CN110273181B - A kind of organic-inorganic hybrid copper-containing polyoxomolybdate crystal material and preparation method thereof - Google Patents
A kind of organic-inorganic hybrid copper-containing polyoxomolybdate crystal material and preparation method thereof Download PDFInfo
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Abstract
An organic-inorganic hybrid copper-containing polyoxometallate crystal material and a preparation method thereof, belonging to organic-inorganic hybrid materials and polyoxometallateThe field of acid salt materials. Has a chemical formula of (C)4H6N2)8Cu4[Mo8O26](ii) a Triclinic system, space group P-1, cell parameters
α＝73.297(8)o，β＝70.196(8)o，γ＝76.896(8)o. The polymolyloximate crystal material is prepared by a hydrothermal synthesis method, and is prepared by placing ammonium molybdate, 1-methylimidazole, copper sulfate and water in a closed system. The poly-molybdate oxygen salt crystal material can play a role in catalysis when cyclopentene is oxidized by hydrogen peroxide to prepare glutaraldehyde, so that the product yield can reach 62%, and good catalytic activity is shown.
Description
Technical Field
The invention belongs to the field of organic-inorganic hybrid materials and polyoxometallate materials, and particularly relates to an organic-inorganic hybrid copper-containing polyoxometallate crystal material and a preparation method thereof.
Background
Some transition metals, such as niobium, tantalum, molybdenum, tungsten, etc., can form polyoxometallate in a high oxidation state, and the materials have unique electronic structures, often show some excellent characteristics, such as conductivity, magnetism, redox, catalysis, optical nonlinearity, etc., and have wide application in analysis, clinical diagnosis, catalysis (including photocatalysis), biochemistry, medicine, material science, etc. The preparation of such polyoxometallates having specific compositions and functions is therefore gaining increasing attention.
With the research of polyoxometallate materials, organic components and inorganic polyoxometallate units are hybridized to form organic-inorganic hybrid materials. It is particularly emphasized that catalytic activity is an important commonality of such materials. Compared with other catalytic materials, the material has high catalytic activity, low toxicity and few catalytic byproducts, so that the design and preparation of the material are realistic and meaningful works. The recent challenge in this field of research is how to select a suitable method, construct crystals of a desired structure using basic building blocks (modules), and further improve the catalytic performance of such materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an organic-inorganic hybrid copper-containing polyoxometallate crystal material and a preparation method thereof.
In order to solve the technical problem of the invention, the adopted technical scheme is as follows: an organic-inorganic hybrid copper-containing polyoxometallate crystal material consists of polyoxometallate crystals with a chemical formula of (C)4H6N2)8Cu4[Mo8O26]The structural formula is shown in figure 1.
The organic-inorganic hybrid copper-containing polyoxometallate crystal material is prepared by a hydrothermal synthesis method, wherein 0.08-0.12 part by weight of ammonium molybdate, 0.10-0.15 part by weight of copper sulfate, 0.02-0.05 part by weight of 1-methylimidazole and 15-20 parts by weight of water are uniformly mixed to prepare a reaction substrate, and the reaction substrate is hydrothermally synthesized in a reaction container to prepare the organic-inorganic hybrid copper-containing polyoxometallate crystal material, wherein the hydrothermal synthesis temperature is at least 160 ℃, and the hydrothermal synthesis time is at least 10 hours.
Compared with the prior art, the invention has the beneficial effects that:
first, the target product obtained was detected by a single crystal diffractometer, and from the result, the chemical formula of the crystal of the target product was (C)4H6N2)8Cu4[Mo8O26]The crystal belongs to the triclinic system, the space group is P-1, and the unit cell parameter is
α＝73.297(8)°，β＝70.196(8)°，γ＝76.896(8)°，
Z＝2，Dc＝2.417g/cm3. The target product is named as organic-inorganic hybrid copper-containing polyoxometallate crystal material.
II according to the formula (C)4H6N2)8Cu4[Mo8O26]The H, C, N content in the compound was calculated: h2.30%, C18.22%, N10.63%. Elemental analysis shows that the content of H, C, N in the crystalline material is 2.35%, C18.18% and N10.71%, respectively, which is consistent with theoretical calculation.
And thirdly, the organic-inorganic hybrid copper-containing polyoxometallate crystal material can play a role in catalysis when cyclopentene is oxidized by hydrogen peroxide to prepare glutaraldehyde, so that the yield of the product can reach more than 60%.
