CN113956493A - Non-alkyl tin oxide cluster compound and synthesis method and application thereof - Google Patents
Non-alkyl tin oxide cluster compound and synthesis method and application thereof Download PDFInfo
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- CN113956493A CN113956493A CN202010701021.1A CN202010701021A CN113956493A CN 113956493 A CN113956493 A CN 113956493A CN 202010701021 A CN202010701021 A CN 202010701021A CN 113956493 A CN113956493 A CN 113956493A
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Abstract
The invention provides a non-alkyl tin-oxygen cluster and a synthesis method and application thereof, wherein the molecular formula of the tin-oxygen cluster is C48H56Cl12N32O20Sn14(excluding free molecules) Mr 3488.30; the tin-oxygen cluster compound is a pure-phase crystalline substance; the crystal system of the crystalline substance of the tin-oxygen cluster compound is a tetragonal crystal system, the space group is P-421c, and the unit cell parameter a is
b is
c is
Alpha is 90 degrees, beta is 90 degrees, gamma is 90 degrees, and V is
The synthesis method of the cluster compound has the advantages of simple process, easy repetition, low raw material price and convenient production. The non-alkyl tin oxide prepared by the invention has better stability and electrocatalytic carbon dioxide reduction performance, and can be better applied to the fields of environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of crystal material preparation, and particularly relates to a non-alkyl tin oxide cluster compound and a synthesis method and application thereof.
Background
Tin oxide (SnO)2) As an important component of metal oxide materials, it has been widely used in the fields of transparent electrodes, gas sensors, solar cells, and the like. Recently, much research has been devoted to the development of SnO2Radical CO2Reduction of the electrocatalyst will help to achieve an economically and environmentally meaningful carbon neutral energy cycle. In principle, tin-oxo clusters (TOCs) with precise interface structure can be used for CO on molecular level2The reduction mechanism is experimentally and theoretically understood. Tin Oxide Clusters (TOCs) as SnO2The accurate atomic model not only can provide opportunities for mechanism research, but also can expand potential application thereof through structural modulation. However, most of the TOCs reported so far belong to alkyl organotin complexes, are toxic to the human body, and pose serious environmental problems. In addition, because the synthesis reaction directly adopts an organic tin source, and the Sn-C bond is relatively stable, the terminal coordination sites are difficult to obtain by breaking the Sn-C bond, and the tin-oxygen cluster is difficult to modify by introducing additional functional organic ligands. Therefore, it is necessary to develop a new synthesis strategy to synthesize a low-toxicity tin-oxygen cluster compound with relatively high efficiency and stable electrocatalytic carbon dioxide reduction effect, and introduce an inorganic tin source and a functional ligand to obtain the tin-oxygen cluster compound with a higher cluster core and a richer structure.
Disclosure of Invention
In order to achieve the purpose, the invention provides a non-alkyl tin-oxygen cluster compound, a synthesis method and application thereof, wherein the tin-oxygen cluster compound has relatively high efficiency and stable capability of electrocatalytic carbon dioxide reduction, and the method is simple and efficient, has less pollution to the synthesis process, and meets the requirements of environmental protection.
In a first aspect of the invention, there is provided a non-alkyl tin oxygen cluster having the formula C48H56Cl12N32O20Sn14(excluding free molecules) Mr 3488.30; space group is P-421c, cell parameter a is
b is
c is
Alpha is 90 degrees, beta is 90 degrees, gamma is 90 degrees, and V is
The tin-oxygen cluster is a pure-phase crystalline substance, specifically a colorless strip-shaped crystalline substance, and the crystalline system of the crystalline substance of the tin-oxygen cluster is a tetragonal system. The tin-oxygen cluster is a non-alkyl tin-oxygen cluster.
According to an embodiment of the invention, the crystalline state of tin-oxygen clusters has a cluster core size of about 7.00 to 7.2, e.g. about 7.04, 7.12.
According to an embodiment of the present invention, the crystalline state of the tin-oxygen cluster has a symmetrical structure.
According to an embodiment of the present invention, the crystal parameters of the crystalline state of the tin-oxygen cluster are shown in table 1:
TABLE 1
In a second aspect of the present invention, there is provided a method for synthesizing a non-alkyl tin oxide cluster compound, the method comprising the steps of: and mixing tin salt and nitrogen heterocyclic ligand, and carrying out solvothermal reaction to obtain the tin-oxygen cluster compound.
