CN114011439A - 3D structure compound formed by Anderson type polyacid and transition metal copper, preparation method and catalytic application - Google Patents

3D structure compound formed by Anderson type polyacid and transition metal copper, preparation method and catalytic application Download PDF

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CN114011439A
CN114011439A CN202111500386.9A CN202111500386A CN114011439A CN 114011439 A CN114011439 A CN 114011439A CN 202111500386 A CN202111500386 A CN 202111500386A CN 114011439 A CN114011439 A CN 114011439A
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polyacid
transition metal
compound
metal copper
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侯玉姣
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Xuchang University
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
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    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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Abstract

The invention belongs to the technical field of novel polyacid chemical materials, and discloses an Anderson-based polyacid { TeMo6A 3D inorganic framework structure compound formed by transition metal and a preparation method and catalytic application thereof. The 3D structure polyacid compound is a triclinic crystal system, and the space group is P-1; the compound has a unit cell parameter of
Figure DDA0003402429660000011
Figure DDA0003402429660000012
α is 70.858(2) °, β is 71.465(3) °, and γ is 84.149(3) °; the invention discloses a methodThe method is synthesized by sodium molybdate, sodium tellurite, potassium chloride and copper chloride in a conventional aqueous solution in a one-pot method, and has the advantages of low raw material price, high synthesis yield and good catalytic performance for selectively oxidizing thioether compounds; the preparation process is simple, the product purity is high, and the catalyst has potential catalytic application prospect.