Fourthly, the preparation of the organic-inorganic hybrid copper-containing polyoxometallate crystal material is realized by a hydrothermal synthesis method, the synthesis method is simple and easy to operate, and the reaction yield is high.
Fifthly, the hydrothermal synthesis temperature in the preparation method of the organic-inorganic hybrid copper-containing polyoxometallate crystal material is at least 160 ℃, otherwise, the crystal material cannot be prepared.
As a further embodiment of the beneficial effects: firstly, the hydrothermal synthesis time is 24-48 h, the hydrothermal synthesis temperature is 180-200 ℃, and the organic-inorganic hybrid copper-containing polyoxometallate crystal material with higher yield is obtained. Secondly, the rate of heating the reaction substrate from room temperature to the hydrothermal synthesis temperature before the hydrothermal synthesis starts is 1-2 ℃/min, and the rate of cooling the reaction substrate from the hydrothermal synthesis temperature to the room temperature after the hydrothermal synthesis is finished is 6-8 ℃/h, so that the polymolyloximate crystal with good form can be obtained. And fourthly, the reaction container is an autoclave arranged in an oven, the temperature rise before the hydrothermal synthesis starts, the heat preservation in the hydrothermal synthesis process and the temperature reduction after the hydrothermal synthesis are regulated and controlled by the oven, the hydrothermal synthesis reaction is carried out in the autoclave so that water is in a subcritical and supercritical state, the reaction is at a molecular level at the moment, and the reactivity is improved, so that the crystal material can be better prepared by adopting the autoclave than other equipment. The oven can conveniently adjust the temperature of the hydrothermal reaction and also can keep the hydrothermal reaction kettle at a proper temperature rising and reducing speed.
Drawings
The present invention will be described in further detail with reference to the following examples and accompanying drawings.
FIG. 1 is a single crystal structural view of an object product obtained by the present invention.
FIG. 2 is one of the results of the characterization of the target product of the present invention using an infrared spectrometer model VECTOR22 FT-IR; wherein the abscissa is the wave number/cm-1And the ordinate represents transmittance/%.
FIG. 3 is one of the results of a thermogravimetric analyzer model Q500 for the target product made in accordance with the present invention; wherein the abscissa is temperature/° c and the ordinate is weight change/%.
Detailed Description
Example 1
0.08g of ammonium molybdate, 0.02g of 1-methylimidazole and 0.10g of copper sulfate were weighed into a 50mL flask, 18mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the high-pressure autoclave is put into an oven, heated to 180 ℃ from room temperature at the speed of 1.5 ℃/min, kept at the temperature for 24 hours, and then cooled to room temperature at the speed of 6 ℃/h, so as to obtain the organic-inorganic hybrid copper-containing polyoxometalate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3, and the yield is about 75 percent.
