CN103992339A - Method for synthesizing metal organic framework material Mg-MOF-74 - Google Patents
Method for synthesizing metal organic framework material Mg-MOF-74 Download PDFInfo
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Abstract
The invention relates to a method for synthesizing metal organic framework material Mg-MOF-74 and relates to a synthesis method of Mg-MOF-74. The invention aims at solving the problems of high post-treatment temperature and high cost of a traditional method for preparing the Mg-MOF-74 material. The method provided by the invention comprises the following steps: 1) mixing DMF, methanol and deionized water or DMF and deionized water or DMF and ethanol; 2) performing ultrasonic treatment on magnesium nitrate hexahydrate and DHTA to obtain a hydrothermal precursor; 3) placing into a reaction kettle and performing hydrothermal drying at the temperature of 125 DEG C for 24h; 4) replacing the reaction solution with methanol every 12 hours for 4 times; 5) performing vacuum drying for 6h at the temperature of 100 DEG C to prepare the Mg-MOF-74 material. Methanol used in the method provided by the invention is used to substitute ethanol in a mixed solvent, so that the production cost can be reduced and an organic solvent in a pore canal of a sample can be removed at the post-treatment temperature. The method provided by the invention is applied in the field of synthesis of the Mg-MOF-74.
Description
Technical field
The present invention relates to the synthetic method of Mg-MOF-74.
Background technology
Metal organic frame thing material (Metal-Organic Frameworks is called for short MOFs) is a kind of novel porous material, claims again ligand polymer.It is the crystalline material with one dimension, two dimension or three-dimensional infinite network structure that utilizes that organic ligand and metal ion or metal cluster form by coordinate bond or intermolecular interaction self-assembly.Because its porosity is high, specific surface area is large, be easy to synthesize, hole size is variable and can make the advantages such as chemically modified, structure be abundant according to target call, can potentially be applied to the fields such as gas adsorption, catalysis, photoelectric material.Compare with other metal organic frame materials, Mg-MOF-74 material, with its higher specific surface area, high porosity, outstanding advantages such as thermostability, has obtained extensive concern.Especially Mg-MOF-74 material is in the situation that the dividing potential drop of carbonic acid gas is lower, and its adsorption effect is obviously better than other porous materials, so Mg-MOF-74 material is to alleviate the optimal sorbing material of Greenhouse effect.At present, domestic also less to the report of the R and D of Mg-MOF-74 material, therefore, preparation Mg-MOF-74 material has important scientific meaning and wide application prospect.
At present, the method of preparing Mg-MOF-74 material is mainly hydrothermal synthesis method, tradition method for making is that magnesium nitrate hexahydrate and DHTA, in DMF/ ethanol/water mixed solution, self-assembly occurs, and after methyl alcohol replacement solvent, organic solvent in duct is removed in vacuum-drying for 6 hours at 250 ℃.Tradition method for making exists cost low, and post-processing temperature is high, is unfavorable for preparing the Mg-MOF-74 crystal of good, the free from foreign meter solvent of crystallinity, good thermal stability.
Summary of the invention
The object of the invention is to prepare Mg-MOF-74 material and have the problem that post-processing temperature is high and cost is high in order to solve traditional method, and the method for synthetic metal organic frame thing material Mg-MOF-74 is provided.
The method of synthetic metal organic frame thing material Mg-MOF-74 of the present invention is according to following steps:
One, measure respectively DMF, methyl alcohol and deionized water and be placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ methyl alcohol/deionized water is 15:1:1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
The method of synthetic metal organic frame thing material Mg-MOF-74 of the present invention is according to following steps:
One, measure DMF respectively and deionized water is placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ deionized water is (10～15): 1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
The method of synthetic metal organic frame thing material Mg-MOF-74 of the present invention is according to following steps:
One, measure DMF respectively and dehydrated alcohol is placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ dehydrated alcohol is (10～15): 1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
The present invention comprises following beneficial effect:
Synthetic method of the present invention is than the prior synthesizing method of Mg-MOF-74, and the present invention uses methyl alcohol to replace the ethanol in mixed solvent, not only can reduce production costs, and can also under lower post-processing temperature, remove organic solvent in sample duct.Traditional method remove organic solvent need to be at 250 ℃ vacuum-drying 6 hours, and the present invention only need to be at 100 ℃ vacuum-drying within 6 hours, can make the Mg-MOF-74 crystal of good, the free from foreign meter solvent of crystallinity, good thermal stability, when significantly having saved experimental period, also can reduce experimental cost.
