CN110483793A - A kind of polyacid supramolecular complex material and preparation method thereof - Google Patents
A kind of polyacid supramolecular complex material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polyacid supramolecular complex materials and preparation method thereof.Preparation method of the present invention is the following steps are included: 50mL solution A, 50mL solution B are added dropwise in beaker with the speed of 29~31 seconds/drop by (1) simultaneously；Wherein, 0.020g heteropolyacid salt (NH is contained in 50mL solution A4)3[CrMo6O24H6]·7H2Contain 0.005g (DABCO2HBF in O, 50mL solution B4) salt；(2) solution in beaker is siphoned away into 50mL after completion dropping liquid, repeats step (1), stands 5 days, obtain the rodlike polyacid supramolecular complex material of purple.The present invention grows into preferable crystalline material by double ingredient drop methods, while the speed that can be added dropwise by control obtains the crystal of different number, it might even be possible to make nano crystals material；The polyacid supramolecular complex material that the present invention is prepared can be widely used in information storage material, dielectric material, polyacid catalysis material, new electrode materials, energy storage material etc..
Description
Technical field
The invention belongs to Inorganic synthese technical field more particularly to a kind of polyacid supramolecular complex material and its preparation sides
Method.
Background technique
In recent years, Anderson type polyoxometallate shows good answer in fields such as electrochemistry, photocatalysis, magnetism
With prospect, cause the extensive discussion of researcher.Anderson type polyoxometallate is the metal oxygen cluster with nano-scale, can
It is combined with organic molecule and is built into novel hybrid material.Research and develop at present most heteropoly acids can be divided mainly into molybdenum system and
Tungsten system two major classes.Since two kinds of reactant salt rates in same solution are exceedingly fast, it is difficult to obtain crystal, therefore, the prior art is general
All over being difficult to control there is reaction rate and be difficult to control the problem of producing volume biggish monocrystalline.
Summary of the invention
The purpose of the present invention is to provide a kind of polyacid supramolecular complex material and preparation method thereof, preparation methods of the present invention
Reaction rate is easily-controllable, can be good at the polyacid for being readily able to precipitate and organic molecule grows into monocrystalline, preparation-obtained
The monocrystalline volume of polyacid supramolecular complex material is bigger.
The invention is realized in this way a kind of preparation method of polyacid supramolecular complex material, this method include following step
It is rapid:
(1) 50mL solution A, 50mL solution B are added dropwise in beaker with the speed of 29~31 seconds/drop simultaneously；Wherein, 50mL
Contain 0.020g heteropolyacid salt (NH in solution A4)3[CrMo6O24H6]·7H2Contain 0.005g (DABCO in O, 50mL solution B
2HBF4) salt；
(2) solution in beaker is siphoned away into 50mL after completion dropping liquid, repeats step (1), stands 5 days, it is rodlike to obtain purple
Polyacid supramolecular complex material.
Preferably, in step (1), (DABCO2HBF4) salt synthesis process are as follows: by 10mL solution 1 instill contain
After being placed in the container of 10mL solution 2, container tissue-wrapped and rubber band are sealed, are evaporated to solvent absolutely dry, is obtained
(DABCO·2HBF4) salt；Wherein, the solution 1 is the 10mL methanol dissolved with 0.500g DABCO, and the solution 2 is dissolution
There is the 10mL methanol of 40% tetrafluoro boric acid of 1.9568g.Existing (DABCO2HBF4) synthesis of salt is anti-by high temperature
Kettle is answered to synthesize at high temperature under high pressure, in the present invention (DABCO2HBF4) salt synthetic method in, it is only necessary to pass through constant-temperature evaporation
Mode can be prepared.In addition, in the present invention, the purpose that container tissue-wrapped and rubber band are sealed is, due to
Paper handkerchief is ventilative, will not influence the solution evaporation of beaker, other foreign matters that can be effectively prevented in air enter beaker.
