator | |
| CN113004275A (en) | Copper complex and preparation method and application thereof | |
| CN106745174B (en) | A kind of preparation process of rare earth oxide specific surface area control | |
| CN108285152A (en) | A kind of green high-efficient synthetic method of Copper-cladding Aluminum Bar SBA-15 meso-porous molecular sieve materials | |
| CN105646552A (en) | Zn(II) complex based on 5-hydroxynictinic acid and preparation method and application thereof | |
| CN109574036A (en) | A kind of preparation method of DNL-1 molecular sieve | |
| CN106589394B (en) | A kind of cobalt coordination polymer and preparation method thereof | |
| CN114933710B (en) | Aluminum metal organic framework material with MIL-101 structure and preparation method thereof | |
| CN108822051B (en) | Synthesis method and application of fluorescent three-dimensional Zn (II) complex | |
| CN106278869B (en) | A method of with the Fast back-projection algorithm MOFs materials of molecular sieve recycling design | |
| CN108424527A (en) | The synthetic method of Zn (II) complex of three-dimensional hybrid ligand and fluorescence probe application | |
| CN107377010B (en) | Novel microporous chalcogenide, method for the production thereof and use thereof | |
| CN108585050B (en) | Low-temperature green synthesis method of manganous-manganic oxide nanoring | |
| CN109400901B (en) | Magnetic cobalt (II) coordination polymer and preparation method thereof | |
| RU2784345C1 (en) | Method for producing a zirconium-based organometallic framework | |
| CN109879317A (en) | A kind of multi-stage porous ZrO2Solid material, preparation method and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |