CN106883419B - Rapid synthesis method and application of cobalt-based metal-organic framework material - Google Patents
Rapid synthesis method and application of cobalt-based metal-organic framework material Download PDFInfo
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
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Abstract
The invention discloses a rapid synthesis method and application of a cobalt-based metal-organic framework material, wherein the synthesis method comprises the following steps: firstly, adding metal cobalt salt, hydrofluoric acid, aromatic dicarboxylic acid and water into a container, and fully mixing, stirring and reacting to obtain a pre-reaction precursor solution; then putting the pre-reaction precursor solution into a closed reaction kettle, putting the closed reaction kettle into a rotary crystallization device for rotary crystallization reaction, taking out the reaction kettle after the reaction is finished, and carrying out quenching cooling to room temperature to obtain a reaction product liquid; and finally, carrying out suction filtration treatment on the reaction product liquid for the first time, taking the filter cake, sequentially washing and hot washing, carrying out suction filtration treatment for the second time, taking the filter cake, sequentially washing and drying, and thus obtaining the cobalt-based metal-organic framework material. The synthesis method of the invention adopts a rotary crystallization mode, thereby greatly shortening the synthesis time; moreover, the obtained cobalt-based metal-organic framework material has controllable morphology and high catalytic activity.
Description
Technical Field
The invention relates to the technical field of preparation of inorganic non-metallic catalytic materials, in particular to a rapid synthesis method and application of a cobalt-based metal-organic framework material.
Background
Metal-organic frameworks (MOFs) are attracting more and more attention as a unique inorganic and organic hybrid porous material with controllable size and morphology formed by the mutual coupling and self-assembly of metal ions or metal ion clusters and suitable multidentate bridging ligands through covalent bonds or ion-covalent bonds. The most commonly used organic linking ligands are rigid ligands containing atoms such as N, O that provide a lone electron pair, such as polycarboxylic acids, polyphosphoric acids, polysulfonic acids, pyridine, pyrimidine, and the like. The central metal ion covers almost all ions formed by transition metal elements, even including tetravalent metal ions. Due to the selection of different metal ions and organic ligands and various coordination modes, the porous material with diversified structures, different pore diameters and functionalized internal environment can be prepared. Compared with the traditional activated carbon and zeolite porous materials, the metal organic framework material has a highly ordered pore structure, adjustable pore size, functionalized pore environment, higher specific surface area, pore volume and the like, so that the metal organic framework material has better application prospects in the aspects of adsorption separation, catalysis and the like.
The synthesis mechanism of crystalline MOFs can be considered as a process comprising nucleation, oligomerization, aggregation and growth of crystal grains and final crystallization, and the synthesis of MOFs by the hydrothermal (solvothermal) method is a coordination reaction of an organic ligand and metal ions in a solvent at a proper temperature and an autogenous pressure, and the synthesis method generally comprises the steps of mixing a precursor with a solvent such as organic amine, deionized water, ethanol and methanol, placing the mixture into a sealed container, heating the mixture to a certain temperature (25-250 ℃), reacting the mixture at the autogenous pressure (which can be as high as 1 × 103kPa), wherein the synthesis time is matched with the problem of insolubility of the precursor, and the formation of a coordination bond is a key for nucleation and crystallization by adjusting the conditions of the reaction and the deprotonation rate of the ligand.