Description

3D structure compound formed by Anderson type polyacid and transition metal copper, preparation method and catalytic application
Technical Field
The invention belongs to the technical field of novel polyacid chemical materials, and particularly relates to a 3D structure compound formed by Anderson type polyacid and transition metal copper, a preparation method and catalytic application.
Background
Polyoxometalates (polyacid) is a group of compounds consisting of early transition metal ions (Mo)Ⅵ，WⅥ，VⅤ，NbⅤAnd TaⅤEtc.) are combined with oxygen atoms, which makes the polyacid have important applications in the fields of catalysis, optics, pharmacy, etc. in recent years due to its higher thermal stability, oxidation-reduction property, solubility, acid-base property, etc. (a.proust, b.matt, et al.chem.soc.rev,2012,41, 7605-; long, E.Burkholder, et al.Cronin.chem.Soc.Rev,2007,36, 105-121; K.Kamata, K.Yonehara, Y.Sumida, K.Yamaguchi, S.Hikichi, N.Mizuno. et al science, 2003,300, 964-substituted 966; J.T.Rhule, C.L.Hill.D.A.Judd.et al.chem.Rev.,1998,98, 327-358). To date, the synthesis of polyacids has been studied for nearly 200 years, while 3D polyacids are relatively few, especially 3D polyacids constructed from pure inorganic elements, and therefore, it is a challenging subject to select appropriate polyacids and metal nodes to synthesize 3D polyacid inorganic functional materials.
The Anderson-type polymolybdates also have received much attention as an important class of branch in polyacids. This is due to the fact that the anion of the Anderson type polyacid has a terminal oxygen atom with high reactivity, and thus a large number of organic-inorganic hybrid compounds based on the Anderson type polyacid have been reported (X.X.Li, Y.X.Wang, R.H.Wang.et al.Angew.chem.Int.Ed.2016,128, 6572-6576; M.Zeng, J.Tan, K.Chen, et al.ACS appl.Mater.Interfaces.2019,11,8, 8537-. But are currently based on Anderson type polyacids { TeMo6No inorganic framework materials formed with transition metal ion copper have been reported. Meanwhile, the transition metal not only has better coordination capability, but also has potential application in the aspects of catalysis, medicaments, laser and the like. Thus based on Anderson type polyacid { TeMo6The synthesis of high-dimensional inorganic frame materials with transition metals is faced with more difficulties and opportunities.
Selective catalytic oxidation of organic compounds has been an important component of polyacid catalytic application, and sulfoxides and sulfones compounds obtained by selective catalytic oxidation of thioethers are important intermediates of medicinal chemicals, so that a large amount of polyacids are used for catalytic oxidation of sulfur-containing compounds (Y.Yang, B.Zhang, Y.Wang, et al.J.Am.chem.Soc,2013,135,14500-ng, S.Yang, et al.Crystal.growth Des,2015,15, 1907-; zhu, L.K.Yan, W.Guan, et al.Dalton trains 2015,44, 9063-9070; han, Y.Niu, R.Wan, et al.chem.Eur.J., 2018,24, 11059-11066; J.Wang, Y.Niu, M.Zhang, et al.2018,57, 1796-one 1805; wang, Y.Niu, D.ZHao, et al.Inorg.chem,2017,56, 14053-14059). At present, in the research aspect of polyacid catalyzed thioether oxidation reaction, organic and inorganic hybrid compounds are mainly focused on, and inorganic framework structures are relatively few. Meanwhile, Anderson type polyacid { TeMo6Catalytic oxidation of thioethers by compounds that form a pure inorganic framework structure with transition metals has not been reported, and therefore the synthesis of catalysts based on transition metals and Anderson type polyacids { TeMo }6The compounds of (1) and having better catalytic oxidation of thioethers are a challenge but have practical application value.
Disclosure of Invention
The invention aims to solve the existing problems and provides a 3D structure compound formed by Anderson type polyacid and transition metal copper, a preparation method and catalytic application.
The invention is realized by the following technical scheme:
anderson type polyacid { TeMo6The compound of 3D structure with transition metal has the chemical formula of [ K (H)2O)]2[Cu(H2O)4][Cu(H2O)2][TeMo6O24]The polyacid species is a triclinic system, and the space group is P-1; the compound has a unit cell parameter of
Figure BDA0003402429640000021
α＝70.858(2)°，β＝71.465(3)°，γ＝84.149(3)°。
The structure of the polyacid compound: in asymmetric units there is a crystallographically independent [ TeMo ]6O24]6-Polyacid anion, two transition metal copper ions and one potassium ion; both copper ions adopt six coordination to form an octahedral configuration, and potassium ions also adopt six ligands to form the octahedral configuration; firstly [ TeMo ]6O24]6-The units form a 1D chain structure through chemical bonds Cu-O-Mo, and the 1D chains are connected through the chemical bonds Cu-O-MoForming a 2D net structure, wherein the 2D net structure forms a 3D frame structure through the action of chemical bonds K-O-Mo.
Based on Anderson type polyacid { TeMo6The preparation method of the compound with the 3D structure of the transition metal comprises the following steps:
mixing sodium molybdate and sodium tellurite, dissolving, adding KCl, adjusting pH to 3.5 with HCl, stirring at room temperature for a while, stirring in water bath at 80 deg.C for 1 hr, adding transition metal CuCl2And adjusting the pH value to 3-5, heating and refluxing for 8-12 h at 80-100 ℃, cooling the solution, filtering, standing until crystals are generated, and washing and drying the crystals to obtain the 3D polymolybdate.
Said Na2MoO4、Na2TeO3KCl and CuCl2The amount ratio of the substances is 6:1:3 to 5: 3.
The hydrochloric acid solution is 2 mol/L.
Compared with the prior art, the invention has the following advantages:
(1) the 3D polyacid compound provided by the invention has a definite structure, and is the first example of Anderson type polyacid { TeMo6And 3D inorganic framework structure of transition metal, and the species shows better performance of selectively catalyzing and oxidizing thioether compounds. Therefore, the invention has potential application prospect in catalysis.
(2) The 3D polyacid material disclosed by the invention is used as a heterogeneous catalyst in a thioether oxidation reaction, and has the advantages of easiness in recovery and repeated utilization. After the catalytic reaction is finished, solid powder obtained by filtering is used as a catalyst, and repeated catalytic experiments are carried out for many times, and the catalytic result shows that the reaction yield is not obviously reduced.
(3) The method for preparing the 3D polyacid material is a conventional aqueous solution method, and has the advantages of safe and simple operation, low raw material cost and 46% yield.
Drawings
FIG. 1 is a diagram of an asymmetric unit of the polyacid compound of the present invention;
FIG. 2 is a 1D structural diagram of the polyacid compound of the present invention;
FIG. 3 is a 2D structural diagram of the polyacid compound of the present invention;
FIG. 4 is a 3D structural diagram of the polyacid compound of the present invention;
FIG. 5 is a 3D topology of the polyacid compound of the present invention;
FIG. 6 shows the catalytic efficiency of the polyacid compound obtained in example 1 of the present invention after 5 times of recycling;
FIG. 7 shows IR spectra before and after catalysis of the polyacid compound obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are provided herein for purposes of illustration and are not intended to be limiting.
Example 1
The preparation of the polyacid compound comprises the following steps:
mixing sodium molybdate and sodium tellurite, dissolving, adding KCl, adjusting pH to 3.5 with HCl, stirring at room temperature for a while, stirring in water bath at 80 deg.C for 1 hr, adding transition metal CuCl2Adjusting the pH value to 4.0, heating and refluxing for 12h at 80 ℃, cooling the solution, filtering, standing until crystals are generated, and washing and drying the crystals to obtain the 3D polymolybdate. Wherein Na2MoO4、Na2TeO3KCl and CuCl2The ratio of the amounts of the substances of (a) to (b) is 6:1:3: 3.
Example 2
The preparation of the polyacid compound comprises the following steps:
mixing sodium molybdate and sodium tellurite, dissolving, adding KCl, adjusting pH to 3.5 with HCl, stirring at room temperature for a while, stirring in water bath at 80 deg.C for 1 hr, adding transition metal CuCl2Adjusting the pH value to 4.0, heating and refluxing for 12h at 100 ℃, cooling the solution, filtering, standing until crystals are generated, and washing and drying the crystals to obtain the 3D polymolybdate. Wherein Na2MoO4、Na2TeO3KCl and CuCl2The ratio of the amounts of the substances of (a) to (b) is 6:1:3: 3.
Example 3
The preparation of the polyacid compound comprises the following steps:
mixing sodium molybdate and sodium tellurite, dissolving, adding potassium chloride, adjusting pH to 3.5 by HCl, stirring for a period of time at room temperature, stirring for 1h in water bath at 80 ℃, adding transition metal copper chloride, adjusting pH to 5.0, heating and refluxing for 12h at 90 ℃, cooling the solution, filtering, standing until crystals are generated, and washing and drying the crystals to obtain the 3D polymolybdate. Wherein Na2MoO4、Na2TeO3KCl and CuCl2The ratio of the amounts of the substances of (a) to (b) is 6:1:3: 3.
The products of the above examples were examined to obtain a compound of the formula [ K (H)2O)]2[Cu(H2O)4][Cu(H2O)2][TeMo6O24]The crystal structures of the polyacid compounds of the present invention are shown in FIGS. 1, 2, 3, 4 and 5.
The performance of the polyacid compound for selectively catalyzing and oxidizing the thioether compounds is measured by using a gas chromatograph and acetonitrile as a solvent. Table 1 shows that the invention selectively catalyzes various thioethers by utilizing the redox performance of transition metal ions and polyacid, and the yield reaches 97.1 percent in experiments for catalyzing the thioethers. Thus, the Anderson type polyacid { TeMo of the present invention6Compounds formed with transition metals can be used as catalytic materials for selective catalytic oxidation of thioethers. Fig. 6 and 7 show that after the catalyst of the present invention is subjected to a catalytic reaction, the solid powder catalyst can be recovered by filtration, and then the catalytic experiment is repeated, and the catalytic result shows that the reaction yield is not significantly reduced, which indicates that the catalyst is a stable heterogeneous catalyst.
TABLE 1 Table of compounds for the catalytic oxidation of thioethers
Figure BDA0003402429640000041
Figure BDA0003402429640000051
Reaction conditions are as follows: phenylmethyl sulfide(0.25mmol), catalyst 1.5 mmol%, H2O2(0.3mmol), internal standard naphthalene (0.25mmol), solvent acetonitrile 0.5mL, room temperature (25 deg.C) reaction, using gas chromatography to determine reaction conversion and selectivity.