The crystal structure of the target product obtained in this example was measured by a single crystal diffractometer, and the results were as follows:
crystal data:
crystal bond length
Data:
| Mo(1)-O(1) | 1.689(2) | Mo(2)-O(7) | 1.899(2) | Mo(3)-O(5) | 2.452(2) |
| Mo(1)-O(3) | 1.745(2) | Mo(2)-O(4) | 1.994(2) | Mo(4)-O(13) | 1.697(2) |
| Mo(1)-O(2) | 1.944(1) | Mo(2)-O(5) | 2.337(1) | Mo(4)-O(12) | 1.698(7) |
| Mo(1)-O(4) | 1.947(1) | Mo(3)-O(9) | 1.701(2) | Mo(4)-O(11) | 1.895(2) |
| Mo(1)-O(5) | 2.131(1) | Mo(3)-O(10) | 1.704(2) | Mo(4)-O(2) | 1.995(2) |
| Mo(2)-O(6) | 1.694(2) | Mo(3)-O(7) | 1.922(2) | Mo(4)-O(5) | 2.345(1) |
| Mo(2)-O(8) | 1.703(2) | Mo(3)-O(11) | 1.923(2) | Cu(1)-N(1) | 1.870(2) |
| N(7)-Cu(2) | 1.873(3) | N(5)-Cu(2) | 1.868(2) | Cu(1)-N(3) | 1.870(2) |
crystal bond angle (o) Data:
| O(1)-Mo(1)-O(3) | 104.34(8) | O(8)-Mo(2)-O(5) | 95.64(7) | O(11)-Mo(3)-O(5) | 74.12(6) |
| O(1)-Mo(1)-O(2) | 101.06(7) | O(7)-Mo(2)-O(5) | 77.11(6) | O(13)-Mo(4)-O(12) | 104.67(9) |
| O(3)-Mo(1)-O(2) | 96.87(7) | O(4)-Mo(2)-O(5) | 73.03(6) | O(13)-Mo(4)-O(11) | 101.71(8) |
| O(1)-Mo(1)-O(4) | 101.56(7) | O(9)-Mo(3)-O(10) | 105.18(1) | O(12)-Mo(4)-O(11) | 101.13(8) |
| O(3)-Mo(1)-O(4) | 95.86(7) | O(9)-Mo(3)-O(7) | 102.07(8) | O(13)-Mo(4)-O(2) | 100.73(8) |
| O(2)-Mo(1)-O(4) | 150.34(6) | O(10)-Mo(3)-O(7) | 98.63(8) | O(12)-Mo(4)-O(2) | 98.27(8) |
| O(1)-Mo(1)-O(5) | 99.49(7) | O(9)-Mo(3)-O(11) | 102.78(8) | O(11)-Mo(4)-O(2) | 145.37(6) |
| O(3)-Mo(1)-O(5) | 156.17(6) | O(6)-Mo(2)-O(8) | 104.91(9) | O(13)-Mo(4)-O(5) | 160.16(7) |
| O(2)-Mo(1)-O(5) | 78.75(6) | Mo(2)-O(5)-Mo(4) | 163.99(7) | O(12)-Mo(4)-O(5) | 94.89(7) |
| O(4)-Mo(1)-O(5) | 78.81(6) | Mo(1)-O(5)-Mo(3) | 164.76(7) | O(11)-Mo(4)-O(5) | 77.25(6) |
| O(6)-Mo(2)-O(8) | 104.91(9) | Mo(2)-O(5)-Mo(3) | 86.19(5) | O(2)-Mo(4)-O(5) | 72.73(6) |
| O(6)-Mo(2)-O(7) | 101.37(8) | Mo(4)-O(5)-Mo(3) | 85.65(5) | Mo(1)-O(2)-Mo(4) | 109.91(7) |
| O(8)-Mo(2)-O(7) | 101.82(8) | O(10)-Mo(3)-O(11) | 98.76(8) | Mo(1)-O(4)-Mo(2) | 109.64(7) |
| O(6)-Mo(2)-O(4) | 100.84(8) | O(7)-Mo(3)-O(11) | 144.58(7) | Mo(1)-O(5)-Mo(2) | 92.16(5) |
| O(8)-Mo(2)-O(4) | 96.86(8) | O(9)-Mo(3)-O(5) | 159.98(8) | Mo(1)-O(5)-Mo(4) | 92.10(5) |
| O(7)-Mo(2)-O(4) | 146.05(6) | O(10)-Mo(3)-O(5) | 94.83(8) | N(1)-Cu(1)-N(3) | 169.85(9) |
| O(6)-Mo(2)-O(5) | 159.20(7) | O(7)-Mo(3)-O(5) | 73.86(6) | N(5)-Cu(2)-N(7) | 176.11(1) |
and (3) analyzing a crystal structure:
referring to FIG. 1, the crystal structure contains a polymolybdenum oxyanion [ Mo ]8O26]4-Complex cation [ (C) coordinated with four 1-methylimidazole and copper ions4H6N2)2Cu]+. Polymolybdenum oxyanion [ Mo ]8O26]4-Can be seen as two identical Mo4O13}2-The whole structure is composed of eight similar MoO6Polyhedrons, which are connected in a common edge. The eight molybdenum atoms can be divided into two groups, four of which are in the same plane. In the presence of poly-molybdenum oxyanion [ Mo ]8O26]4-In (A), Mo-O bonds can be classified into four types: (i) Mo-Ot(terminal oxygen) at a distance of
To (c) to (d); (ii) Mo-Oμ-2(bridge oxygen) at a distance of
To (c) to (d); (iii) Mo-Oμ-3(bridge oxygen) at a distance of
To (c) to (d); (iv) Mo-Oμ-4(bridge oxygen) at a distance of
In the meantime.