In step 4 of the present invention, adopt washed with methanol, be mainly used for replacing the DMF solvent in former solvent, DMF boiling point is 152.8 ℃, and methyl alcohol is 64.5 ℃, and methyl alcohol very easily removes, so adopt methyl alcohol as cleaning solvent.
Accompanying drawing explanation
Fig. 1 is the synthetic Mg-MOF-74 scanning of materials Electronic Speculum figure of embodiment 1;
Fig. 2 is the synthetic Mg-MOF-74 material X-ray diffractogram of embodiment 1; Wherein, A is the X-ray diffractogram of embodiment 1, and B is the X-ray diffractogram of simulation;
Fig. 3 is Mg-MOF-74 material XRD figure synthetic under different drying temperatures;
Fig. 4 is the thermogravimetric curve figure of Mg-MOF-74 material synthetic under 100 ℃ and 250 ℃ of drying temperatures; Wherein, A is the thermogravimetric curve of Mg-MOF-74 material synthetic under 250 ℃ of drying temperatures, and B is the thermogravimetric curve of Mg-MOF-74 material synthetic under 100 ℃ of drying temperatures;
Fig. 5 is the synthetic Mg-MOF-74 material XRD figure of embodiment 1 to 3;
Fig. 6 is the synthetic Mg-MOF-74 scanning of materials Electronic Speculum figure of embodiment 2;
Fig. 7 is the synthetic Mg-MOF-74 scanning of materials Electronic Speculum figure of embodiment 3;
Fig. 8 is the scanning electron microscope (SEM) photograph of Mg-MOF-74 material synthetic under 150 ℃ of drying temperatures;
Fig. 9 is the scanning electron microscope (SEM) photograph of Mg-MOF-74 material synthetic under 200 ℃ of drying temperatures.
Embodiment
Embodiment one: the method for the synthetic metal organic frame thing material Mg-MOF-74 of present embodiment is according to following steps:
One, measure respectively DMF, methyl alcohol and deionized water and be placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ methyl alcohol/deionized water is 15:1:1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
The synthetic method of present embodiment is than the prior synthesizing method of Mg-MOF-74, present embodiment is used methyl alcohol to replace the ethanol in mixed solvent, not only can reduce production costs, can also under lower post-processing temperature, remove organic solvent in sample duct.Traditional method remove organic solvent need to be at 250 ℃ vacuum-drying 6 hours, and present embodiment only need to be at 100 ℃ vacuum-drying within 6 hours, can make the Mg-MOF-74 crystal of good, the free from foreign meter solvent of crystallinity, good thermal stability, when significantly having saved experimental period, also can reduce experimental cost.
In present embodiment step 4, adopt washed with methanol, be mainly used for replacing the DMF solvent in former solvent, DMF boiling point is 152.8 ℃, and methyl alcohol is 64.5 ℃, and methyl alcohol very easily removes, so adopt methyl alcohol as cleaning solvent.
Embodiment two: present embodiment is different from embodiment one: the mol ratio of the magnesium nitrate hexahydrate described in step 2 and 2,5-Dihydroxyterephthalic acid is 3.34:1.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: described in step 4 is to adopt the method for suction filtration to replace in reactor with methyl alcohol replacement reaction soln.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: described in step 5 is vacuum-drying 6 hours at 100 ℃～150 ℃ in temperature.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: described in step 5 is vacuum-drying 6 hours at 100 ℃ in temperature.Other is identical with one of embodiment one to four.
Embodiment five: the method for the synthetic metal organic frame thing material Mg-MOF-74 of present embodiment is according to following steps:
One, measure DMF respectively and deionized water is placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ deionized water is (10～15): 1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
The synthetic method of present embodiment is than the prior synthesizing method of Mg-MOF-74, present embodiment is used methyl alcohol to replace the ethanol in mixed solvent, not only can reduce production costs, can also under lower post-processing temperature, remove organic solvent in sample duct.Traditional method remove organic solvent need to be at 250 ℃ vacuum-drying 6 hours, and present embodiment only need to be at 100 ℃ vacuum-drying within 6 hours, can make the Mg-MOF-74 crystal of good, the free from foreign meter solvent of crystallinity, good thermal stability, when significantly having saved experimental period, also can reduce experimental cost.
In present embodiment step 4, adopt washed with methanol, be mainly used for replacing the DMF solvent in former solvent, DMF boiling point is 152.8 ℃, and methyl alcohol is 64.5 ℃, and methyl alcohol very easily removes, so adopt methyl alcohol as cleaning solvent.
Embodiment six: present embodiment is different from embodiment five: the mol ratio of the magnesium nitrate hexahydrate described in step 2 and 2,5-Dihydroxyterephthalic acid is 3.34:1.Other is identical with embodiment five.
Embodiment seven: present embodiment is different from embodiment five or six: described in step 4 is to adopt the method for suction filtration to replace in reactor with methyl alcohol replacement reaction soln.Other is identical with embodiment five or six.
Embodiment eight: present embodiment is different from one of embodiment five to seven: described in step 5 is vacuum-drying 6 hours at 100 ℃～150 ℃ in temperature.Other is identical with one of embodiment five to seven.
Embodiment nine: present embodiment is different from one of embodiment five to eight: described in step 5 is vacuum-drying 6 hours at 100 ℃ in temperature.Other is identical with one of embodiment five to eight.
Embodiment ten: the method for the synthetic metal organic frame thing material Mg-MOF-74 of present embodiment is according to following steps:
One, measure DMF respectively and dehydrated alcohol is placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ dehydrated alcohol is (10～15): 1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
The synthetic method of present embodiment is than the prior synthesizing method of Mg-MOF-74, present embodiment is used methyl alcohol to replace the ethanol in mixed solvent, not only can reduce production costs, can also under lower post-processing temperature, remove organic solvent in sample duct.Traditional method remove organic solvent need to be at 250 ℃ vacuum-drying 6 hours, and present embodiment only need to be at 100 ℃ vacuum-drying within 6 hours, can make the Mg-MOF-74 crystal of good, the free from foreign meter solvent of crystallinity, good thermal stability, when significantly having saved experimental period, also can reduce experimental cost.
In present embodiment step 4, adopt washed with methanol, be mainly used for replacing the DMF solvent in former solvent, DMF boiling point is 152.8 ℃, and methyl alcohol is 64.5 ℃, and methyl alcohol very easily removes, so adopt methyl alcohol as cleaning solvent.
Embodiment 11: present embodiment is different from embodiment ten: the mol ratio of the magnesium nitrate hexahydrate described in step 2 and 2,5-Dihydroxyterephthalic acid is 3.34:1.Other is identical with embodiment ten.
Embodiment 12: present embodiment is different from embodiment ten or 11: described in step 4 is to adopt the method for suction filtration to replace in reactor with methyl alcohol replacement reaction soln.Other is identical with embodiment ten or 11.
Embodiment 13: present embodiment is different from one of embodiment 11 to 12: described in step 5 is vacuum-drying 6 hours at 100 ℃～150 ℃ in temperature.Other is identical with one of embodiment 11 to 12.
Embodiment 14: present embodiment is different from one of embodiment 11 to 13: described in step 5 is vacuum-drying 6 hours at 100 ℃ in temperature.Other is identical with one of embodiment 11 to 13.
By following examples, verify beneficial effect of the present invention:
Embodiment 1
The method of the synthetic metal organic frame thing material Mg-MOF-74 of the present embodiment is according to following steps:
One, the deionized water that measures respectively the DMF of 27mL, the methyl alcohol of 1.8mL and 1.8mL is placed in 200mL beaker, after mixing, makes mixing solutions;
Two, take respectively 2 of the magnesium nitrate hexahydrate of 0.285g and 0.0672g, 5-dihydric para-phthalic acid (DHTA), and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains hydro-thermal presoma; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is 3.34:1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 125 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, methyl alcohol is filled with to reactor, for guaranteeing that product does not run off, every 12 hours, separately got methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, first crystal being transferred to watch-glass from polytetrafluoroethyllining lining, is vacuum-drying 6 hours at 100 ℃ in temperature, cooling rear taking-up, and sealing is preserved, and makes Mg-MOF-74 material.
As shown in Figure 1, its X-ray diffractogram as shown in Figure 2, is pure phase Mg-MOF-74 crystal by Fig. 1 and the prepared Mg-MOF-74 material of the known the present embodiment of Fig. 2 to the synthetic Mg-MOF-74 scanning of materials Electronic Speculum picture of the present embodiment, and pattern homogeneous.
The synthetic method of the present embodiment is than the prior synthesizing method of Mg-MOF-74, and the present embodiment is used methyl alcohol to replace the ethanol in mixed solvent, not only can reduce production costs, and can also under lower post-processing temperature, remove organic solvent in sample duct.Traditional method remove organic solvent need to be at 250 ℃ vacuum-drying 6 hours, and the present embodiment only need to be at 100 ℃ vacuum-drying within 6 hours, can make the Mg-MOF-74 crystal of good, the free from foreign meter solvent of crystallinity, good thermal stability, when significantly having saved experimental period, also can reduce experimental cost.
In addition, by changing the drying temperature of the present embodiment step 5, to investigate the synthetic impact on Mg-MOF-74 material of drying temperature.
Concrete drying temperature is changed into: in temperature, be vacuum-drying 6 hours at 150 ℃;
In temperature, be vacuum-drying 6 hours at 200 ℃;
In temperature, be vacuum-drying 6 hours at 250 ℃;
Under different drying temperatures, synthetic Mg-MOF-74 material XRD figure as shown in Figure 3, the present embodiment vacuum-drying 6 hours at 100 ℃, synthetic Mg-MOF-74 material hot weightless picture, and be that at 250 ℃ 6 hours synthetic Mg-MOF-74 material hot weightless pictures of vacuum-drying are as shown in Figure 4 in temperature, from Fig. 3 and Fig. 4, the drying temperature of the present embodiment is compared with under other drying temperature, it is complete that the synthetic Mg-MOF-74 material obtaining has crystalline structure, the less excellent properties of defect, the integrated degree of crystalline structure is the assurance of porous material good adsorption properties, in addition, under low temperature, vacuum-drying can be saved time, again can be cost-saving.
Embodiment 2
The method of the synthetic metal organic frame thing material Mg-MOF-74 of the present embodiment is according to following steps:
One, measure respectively the DMF of 27mL and the deionized water of 1.8mL is placed in 200mL beaker, after mixing, make mixing solutions;
Two, take respectively 2 of the magnesium nitrate hexahydrate of 0.285g and 0.0672g, 5-dihydric para-phthalic acid (DHTA), and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains hydro-thermal presoma; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is 3.34:1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 125 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, methyl alcohol is filled with to reactor, for guaranteeing that product does not run off, every 12 hours, separately got methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, first crystal being transferred to watch-glass from polytetrafluoroethyllining lining, is vacuum-drying 6 hours at 100 ℃ in temperature, cooling rear taking-up, and sealing is preserved, and makes Mg-MOF-74 material.
The synthetic Mg-MOF-74 scanning of materials Electronic Speculum figure of the present embodiment is as shown in 6, and as shown in Figure 6, the present embodiment synthesizes pure phase Mg-MOF-74 crystal, and pattern homogeneous.