According to an embodiment of the invention, the method comprises in particular the steps of:
1) uniformly mixing tin salt and nitrogen heterocyclic ligand, and heating to perform solvothermal reaction to obtain a mixture;
2) separating the mixture obtained after the reaction in the step 1), cleaning the obtained solid phase with alcohol, and drying to prepare the stannoxy cluster compound.
According to an embodiment of the present invention, the tin salt is a simple inorganic compound, and the tin salt may be one or more combinations of tin tetrachloride pentahydrate, stannous chloride dihydrate and tin sulfate, preferably tin tetrachloride pentahydrate.
According to an embodiment of the present invention, the azacyclic ligand may be one or more of pyrazole, imidazole, pyrazine, piperazine, benzimidazole, etc.; pyrazole is preferred.
According to an embodiment of the invention, the molar ratio of the tin salt to the nitrogen heterocycle is 1 (15-33).
According to the embodiment of the invention, the temperature of the solvothermal reaction is 40-160 ℃; preferably 60 to 100 deg.C, such as 80 deg.C. If the reaction temperature is too low, the reaction time is long and the crystal size is small.
According to the invention, the solvothermal reaction time is 24-240 hours; preferably 48 to 150 hours, such as 72 hours and 120 hours.
As a preferred embodiment of the present invention, the reaction may be carried out at 100 ℃ for 72 hours or 96 hours.
The tin-oxygen cluster compound of the first aspect is prepared by the method, and the yield of the tin-oxygen cluster compound prepared by the preparation method can reach more than 20% by taking Sn as a reference.
In a third aspect, the invention provides a use of the above tin oxygen cluster compound, which can be used in electrocatalytic carbon dioxide reduction.
The invention has the beneficial effects that:
(1) the invention provides a novel class of materials, namely non-alkyl tin oxide clusters, which are symmetrical structures and have dimensions of about
The tin-oxygen cluster compound has relatively high-efficiency and stable electrocatalytic carbon dioxide reduction effect.
(2) The invention also provides a brand new method for preparing the tin-oxygen cluster compound, which utilizes a solvothermal synthesis method to simply mix reaction raw materials and obtain the tin-oxygen cluster compound through one-step self-assembly reaction. The method has the advantages of simple synthesis requirement, low requirement on the purity of raw materials, easy acquisition of the raw materials and low price, all the used raw materials can be purchased with chemically pure reagents, no further purification is needed, and the yield reaches more than 20 percent by taking Sn as a reference. In addition, the post-treatment of the method is simple and feasible, and a pure-phase crystalline product can be obtained only by simple alcohol washing separation and room-temperature air drying; moreover, the method has less pollution and meets the requirement of green environmental protection.
Drawings
FIG. 1 is a schematic representation of the crystal structure of the crystalline product prepared in example 1;
FIG. 2 is an X-ray powder diffraction pattern of the crystalline product prepared in example 1, each line from bottom to top representing a simulated powder diffraction pattern, the powder diffraction pattern of crystals placed in air, respectively;
FIG. 3 is an infrared spectrum of a crystalline product prepared in example 1;
FIG. 4 is a product photograph of the crystalline product prepared in example 1;
FIG. 5 is a schematic representation of the crystal structure of the crystalline product prepared in example 2;
FIG. 6 is an X-ray powder diffraction pattern of the crystalline product prepared in example 2, each line from bottom to top representing a simulated powder diffraction pattern, the powder diffraction pattern of the crystals in air;
FIG. 7 is an infrared spectrum of a crystalline product prepared in example 2;
fig. 8 is a product photograph of the crystalline product prepared in example 2.
Detailed Description
The compounds of the general formula and the preparation and use thereof according to the present invention will be described in further detail with reference to the following examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The single crystal structure analysis of the present invention uses a supernova single crystal diffractometer in japan.
X-ray powder diffraction pattern the radiation source used was Cu-K alpha radiation.
Example 1
A synthetic method of a non-alkyl tin oxide cluster compound comprises the following specific steps:
putting tin tetrachloride pentahydrate (1.0mmol) and pyrazole (29.38mmol) into a 20ml glass bottle, uniformly mixing at room temperature, keeping the temperature in an oven at 100 ℃ for 4 days, taking out, naturally cooling to room temperature, separating out a solid phase, and washing with ethanol to obtain a colorless strip-shaped crystalline target product, wherein the yield is 25% by taking Sn as a reference.