The present invention further discloses the polyacid supramolecular complex materials that the above method is prepared.
The present invention overcomes the deficiencies of the prior art and provide a kind of polyacid supramolecular complex material and preparation method thereof and answers
With.In the present invention, the accurate control of the rate by drop method and to the concentration and dropwise addition of two kinds of salt, to reach to two kinds
The fine control of the reaction rate of salt, and more perfect monocrystal material is prepared under specified criteria of the present invention.The present invention
The reaction process of each substance is as follows in preparation method:
Compared with the prior art the shortcomings that and deficiency, the invention has the following advantages: the present invention is by double at branch
Drop method grows into preferable crystalline material, while the speed that can be added dropwise by control obtains the crystal of different number, or even can
To make nano crystals material；The polyacid supramolecular complex material that the present invention is prepared can be widely used in information storage material
Material, dielectric material, polyacid catalysis material, new electrode materials, energy storage material etc..
Detailed description of the invention
Fig. 1 is (DABCO2HBF in the embodiment of the present invention4) salt infrared spectrum；
Fig. 2 is drop method schematic diagram in the embodiment of the present invention；
Fig. 3 is the infrared spectrum of crystal 1 in the embodiment of the present invention；
Fig. 4 is the most simple component-part diagram of 100K crystal 1 in the embodiment of the present invention；
Fig. 5 is the most simple component-part diagram of 298K crystal 1 in the embodiment of the present invention；
Fig. 6 is 1 inside hydrogen bond figure of 100K crystal in the embodiment of the present invention；
Fig. 7 is 1 inside hydrogen bond figure of 298K crystal in the embodiment of the present invention；
Fig. 8 is the whole arrangement figures of 100K crystal 1 in the embodiment of the present invention；
Fig. 9 is the thermogravimetric curve of crystal 1 in the embodiment of the present invention；
Figure 10 is 1 dielectric constant with temperature change curve of crystal in the embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
1 heteropolyacid salt (NH of embodiment4)3[CrMo6O24H6]·7H2The synthesis process of O
(1) chromium sulfate 3.100g is weighed, the 80mL aqueous solution of ammonium molybdate is heated to boiling by ammonium molybdate 5.012g, and (oil bath adds
140 DEG C of heat)；
(2) the 20mL aqueous solution of chromium sulfate is added thereto, solution becomes black-and-blue；
(3) solution is cooled to room temperature, then water-bath is evaporated to a large amount of purple substances and is precipitated, when the solution a small amount of liquid of residue
(about two hours)；
(4) after filtering remaining hot solution while hot, filtrate film seal is taken, prevents from polluting；
(5) filtrate places 1 to 2 day remaining a small amount of liquid, filters, is dry, obtaining product 1, yield is weighed as 3.286g.And
The product 1 carries out infrared spectrum analysis, and consistent in document, determines that the product 1 is heteropolyacid salt (NH4)3[CrMo6O24H6]·
7H2O。
2 (DABCO2HBF of embodiment4) salt synthesis
The DABCO for weighing 0.500g is dissolved with the methanol of 10mL, then weighs the 40% tetrafluoro boric acid 10mL of 1.9568g
Methanol dissolution, will the latter instill before generate whiteness at once in kind of solution, sealed with paper handkerchief and rubber band, be evaporated to solvent
It is absolutely dry, obtain product 2.Infrared spectrum analysis is carried out to product 2, as a result as shown in Figure 1, passing through original known to the analysis of its infrared spectrum
Substance needed for material synthesis exists, and determines that the product 2 is target material (DABCO2HBF4) salt.