The synthetic method of the present embodiment is than the prior synthesizing method of Mg-MOF-74, and the present embodiment is used methyl alcohol to replace the ethanol in mixed solvent, not only can reduce production costs, and can also under lower post-processing temperature, remove organic solvent in sample duct.Traditional method remove organic solvent need to be at 250 ℃ vacuum-drying 6 hours, and the present embodiment only need to be at 100 ℃ vacuum-drying within 6 hours, can make the Mg-MOF-74 crystal of good, the free from foreign meter solvent of crystallinity, good thermal stability, when significantly having saved experimental period, also can reduce experimental cost.
In addition, by changing the drying temperature of the present embodiment step 5, to investigate the synthetic impact on Mg-MOF-74 material of drying temperature.
Concrete drying temperature is changed into: in temperature, be vacuum-drying 6 hours at 150 ℃;
In temperature, be vacuum-drying 6 hours at 200 ℃;
In temperature, be vacuum-drying 6 hours at 250 ℃;
Under different drying temperatures, synthetic Mg-MOF-74 material XRD figure as shown in Figure 3, as shown in Figure 3, the present embodiment is vacuum-drying 6 hours at 100 ℃ in temperature, with under other drying temperature, compare, it is complete that the synthetic Mg-MOF-74 material obtaining has crystalline structure, the less excellent properties of defect, the integrated degree of crystalline structure is the assurance of porous material good adsorption properties, in addition, under low temperature, vacuum-drying can be saved time, again can be cost-saving.
Embodiment 3
The method of the synthetic metal organic frame thing material Mg-MOF-74 of the present embodiment is according to following steps:
One, measure respectively the DMF of 27mL and the dehydrated alcohol of 1.8mL is placed in 200mL beaker, after mixing, make mixing solutions;
Two, take respectively 2 of the magnesium nitrate hexahydrate of 0.285g and 0.0672g, 5-dihydric para-phthalic acid (DHTA), and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains hydro-thermal presoma; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is 3.34:1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 125 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, methyl alcohol is filled with to reactor, for guaranteeing that product does not run off, every 12 hours, separately got methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, first crystal being transferred to watch-glass from polytetrafluoroethyllining lining, is vacuum-drying 6 hours at 100 ℃ in temperature, cooling rear taking-up, and sealing is preserved, and makes Mg-MOF-74 material.
The synthetic Mg-MOF-74 scanning of materials Electronic Speculum figure of the present embodiment is as shown in 7, and as shown in Figure 7, the present embodiment synthesizes pure phase Mg-MOF-74 crystal, and pattern homogeneous.
The synthetic method of the present embodiment is than the prior synthesizing method of Mg-MOF-74, and the present embodiment is used methyl alcohol to replace the ethanol in mixed solvent, not only can reduce production costs, and can also under lower post-processing temperature, remove organic solvent in sample duct.Traditional method remove organic solvent need to be at 250 ℃ vacuum-drying 6 hours, and the present embodiment only need to be at 100 ℃ vacuum-drying within 6 hours, can make the Mg-MOF-74 crystal of good, the free from foreign meter solvent of crystallinity, good thermal stability, when significantly having saved experimental period, also can reduce experimental cost.
In addition, by changing the drying temperature of the present embodiment step 5, to investigate the synthetic impact on Mg-MOF-74 material of drying temperature.
Concrete drying temperature is changed into: in temperature, be vacuum-drying 6 hours at 150 ℃;
In temperature, be vacuum-drying 6 hours at 200 ℃;
In temperature, be vacuum-drying 6 hours at 250 ℃;
Under different drying temperatures, synthetic Mg-MOF-74 material XRD figure as shown in Figure 3, as shown in Figure 3, the present embodiment is vacuum-drying 6 hours at 100 ℃ in temperature, with under other drying temperature, compare, it is complete that the synthetic Mg-MOF-74 material obtaining has crystalline structure, the less excellent properties of defect, the integrated degree of crystalline structure is the assurance of porous material good adsorption properties, in addition, under low temperature, vacuum-drying can be saved time, again can be cost-saving.