As can be seen from FIG. 2, 3133 and 3107cm in the infrared spectrum-1The peak is C-H telescopic vibration absorption on the imidazole ring; 2920cm-1C-H stretching with a peak on the methyl groupAbsorbing vibration; 1542-1024cm-1The peak is the vibrational absorption of the imidazole ring. 931. 893, 795, 745, 668, 565cm-1The series of absorption peaks of (a) are characteristic stretching vibration peaks of Mo ═ O and Mo-O-Mo. According to the infrared spectrum, the vibration position of the absorption peak is consistent with the structural analysis of the target product.
As can be seen from fig. 3, such crystals remain stable until 220 c and begin to decompose rapidly at 310 c.
Example 2
0.09g of ammonium molybdate, 0.03g of 1-methylimidazole and 0.12g of copper sulfate were weighed into a 50mL flask, 18mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the high-pressure autoclave is put into an oven, the high-pressure autoclave is heated to 190 ℃ from room temperature at the speed of 1.5 ℃/min, the temperature is kept for 24 hours, and then the high-pressure autoclave is cooled to room temperature at the speed of 8 ℃/h, so that the organic-inorganic hybrid copper-containing polyoxometalate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3 is obtained, and the yield is about 73 percent.
Example 3
0.10g of ammonium molybdate, 0.04g of 1-methylimidazole and 0.12g of copper sulfate were weighed into a 50mL flask, 18mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the high-pressure autoclave is put into an oven, heated to 180 ℃ from room temperature at the speed of 2 ℃/min, kept at the temperature for 24 hours, and then cooled to room temperature at the speed of 6 ℃/h, so as to obtain the organic-inorganic hybrid copper-containing polyoxometalate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3, and the yield is about 69 percent.
Example 4
0.11g of ammonium molybdate, 0.04g of 1-methylimidazole and 0.14g of copper sulfate were weighed into a 50mL flask, 18mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the autoclave is put into an oven and heated to 180 ℃ from room temperature at the rate of 1.5 ℃/min, the temperature is kept for 24 hours, and then the temperature is reduced to room temperature at the rate of 7 ℃/h, thus obtaining the organic-inorganic hybrid copper-containing polyoxometalate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3, and the yield is about 71 percent.
Example 5
0.12g of ammonium molybdate, 0.02g of 1-methylimidazole and 0.13g of copper sulfate were weighed into a 50mL flask, 18mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the high-pressure autoclave is put into an oven, heated to 180 ℃ from room temperature at the speed of 1.5 ℃/min, kept at the temperature for 24 hours, and then cooled to room temperature at the speed of 6 ℃/h, so as to obtain the organic-inorganic hybrid copper-containing polyoxometalate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3, and the yield is about 72 percent.
Example 6
0.11g of ammonium molybdate, 0.03g of 1-methylimidazole and 0.12g of copper sulfate were weighed into a 50mL flask, 20mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the high-pressure autoclave is put into an oven, heated to 180 ℃ from room temperature at the speed of 1.5 ℃/min, kept at the temperature for 30h, and then cooled to room temperature at the speed of 8 ℃/h, so as to obtain the organic-inorganic hybrid copper-containing polyoxometalate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3, and the yield is about 78%.
Example 7
0.11g of ammonium molybdate, 0.03g of 1-methylimidazole and 0.12g of copper sulfate were weighed into a 50mL flask, 20mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the high-pressure autoclave is put into an oven, heated to 200 ℃ from room temperature at the speed of 1.5 ℃/min, kept at the temperature for 30h, and then cooled to room temperature at the speed of 6 ℃/h, so as to obtain the organic-inorganic hybrid copper-containing polyoxometalate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3, and the yield is about 81 percent.
Example 8
0.11g of ammonium molybdate, 0.03g of 1-methylimidazole and 0.12g of copper sulfate were weighed into a 50mL flask, 20mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the high-pressure autoclave is put into an oven, the high-pressure autoclave is heated to 190 ℃ from room temperature at the speed of 1.5 ℃/min, the temperature is kept for 36h, then the temperature is reduced to room temperature at the speed of 8 ℃/h, and the organic-inorganic hybrid copper-containing polyoxometalate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3 is obtained, and the yield is about 83 percent.
Example 9
0.11g of ammonium molybdate, 0.03g of 1-methylimidazole and 0.12g of copper sulfate were weighed into a 50mL flask, 20mL of water was added, and the flask was placed on a magnetic stirrer and stirred and mixed for 30 minutes.
② the mixed solution was transferred to a 25mL autoclave.