Chinese patent CN104086594A discloses a method for rapidly synthesizing metal organic framework material MIL-101(Cr), the invention rapidly synthesizes MIL-101 by the induction action of carbon nano-material, solves the defect of long preparation time of the traditional method, and realizes the rapid and controllable preparation of the metal organic framework material MIL-101. The method adopts carbon nano tubes or carbon fibers as an inducer, and increases the preparation cost of the catalyst. Chinese patent CN 105061512A discloses a method for rapidly synthesizing metal organic framework material MIL-101(Cr) without fluorine and solvent, which is characterized in that Cr (N)O3)3·9H2And mixing O and terephthalic acid, grinding at room temperature, performing crystallization reaction to obtain a solid product, washing with an organic solvent, filtering, and drying the solid product to obtain MIL-101 (Cr). Although the patent successfully produces the metal organic framework material MIL-101(Cr), the solvent-free reaction system has poor flowability, even no flowability, which leads to difficult discharge of reaction heat of exothermic reaction. Chinese patent CN 102336774A discloses a method for rapidly synthesizing a nano-scale metal organic framework nano-material based on 1,3, 5-trimesic acid (BTC) at room temperature, and the method comprises the steps of mixing a metal acetate aqueous solution with a 1,3, 5-trimesic acid solution at room temperature, and then carrying out reaction to obtain the metal organic framework nano-particle based on 1,3, 5-trimesic acid. Although the synthesis method of the patent is successful, the catalyst is easy to dissolve in the reaction system when the materials synthesized at low temperature are used for heating heterogeneous catalytic reaction, and the recovery and separation of the catalyst are not facilitated. Chinese patent CN 102190797A discloses a rapid synthesis method and application of a triazine-based organic framework material, a triazine-based organic oligomer and a triazine-based organic compound with nano holes. However, this patent uses Lewis acid as a catalyst, and the material is dissolved and removed by a hydrochloric acid solution treatment operation during the preparation process, and the catalyst is directly consumed, increasing the production cost.
Although a series of methods for rapidly synthesizing metal organic framework materials disclosed in the above patent successfully synthesize organic framework materials with different structures, no report is found on a method for rapidly synthesizing organic framework MOFs materials by rotational crystallization, and no report is found on the application of the materials synthesized in the above patent in catalytic reactions, especially in catalytic olefin epoxidation.
Disclosure of Invention
The invention aims to provide a rapid synthesis method of a cobalt-based metal-organic framework material and application thereof, wherein the synthesis method adopts a rotational crystallization mode, thereby greatly shortening the synthesis time, greatly reducing the energy consumption and saving the production cost; moreover, the obtained cobalt-based metal-organic framework material (Co-MOF) has controllable morphology and high catalytic activity.
In order to achieve the above object, the present invention provides a method for rapidly synthesizing a cobalt-based metal-organic framework material, comprising the steps of: firstly, adding metal cobalt salt, hydrofluoric acid, aromatic dicarboxylic acid and water into a container, and fully mixing, stirring and reacting to obtain a pre-reaction precursor solution; then putting the pre-reaction precursor solution into a closed reaction kettle, putting the closed reaction kettle into a rotary crystallization device for rotary crystallization reaction, taking out the reaction kettle after the reaction is finished, and carrying out quenching cooling to room temperature to obtain a reaction product liquid; and finally, carrying out suction filtration treatment on the reaction product liquid for the first time, taking the filter cake, sequentially washing and hot washing, carrying out suction filtration treatment for the second time, taking the filter cake, sequentially washing and drying, and thus obtaining the cobalt-based metal-organic framework material.
Furthermore, the addition amounts of the metal cobalt salt, hydrofluoric acid, aromatic dicarboxylic acid and water are that the molar ratio of the metal cobalt salt: hydrofluoric acid: aromatic dicarboxylic acids: water is 1:1: 0.5-1: 185-556.
Further, the metal cobalt salt is selected from one of cobalt acetate, cobalt nitrate, cobalt chloride or cobalt sulfate.
Further, the aromatic dicarboxylic acid is one selected from terephthalic acid, 2-aminoterephthalic acid, 2-hydroxyterephthalic acid, isophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, trimesic acid or biphenyltetracarboxylic acid.
Further, the mixing and stirring reaction is carried out on a magnetic stirrer for 15-30 min; the rotating speed of the rotating crystallization reaction is 70-160 r/min, the crystallization temperature is 80-220 ℃, and the crystallization time is 0.5-2 h.
Further, the hot washing treatment is that N, N' -dimethylformamide and absolute ethyl alcohol are sequentially adopted for hot washing treatment at the temperature of 60-80 ℃.