The synthesis of 3 polyacid supramolecular complex material of embodiment
(NH is weighed respectively4)3[CrMo6O24H6]·7H2O and (DABCO2HBF4) salt 0.020g and 0.005g, and by its
It is dissolved respectively with the deionized water of 50mL, after two kinds of drugs are completely dissolved, the two is transferred to the drop of 100mL respectively
In bottle, the speed that the flow velocity for putting two drop bottles is controlled in 30 seconds/drop left and right is instilled into (such as Fig. 2 in the beaker to make-up solution
It is shown), one day is dripped off again with same method make-up solution to the solution in dropping bottle, but in second of make-up solution
The solution in beaker is first siphoned away into a part with dropper, solution residue 50mL in beaker or so is processed to obtain after 5 days
Purple rhabdolith 1.
Effect example
It chooses the crystal 1 being prepared in embodiment 3 and carries out infrared spectrum analysis, as a result as shown in Figure 3.In Fig. 3, In
1117cm-1、1080cm-1For the stretching vibration of C-N, in 2859cm-1、2982cm-1For-CH2Stretching vibration, in 1409cm-1
For-CH2In-plane bending vibration, it was demonstrated that DABCO exist；In 3307cm-1The hydrone for nearby thering is a broad peak to correspond to compound
Absorption peak.400~450cm-1, 600~700cm-1, 870~950cm-1It can be respectively belonging to three ν (Mo-OX) vibration,
935cm-1、898cm-1、634cm-1It is Anderson polyanionic bone ν (Mo=O), ν (Mo-O-Mo) and ν (Mo-O-Cr) respectively
Absorption peak, it was demonstrated that (NH4)3[CrMo6O24H6]·7H2The presence of O, required substance exists in summary.
It chooses the crystal 1 being prepared in embodiment 3 and carries out the test of X-ray single crystal diffraction.It is suitable to choose size
Crystal (0.18mm × 0.17mm × 0.16mm) carries out the test of X- single crystal diffraction.It is collected using Bruker AXS CCD diffractometer single
Brilliant diffraction data uses the Mo-K alpha ray through graphite monochromator monochromatization for incident light, and wavelength isTest temperature
Degree is respectively 100K and 298K, after obtaining crystal diffraction data, by Sir92 method combination Fourier: tentatively obtaining crystal knot
Structure is modified crystal structure with complete matrix least square method.After non-hydrogen atom accurately determines, thermal parameter anisotropy is carried out
Amendment, anisotropy amendment convergence back end hydrogenation atom.As a result as shown in table 1 below:
The X-ray single crystal diffraction data of 1 crystal 1 of table
It can be seen that the space group of the crystal when temperature is 100K and 298K is P-1 central symmetry space group in table 1,
And molecular formula and relative molecular mass are respectively C6H21Cr1/2Mo3N2O14With 658.9.The cell parameter when test temperature is 100K
For α=76.408 (5) °, β=
76.408 (5) °, γ=84.762 (5) °, cell parameter is that cell parameter is when temperature is 298K α=76.585 (5) °, β=
83.610 (4) °, γ=84.968 (4) °. Δα
=-0.177 °, β=- 7.202 ° of Δ, γ=- 0.206 ° of Δ, it can be seen that crystal 1 is brilliant when temperature is 100K and in 298K
Body either in the length of each axis or structure cell all directions angular dimension have occurred -0.0822 to -0.0082 and -
7.202 ° to -0.177 ° variations differed in size, and variation degree is larger, this imply that crystal 1 is changed in temperature by 100K
It may have occurred same structural phase transition during 298K.
Structure prediction is carried out by monocrystalline analysis software to crystal 1, as shown in Figures 4 and 5.It can be seen that from Fig. 4, Fig. 5
It is by 0.5 [CrMo that the crystal structure when temperature is raised to 298K by 100K of crystal 1, which does not change,6O22H6]3-Anion,