Example 2
Tin tetrachloride pentahydrate (1.0mmol), pyrazole (29.38mmol) and imidazole (2.94mmol) are placed in a 20ml glass bottle, mixed uniformly at room temperature, kept at the constant temperature of a 100 ℃ oven for 2 days, taken out, naturally cooled to room temperature, separated out and washed by ethanol to obtain a colorless block-shaped crystalline target product, wherein the yield is 47% by taking Sn as a reference.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A non-alkyl tin oxygen cluster, wherein the molecular formula of the tin oxygen cluster is C48H56Cl12N32O20Sn14(excluding free molecules) Mr 3488.30; space group is P-421c, cell parameter a is
b is
c is
Alpha is 90 degrees, beta is 90 degrees, gamma is 90 degrees, and V is
2. The non-alkyl tin oxygen cluster of claim 1, wherein the crystalline state of the tin oxygen cluster is tetragonal.
3. The non-alkyl tin oxide cluster of claim 1, wherein the crystalline form of the tin oxide cluster has a cluster core size of
Left and right.
4. The non-alkyl tin oxide cluster of claim 1, wherein the crystalline form of the tin oxide cluster has a symmetrical structure.
5. A method of synthesizing a non-alkyl tin oxide cluster compound as claimed in any one of claims 1 to 4, wherein the method comprises the steps of: and mixing tin salt and nitrogen heterocyclic ligand, and carrying out solvothermal reaction to obtain the tin-oxygen cluster compound.
6. The synthetic method according to claim 5, comprising the steps of:
1) uniformly mixing tin salt and nitrogen heterocyclic ligand, and heating to perform solvothermal reaction to obtain a mixture;
2) separating the mixture obtained after the reaction in the step 1), cleaning the obtained solid phase with alcohol, and drying to prepare the stannoxy cluster compound.
7. The synthesis method according to claim 5, wherein the tin salt can be one or more of tin tetrachloride pentahydrate, stannous chloride dihydrate and tin sulfate, preferably tin tetrachloride pentahydrate;
the nitrogen heterocyclic ligand can be one or more of pyrazole, imidazole, pyrazine, piperazine, benzimidazole and the like; pyrazole is preferred.
8. The synthesis method of claim 5, wherein the molar ratio of the tin salt to the nitrogen heterocycle is 1 (15-33);
the temperature of the solvothermal reaction is 40-160 ℃; preferably 60-100 ℃, and more preferably 80 ℃;
the solvothermal reaction time is 24-240 hours; preferably 48 to 150 hours, more preferably 72 hours or 120 hours.
9. Use of a non-alkyl tin oxide cluster compound according to any one of claims 1 to 4 in electrocatalytic carbon dioxide reduction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114736236A (en) * | 2022-03-21 | 2022-07-12 | 中国科学院福建物质结构研究所 | Polynuclear cyclic organotin-oxygen-sulfur cluster compound and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613123A (en) * | 2013-12-13 | 2014-03-05 | 青岛大学 | Method for preparing monodisperse stannic oxide nanocrystalline particles |
| CN108342749A (en) * | 2018-02-01 | 2018-07-31 | 太原理工大学 | A kind of modified SnO2The preparation method and applications of electrode restore CO in photoelectrocatalysis2Formic acid processed |
| CN108715458A (en) * | 2018-06-20 | 2018-10-30 | 西安工程大学 | A kind of preparation method of nanoscale glass putty |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613123A (en) * | 2013-12-13 | 2014-03-05 | 青岛大学 | Method for preparing monodisperse stannic oxide nanocrystalline particles |
| CN108342749A (en) * | 2018-02-01 | 2018-07-31 | 太原理工大学 | A kind of modified SnO2The preparation method and applications of electrode restore CO in photoelectrocatalysis2Formic acid processed |
| CN108715458A (en) * | 2018-06-20 | 2018-10-30 | 西安工程大学 | A kind of preparation method of nanoscale glass putty |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736236A (en) * | 2022-03-21 | 2022-07-12 | 中国科学院福建物质结构研究所 | Polynuclear cyclic organotin-oxygen-sulfur cluster compound and preparation method and application thereof |
| CN114736236B (en) * | 2022-03-21 | 2023-09-29 | 中国科学院福建物质结构研究所 | Polynuclear annular organotin oxygen sulfur cluster compound and preparation method and application thereof |
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