Further, the rapid synthesis method of the cobalt-based metal-organic framework material specifically comprises the following steps:
1) pre-reaction:
firstly, metal cobalt salt, hydrofluoric acid, aromatic dicarboxylic acid and water are mixed according to the molar ratio of the metal cobalt salt: hydrofluoric acid: aromatic dicarboxylic acids: adding water in a ratio of 1:1: 0.5-1: 185-556 into a container, and mixing and stirring on a magnetic stirrer for reaction for 15-30 min to obtain a pre-reaction precursor solution;
2) rotating crystallization reaction:
putting the pre-reaction precursor solution into a closed reaction kettle, putting the closed reaction kettle into a rotary crystallization device for rotary crystallization reaction, wherein the rotary speed of the rotary crystallization reaction is 70-160 r/min, the crystallization temperature is 80-220 ℃, and the crystallization time is 0.5-2 h, taking out the reaction kettle after the reaction is finished, and cooling the reaction kettle to room temperature to obtain reaction product liquid;
3) and (3) post-treatment:
and carrying out suction filtration treatment on the reaction product liquid for the first time, taking the filter cake, sequentially washing and hot washing, carrying out suction filtration treatment for the second time, taking the filter cake, sequentially washing and drying, and thus obtaining the cobalt-based metal-organic framework material.
The application of the cobalt-based metal-organic framework material is characterized in that the cobalt-based metal-organic framework material is used as a catalyst for preparing α -epoxy pinane through an epoxidation reaction of α -pinene and air.
The method for preparing α -epoxy pinane through epoxidation reaction of α -pinene and air comprises the following steps of sequentially adding N, N' -dimethylformamide, cobalt-based metal-organic framework materials, α -pinene and cumene hydroperoxide into a two-opening round-bottom flask, connecting a low-temperature condensation tube, introducing dry air with the flow rate of 20-40 ml/min, heating reaction liquid in the two-opening round-bottom flask to 80-90 ℃ under rapid magnetic stirring, reacting for 2-6 hours, cooling to room temperature after the reaction is finished, filtering, and finally carrying out reduced pressure distillation and fractionation treatment to obtain the α -epoxy pinane.
Further, the addition amounts of the N, N '-dimethylformamide, the cobalt-based metal-organic framework material, the olefin, and cumene hydroperoxide are, in terms of molar ratio, N' -dimethylformamide: cobalt-based metal-organic framework material: olefin (b): cumene hydroperoxide (135-140: 0.08-0.09: 2.8-3.2: 0.1-0.4).
Compared with the prior art, the invention has the following advantages:
firstly, the synthesis method adopts a rotary crystallization mode, the crystallization method of the material adopts a hydrothermal crystallization mode, the reaction is rapid, the synthesis time is greatly shortened, the energy consumption is greatly reduced, the synthesis method is simple, no harsh conditions exist in the synthesis process, and a plurality of complicated procedures are saved.
Secondly, the hydrothermal crystallization mode adopted by the invention has good fluidity of a reaction system, all the substances are uniformly mixed, and the reaction heat in the exothermic reaction is easily absorbed by the solvent.
Thirdly, the raw material metal salt is cheap and easy to obtain, the synthesized target product cobalt-based metal-organic framework material has high yield, the dosage of the carboxylic acid ligand can be adjusted, the most reasonable proportion is used as far as possible, if the molar weight ratio of the cobalt metal to the ligand is 1:1, the yield of the cobalt-based metal-organic framework material is up to more than 95%, and the waste of raw materials is avoided.
Fourthly, the cobalt-based metal-organic framework material obtained by the invention has uniform particles, greatly shortens the diffusion distance of other substances in the cobalt-based metal-organic framework material, and is beneficial to the application of metal-organic framework compounds in the aspects of catalysis, adsorption, drug carriers and the like.
Fifthly, the cobalt-based metal-organic framework material has high catalytic activity in catalyzing epoxidation reaction of olefin, particularly α -pinene and air, the conversion rate of α -pinene is up to 98.0 mol%, and the selectivity of a target product α -epoxy pinane is up to 97.6%.