Claims (5)

1. A3D structure compound formed by Anderson type polyacid and transition metal copper, which is characterized in that the chemical formula of the 3D polyacid compound is [ K (H)2O)]2[Cu(H2O)4][Cu(H2O)2][TeMo6O24]The species is triclinic, and the space group is P-1; compound 1 has unit cell parameters of
Figure FDA0003402429630000011
Figure FDA0003402429630000012
α＝70.858(2)°，β＝71.465(3)°，γ＝84.149(3)°；
The structure of the polyacid compound: in asymmetric units there is a crystallographically independent [ TeMo ]6O24]6-Polyacid anion, two transition metal copper ions and one potassium ion; both copper ions and potassium ions adopt a hexa-coordination to form an octahedral configuration, firstly [ TeMo6O24]6-The unit forms a 1D chain structure through a chemical bond Cu-O-Mo, the 1D chains form a 2D net structure through the chemical bond Cu-O-Mo, and the 2D net structure forms a 3D frame structure through the chemical bond K-O-Mo.
2. A method for preparing a 3D structured compound of the Anderson-type polyacid of claim 1 and a transition metal copper, wherein a conventional aqueous solution is prepared by the steps of:
mixing Na2MoO4、Na2TeO3Mixing, dissolving, adding KCl, adjusting pH to 3.5 with HCl, stirring at room temperature for a while, stirring in water bath at 80 deg.C for 1 hr, adding transition metal CuCl2Adjusting the pH value to 3-5, and then heating at 80-100 DEG CAnd (3) refluxing for 8-12 h, cooling the solution, filtering, standing until crystals are generated, and washing and drying the crystals to obtain the 3D polymolybdate.
3. The method for preparing a 3D structure compound formed by Anderson type polyacid and transition metal copper according to claim 1, wherein Na is2MoO4、Na2TeO3KCl and CuCl2The amount ratio of the substances is 6:1:3 to 5: 3.
4. The method for preparing a 3D structural compound formed by Anderson type polyacid and transition metal copper according to claim 1, wherein the HCl solution is 2 mol/L.
5. The application of the 3D structure compound formed by the Anderson polyacid and the transition metal copper is characterized in that the 3D structure compound formed by the Anderson polyacid and the transition metal copper is particularly applied to selective catalytic oxidation of thioether compounds.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114653405A (en) * 2022-04-20 2022-06-24 许昌学院 Vase-like polyacid-based three-dimensional metal organic framework material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114653405A (en) * 2022-04-20 2022-06-24 许昌学院 Vase-like polyacid-based three-dimensional metal organic framework material and preparation method and application thereof
CN114653405B (en) * 2022-04-20 2024-03-08 许昌学院 Vase-like polyacid-based three-dimensional metal organic framework material and preparation method and application thereof

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Application publication date: 20220208