Thirdly, the high-pressure autoclave is put into an oven, the high-pressure autoclave is heated to 200 ℃ from room temperature at the speed of 2 ℃/min, the temperature is kept for 48 hours, and then the high-pressure autoclave is cooled to room temperature at the speed of 7 ℃/h, so that the organic-inorganic hybrid copper-containing polyoxometallate crystal material which is shown in the structural formula of figure 1 and shown in the curves of figure 2 and figure 3 is obtained, and the yield is about 85 percent.
Example 10
Application examples
The application of the organic-inorganic hybrid copper-containing polyoxometallate crystal material in catalyzing hydrogen peroxide to oxidize cyclopentene to prepare glutaraldehyde.
0.07g of organic-inorganic hybrid copper-containing polyoxometallate crystal material ground into powder is added into a round-bottomed flask filled with 20mL of tert-butyl alcohol and 8mL of cyclopentene, the reaction temperature is controlled at 36 ℃, and 15mL of hydrogen peroxide is dropwise added. After 3h of reaction, the solution was filtered to remove the catalyst and chromatographed. The result shows that the yield of the obtained product can reach 62 percent, and the product shows better catalytic activity.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. An organic-inorganic hybrid copper-containing polyoxometallate crystal material, which consists of a polyoxometallate crystal and is characterized in that:
the chemical formula of the polyoxometallate crystal is (C)4H6N2)8Cu4[Mo8O26]；
The structural formula of the polymolyoxomolybdate crystal is as follows:
the polymolybdate crystal belongs to the triclinic system with a space group of P-1, unit cell parameters a =10.446(2) A, b =11.904(2) A, c =12.977(2) A,α=73.297(8)o，β=70.196(8)o，γ=76.896(8)o，V=2878.4(1)Å3，Z=2，Dc=2.417g/cm3；
the crystal structure comprises a polymolybdenum oxyanion [ Mo ]8O26]4-Complex cation [ (C) coordinated with four 1-methylimidazole and copper ions4H6N2)2Cu]+(ii) a Polymolybdenum oxyanion [ Mo ]8O26]4-Are two identical { Mo4O13}2-The whole structure is composed of eight { MoO6Polyhedrons which are connected in a common edge manner; eight molybdenum atoms divided into twoGroup, wherein four molybdenum atoms are on the same plane; in the presence of poly-molybdenum oxyanion [ Mo ]8O26]4-In (A), Mo-O bonds are classified into four types: (i) Mo-OtOxygen-terminated, at a distance between 1.689(2) to 1.703(2) A; (ii) Mo-Oµ-2Bridge oxygen at a distance between 1.745(2) and 2.337(1) A; (iii) Mo-Oµ-3Bridge oxygen at a distance between 1.944(1) and 2.345(1) A; (iv) Mo-Oµ-4Bridge oxygen at a distance of from 2.131(1) to 2.452(2) A.
2. A method for producing an organic-inorganic hybrid copper-containing polyoxometalate crystalline material as claimed in claim 1, by hydrothermal synthesis, characterized in that: 0.08-0.12 part by weight of ammonium molybdate, 0.10-0.15 part by weight of copper sulfate, 0.02-0.05 part by weight of 1-methylimidazole and 15-20 parts by weight of water are uniformly mixed to prepare a reaction substrate, the reaction substrate is hydrothermally synthesized in a reaction vessel to prepare the organic-inorganic hybrid copper-containing polyoxometalate crystal material, the hydrothermal synthesis time is 24-48 hours, and the hydrothermal synthesis temperature is 180-200 ℃.
3. The method of claim 2, wherein: before the hydrothermal synthesis is started, the rate of raising the temperature of the reaction substrate from room temperature to the hydrothermal synthesis temperature is 1-2 ℃/min.
4. The method of claim 2, wherein: after the hydrothermal synthesis is finished, the rate of cooling from the hydrothermal synthesis temperature to the room temperature is 6-8 ℃/h.
5. The method of claim 2, wherein: the reaction container is a high-pressure kettle arranged in an oven, and the temperature rise before the hydrothermal synthesis, the heat preservation in the hydrothermal synthesis process and the temperature reduction after the hydrothermal synthesis are regulated and controlled by the oven.
6. An application of the organic-inorganic hybrid copper-containing polyoxometallate crystal material as claimed in claim 1 in catalyzing hydrogen peroxide to oxidize cyclopentene to prepare glutaraldehyde.
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