1 DABCO and 2 moisture is molecular.
Structure prediction is carried out by monocrystalline analysis software to crystal 1, as shown in figs. 6-7.It can be seen that crystalline substance from Fig. 6, Fig. 7
Body 1 is by the N in DABCO1With the O in polyacid6Form N1-H…O6Hydrogen bond.Two molecular waters are connected with polyacid respectively, the O in water2WWith
O in polyacid4Form O4-H…O2WHydrogen bond.O in water3WWith the O in polyacid5Form O5-H…O3WHydrogen bond.It is parsed by monocrystalline
Software tests the hydrogen bond of crystal 1, as a result as shown in table 2 below:
2 crystal of table, 1 hydrogen bond table
As shown in Table 2, when temperature is 100K and 298K, 7 O-H ... O hydrogen bonds and 1 N- have been respectively formed in crystal
H ... O hydrogen bond, average bond length when wherein temperature is 100K areThe average bond angle of hydrogen bond is 164.035 °；In temperature
When for 298K, the average bond length of hydrogen bond isThe average bond angle of hydrogen bond is 163.731 °.
Structure prediction is carried out by monocrystalline analysis software to crystal 1, as a result as shown in Figure 8.As can be seen from Figure 8 crystal
More acid radical anions in 1 are accumulated in three-dimensional space in stratiform, and DABCO is just filled in more acid radical anions by being piled into
Gap in.
Thermogravimetric analysis is carried out to crystal 1, as a result as shown in Figure 9.This temperature range that thermogravimetric analysis of crystal 1 is chosen
For 310K-865K, start to decompose in 400K or so as seen in Figure 9, is broadly divided into three phases decomposition, i.e. 400K
~490K, 490K~560K, 560K~700K three phases, in the phase III, crystal 1 is decomposed completely.
Measurement is carried out to crystal 1, the results are shown in Figure 10.As shown in Figure 10, when temperature is 140K~240K, each frequency
Dielectric data under rate is unchanged, and after temperature is 240K, the variation of friction speed, In takes place in the dielectric data under each frequency
Dielectric data reaches peak value when temperature is 270K.The temperature that may occur due to crystal 1 of abnormal Dielectric changes by 100K
The angle of a, b, c-axis and α, β, γ have occurred caused by biggish variation when for 298K.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (3)
1. a kind of preparation method of polyacid supramolecular complex material, which is characterized in that method includes the following steps:
(1) 50mL solution A, 50mL solution B are added dropwise in beaker with the speed of 29~31 seconds/drop simultaneously；Wherein, 50mL solution
Contain 0.020g heteropolyacid salt (NH in A4)3[CrMo6O24H6]·7H2Contain 0.005g (DABCO in O, 50mL solution B
2HBF4) salt；
(2) solution in beaker is siphoned away into 50mL after completion dropping liquid, repeats step (1), stands 5 days, obtain the rodlike polyacid of purple
Supramolecular complex material.
2. the preparation method of polyacid supramolecular complex material as described in claim 1, which is characterized in that in step (1), institute
State (DABCO2HBF4) salt synthesis process are as follows: by 10mL solution 1 instillation be contained in the container of 10mL solution 2 after, will hold
Device tissue-wrapped and rubber band sealing, are evaporated to absolutely dry to solvent, obtain (DABCO2HBF4) salt；Wherein, the solution 1 is
10mL methanol dissolved with 0.500g DABCO, the solution 2 are the 10mL first of 40% tetrafluoro boric acid dissolved with 1.9568g
Alcohol.
3. the polyacid supramolecular complex material that claim 1 the method is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111604091A (en) * | 2020-06-24 | 2020-09-01 | 新疆农业大学 | Combined supported catalyst and preparation method and application thereof |
| CN111617802A (en) * | 2020-06-24 | 2020-09-04 | 新疆农业大学 | Combined supported catalyst and preparation method and application thereof |
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| CN103359791A (en) * | 2013-07-03 | 2013-10-23 | 吉林化工学院 | Vanadic acid-chrome molybdate mixed cluster polyacid compound structure and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111604091A (en) * | 2020-06-24 | 2020-09-01 | 新疆农业大学 | Combined supported catalyst and preparation method and application thereof |
| CN111617802A (en) * | 2020-06-24 | 2020-09-04 | 新疆农业大学 | Combined supported catalyst and preparation method and application thereof |
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