Fig. 5 is the XRD figure that embodiment 1 to 3 employing different solvents synthesizes Mg-MOF-74 material, all can synthesize as shown in Figure 5 the Mg-MOF-74 crystal of pure phase under DMF/ ethanol and two kinds of conditions of DMF/ water.
Fig. 8 is the scanning electron microscope (SEM) photograph of Mg-MOF-74 material synthetic under 150 ℃ of drying temperatures, finds out as can be seen from Figure 8, and crystal morphology is complete, size homogeneous, but have partially polymerized.Fig. 9 is the scanning electron microscope (SEM) photograph of Mg-MOF-74 material synthetic under 200 ℃ of drying temperatures, finds out as can be seen from Figure 9, and the crystal formation of Mg-MOF-74 material has segmental defect, is unfavorable for gas adsorption.
Claims (10)
1. synthesize the method for metal organic frame thing material Mg-MOF-74, it is characterized in that it is according to following steps:
One, measure respectively DMF, methyl alcohol and deionized water and be placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ methyl alcohol/deionized water is 15:1:1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
2. the method for synthetic metal organic frame thing material Mg-MOF-74 according to claim 1, it is characterized in that described in rapid four with methyl alcohol, to replace reaction soln be in reactor, to adopt the method for suction filtration to replace.
3. the method for synthetic metal organic frame thing material Mg-MOF-74 according to claim 1, is characterized in that described in step 5 in temperature, being vacuum-drying 6 hours at 100 ℃～150 ℃.
4. synthesize the method for metal organic frame thing material Mg-MOF-74, it is characterized in that it is according to following steps:
One, measure DMF respectively and deionized water is placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ deionized water is (10～15): 1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
5. the method for synthetic metal organic frame thing material Mg-MOF-74 according to claim 4, it is characterized in that described in step 4 with methyl alcohol, to replace reaction soln be in reactor, to adopt the method for suction filtration to replace.
6. the method for synthetic metal organic frame thing material Mg-MOF-74 according to claim 4, is characterized in that described in step 5 in temperature, being vacuum-drying 6 hours at 100 ℃～150 ℃.
7. synthesize the method for metal organic frame thing material Mg-MOF-74, it is characterized in that it is according to following steps:
One, measure DMF respectively and dehydrated alcohol is placed in beaker, after mixing, make mixing solutions, wherein the volume ratio of DMF/ dehydrated alcohol is (10～15): 1;
Two, take respectively magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid, and be placed in step 1 gained mixing solutions, in ultrasonic container, water temperature is no more than under the condition that 40 ℃, ultrasonic frequency are 59kHz ultrasonic 30 minutes, obtains mixing solutions; Wherein, the mol ratio of magnesium nitrate hexahydrate and 2,5-Dihydroxyterephthalic acid is (3.3～3.4): 1;
Three, gained hydro-thermal presoma in step 2 being transferred in the stainless steel hydro-thermal still of teflon lined, put into thermostatic drying chamber, is 120～130 ℃ of Water Under heat 24 hours in temperature, and question response still is cooled to room temperature, takes out reactor;
Four, the original solution in step 3 reactor is all poured out, and then methyl alcohol is filled with to reactor, then every 12 hours, separately get methyl alcohol and replace original methyl alcohol in reactor, replace altogether 4 times;
Five, in temperature, be vacuum-drying 6 hours at 100 ℃～200 ℃, make Mg-MOF-74 material.
8. the method for synthetic metal organic frame thing material Mg-MOF-74 according to claim 7, it is characterized in that described in step 4 with methyl alcohol, to replace reaction soln be in reactor, to adopt the method for suction filtration to replace.
9. the method for synthetic metal organic frame thing material Mg-MOF-74 according to claim 7, is characterized in that described in step 5 in temperature, being vacuum-drying 6 hours at 100 ℃～150 ℃.
10. the method for synthetic metal organic frame thing material Mg-MOF-74 according to claim 7, is characterized in that described in step 5 in temperature, being vacuum-drying 6 hours at 100 ℃.
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