Drawings
FIG. 1 is an X-ray diffraction pattern of a cobalt-based metal-organic framework material (Co-MOF) produced in example 1, example 3, example 4, example 11 or example 12 of the present invention;
FIG. 2 is a scanning electron microscope photograph of a cobalt-based metal-organic framework material prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
Example 1
(1) The rapid synthesis method of the cobalt-based metal-organic framework material comprises the following steps:
adding 1.494g of cobalt acetate, 0.3g of hydrofluoric acid and 1.0g of terephthalic acid into a beaker, adding 60g of deionized water (metal cobalt salt: hydrofluoric acid: terephthalic acid: water in a molar mass ratio of 1:1:1:556), stirring and mixing at normal temperature on a magnetic stirrer for 15min to obtain a uniformly mixed pre-reaction precursor solution. Then adding the pre-reaction precursor solution into a 100mL closed reaction kettle, sealing the reaction kettle, putting the reaction kettle into a rotary crystallization device, and rotating the closed reaction kettle around a horizontal rotating shaft for rotary crystallization reaction for 3 hours at the temperature of 200 ℃ and at the speed of 150 r/min; after the reaction is finished, rapidly taking out the reaction kettle, quenching and cooling to room temperature, carrying out suction filtration treatment for the first time, washing a filter cake by using deionized water, sequentially using 20mL of N, N' -Dimethylformamide (DMF) and 20mL of absolute ethyl alcohol to carry out hot washing for 1 time respectively at the temperature of 60-80 ℃, carrying out suction filtration for the second time, removing the filter cake, washing, and carrying out vacuum drying at the temperature of 80 ℃ to obtain the metal organic framework material Co-MOF.
(2) α -pinene and air epoxidation reaction to prepare α -epoxy pinane, which comprises the following steps:
adding 10g of N, N' -Dimethylformamide (DMF), 30mg of Co-MOF catalyst, 3mmol of α -pinene and 0.3mmol of cumene hydroperoxide (70 mass percent of cumene hydroperoxide aqueous solution) into a 50ml round bottom flask, connecting to a low-temperature condensing tube (the temperature is kept at-15 ℃) and introducing dry air with the flow rate of 40ml/min, heating the reactor to 90 ℃ under rapid magnetic stirring for reaction for 5 hours, cooling to room temperature after the reaction is finished, filtering, and finally carrying out reduced pressure distillation and fractional distillation to obtain the α -epoxy pinane.
In the quantitative analysis process, before reduced pressure distillation and fractionation treatment, adding chlorobenzene as an internal standard substance into the filtrate, and then carrying out quantitative analysis by using a chromatograph, wherein the gas chromatograph is used for carrying out analysis, the capillary column model is Rtx @5, and the gas chromatograph setting procedure is as follows: the column temperature is 70 ℃, the vaporization chamber temperature is 285 ℃, the FID detector temperature is 285 ℃, and the split ratio is 1: 50.
Examples 2 to 14
In examples 2 to 14, according to the technical scheme provided by the present invention, the ratio of the raw materials is adjusted within the given range, and the obtained product has equivalent properties, the implementation process is the same as that of example 1 except for the following differences, and the relevant results are shown in table 1 as the formula of examples 1 to 14 and table 2 as the formula and test results of catalyzing the epoxidation of α -pinene and air.
TABLE 1
TABLE 2
Effect example 1: x-ray diffraction
X-ray diffraction on a Rigaku D/MAX-IIIC X-ray diffractometer (CuK α:
) And (4) carrying out measurement. Grinding the sample sufficiently, taking about 20mg of the sample, loading into a tablet press at 500kg/cm2Pressed into a sheet under pressure.
As can be seen from FIG. 1, the main X-ray powder diffraction lines of the Co-MOFs synthesized by the methods of examples 1,3, 4, 11 and 12 are consistent, and the samples are relatively pure target Co-MOFs. In the figure, the 2 theta is 8.8 degrees, and the 17.9-degree diffraction peak is the skeleton characteristic diffraction peak data of the Co-MOF.
Effect example 2: scanning electron microscopy
Scanning Electron microscope the measurement was carried out on a JSM-6510A scanning electron microscope manufactured by Japan Electron Ltd. The scanning voltage of the tungsten lamp is 30Kv, the diameter of a sample to be detected can be amplified to 150mm, and an EDS (X-ray energy spectrometer) module is additionally arranged.
As can be seen from FIG. 2, the surface morphology of the Co-MOF synthesized in example 1 of the present invention is regular long column shape, with a length of about 5.1um and a width of about 0.68um, and the shape is very regular.
Claims (4)
1. A rapid synthesis method of a cobalt-based metal-organic framework material is characterized by comprising the following steps:
1) pre-reaction:
adding cobalt acetate, hydrofluoric acid and terephthalic acid into a beaker, adding deionized water, wherein the ratio of cobalt acetate: hydrofluoric acid: terephthalic acid: stirring and mixing water on a magnetic stirrer at normal temperature according to the molar mass ratio of 1:1:1:556, wherein the stirring and mixing time at normal temperature is 15min, so as to obtain a uniformly mixed pre-reaction precursor solution;
2) rotating crystallization reaction:
then adding the pre-reaction precursor solution into a 100mL closed reaction kettle, sealing the reaction kettle, putting the reaction kettle into a rotary crystallization device, and rotating the closed reaction kettle around a horizontal rotating shaft for rotary crystallization reaction for 3 hours at the temperature of 200 ℃ and at the speed of 150 r/min; after the reaction is finished, quickly taking out the reaction kettle, and then cooling to room temperature by quenching to obtain reaction product liquid;
3) and (3) post-treatment:
then carrying out suction filtration treatment on the reaction product liquid for the first time, taking a filter cake, washing the filter cake with deionized water, sequentially carrying out hot washing on the filter cake for 1 time by using 20mL of N, N' -dimethylformamide and 20mL of absolute ethyl alcohol at the temperature of 60-80 ℃, carrying out suction filtration for the second time, removing the filter cake, washing, and carrying out vacuum drying at the temperature of 80 ℃ to obtain the metal organic framework material;
the surface morphology of the cobalt-based metal-organic framework material is a regular long column shape, and the framework X-ray characteristic diffraction peak 2 theta of the cobalt-based metal-organic framework material is 8.8 degrees and 17.9 degrees.
2. The application of the cobalt-based metal-organic framework material is characterized in that the cobalt-based metal-organic framework material is prepared by the rapid synthesis method of claim 1, and the cobalt-based metal-organic framework material is used as a catalyst for preparing α -epoxy pinane through epoxidation reaction of α -pinene and air.
3. The application of the cobalt-based metal-organic framework material of claim 2, wherein the method for preparing α -epoxy pinane through epoxidation reaction of α -pinene and air comprises the following steps of sequentially adding N, N' -dimethylformamide, the cobalt-based metal-organic framework material, α -pinene and cumene hydroperoxide into a two-neck round-bottom flask, connecting a low-temperature condenser tube, introducing dry air with the flow rate of 40ml/min, heating reaction liquid in the two-neck round-bottom flask to 90 ℃ under rapid magnetic stirring, reacting for 5 hours, cooling to room temperature after the reaction is finished, filtering, and finally carrying out reduced pressure distillation and fractional distillation to obtain α -epoxy pinane.
4. Use of a cobalt-based metal-organic framework material according to claim 3, wherein the N, N '-dimethylformamide, cobalt-based metal-organic framework material, olefin, cumene hydroperoxide are added in a molar ratio of N, N' -dimethylformamide: cobalt-based metal-organic framework material: olefin (b): cumene hydroperoxide (135-140: 0.08-0.09: 3.0: 0.3).
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| CN108565420A (en) * | 2018-04-08 | 2018-09-21 | 湖北大学 | Co is carried on the material, preparation method and application of MIL-101 |
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| CN113699536B (en) * | 2021-07-26 | 2022-12-23 | 安徽理工大学 | Metal phosphide electrocatalyst based on MOF derivation, preparation method and application |
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