CN115710016A - Surface-vulcanized metal compound composite material MS @ MX and preparation method thereof - Google Patents
Surface-vulcanized metal compound composite material MS @ MX and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a surface-vulcanized metal compound composite material MS @ MX and a preparation method thereof, and relates to the technical field of material preparation. The method comprises the steps of mixing a reduced glutathione solution containing sulfur groups at a certain concentration and a metal compound MX with a certain mass, carrying out hydrothermal reaction, forming vulcanized MS on the surface of the metal compound MX, and preparing an MS @ MX composite material, wherein M in the metal compound MX and the vulcanized MS is a metal cation. The invention utilizes the complexation of the reduced glutathione and the metal cations to connect the sulfur groups in the reduced glutathione with the metal cations, so that the sulfur groups react with the surfaces of various metal compounds MX in a hydrothermal reaction to form an MS shell, a preparation method with strong universality and simple preparation process is obtained, and the preparation difficulty of preparing the metal compound composite material is reduced.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a surface-vulcanized metal compound composite material MS @ MX and a preparation method thereof.
Background
In the field of material preparation, people research the properties of single-component metal compounds such as Bi2Te3, pbTe and Sb2Te3, so that a lot of work is done in the aspects of wide thermoelectric field, optical field, magnetic field and the like, such as doping, surface modification and the like, and the strategies can change the energy band structure and morphological characteristics of the material to a certain extent, thereby changing the properties of the material such as electricity, optics and the like. However, electrons and holes of a single-component material are easy to recombine, and the properties of light, electricity and the like cannot be further improved due to rapid recombination. In countless studies, it has been found that the selection of the material components of the core and shell of the composite material by proper design can adjust the band gap arrangement and limit the potential, and the electrical and optical properties can be significantly changed due to the tunability of the band structure and the effective separation and transportation of electron holes, so that the composite material is one of the most effective strategies for balancing the harsh conditions and achieving the improvement of the material properties.
The preparation of a plurality of composite materials needs a plurality of chemical substances, most of the composite materials need various high molecular polymers, have various functional groups, multilayer precursors and the like, the complicated preparation process is complicated, and the preparation method of the metal compound composite material is difficult to be applied to the preparation process of other metal compound composite materials in a template way. Therefore, it is very important to find a preparation method of universal composite materials to simply and quickly improve the material performance.
Disclosure of Invention
The invention aims to provide a surface-vulcanized metal compound composite material MS @ MX and a preparation method thereof, and aims to solve the problem that a preparation method of a universal metal compound composite material is lacked in the prior art.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a surface sulfuration metal compound composite material MS @ MX and a preparation method thereof are disclosed. Reduced glutathione containing a sulfur group forms a complex with one or more metal cations, and the formed complex is positioned on the surface of the metal compound MX. And the sulfur group is connected with the corresponding metal cation after the complex is formed, and the sulfur group reacts with the surface of the metal compound in the hydrothermal reaction to form the shell material of the MS. Therefore, after a complex is formed on the surface of the metal compound MX, a metal compound composite material with the MS as a shell and the MX as an inner core is prepared.
LGTA refers to reduced glutathione containing a sulfur group, which is complexed with a metal cation to form a complex such that the sulfur group is linked together by the LGTA and the metal compound. Therefore, when hydrothermal reaction is carried out, the sulfur group reacts with the metal compound to form MS.
By adopting the method, the corresponding metal compound composite material can be prepared by adopting various metals, and the problem of complicated preparation procedures when different metals are required to prepare the corresponding metal compound composite material is solved. And the process can be applied to a variety of metal cations capable of complexing with LGTA. By the method, the band gap arrangement and the limiting potential of various metal compounds can be selectively adjusted, so that the properties of the core-shell structure, such as electricity, optics and the like, can be changed. Different metal compounds can generate different core-shell structures, and the core-shell structures with different properties can be widely applied to the thermoelectric field, the electrocatalysis field, the optical field, the magnetic field and the like. Therefore, the technical scheme of the invention has the characteristic of strong universality, and various metal compounds can be processed by a modularized preparation method, so that the corresponding composite material is prepared.
X in MX is an element in the VI main group of the periodic table of elements. And X is taken as an anion in the metal compound, so that the element Se and/or the element Te are selected as the X. In the metal compound MX for hydrothermal reaction, X may be only Se element or only Te element, or both Se element and Te element may be possessed. The Se element and the Te element are connected with the metal cation through covalent bonds or ionic bonds.
M in the metal compound MX is one or more metal cations. Such as cations of the Bi element or Pb element.
In the mixing process before the hydrothermal reaction, a certain amount of reduced glutathione solution, a certain amount of metal compound MX and a certain amount of deionized water are fully stirred and mixed, and the metal compound MX is usually insoluble in water, so the metal compound MX is in a powder shape. After fully mixing and stirring, transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction. The purpose of adding deionized water is two, one is to dissolve reduced glutathione so that it can form a complex with a metal compound, and the other is to evaporate high pressure in the hydrothermal reaction to accelerate the reaction efficiency. Because the hydrothermal reaction is carried out in the closed reaction kettle, part of deionized water is vaporized when the reaction kettle is heated, the pressure in the reaction kettle is increased, and the effect of accelerating the reaction speed is achieved.
The reaction temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is more than 3 h. After the hydrothermal reaction is completed, the prepared metal compound composite material is mixed in a solution. Therefore, after the hydrothermal reaction is finished and the subsequent treatment is carried out, the metal compound composite material MS @ MX can be obtained.
Under the condition of no metal compound, the method also comprises a preparation step of a metal compound MX, wherein the metal compound MX is obtained by grinding the simple substance M and the simple substance X in an oxygen-isolated environment, and the powdery composite heterostructure material taking the metal compound MX as a matrix is subjected to hydrothermal reaction with a reduced glutathione solution. The purpose of isolating oxygen is to avoid the material waste caused by the reaction between the simple substance M and the simple substance X and the oxygen in the milling process. That is, the composite heterostructure material mixed with the reduced glutathione solution and the deionized water is actually a powder-like composite heterostructure material with the metal compound MX as a matrix. And the metal compound MX reacts with the reduced glutathione in the hydrothermal reaction.
And after the hydrothermal reaction is finished, a centrifugation step is further included, a first intermediate product is obtained after the hydrothermal reaction is finished, the first intermediate product is taken out, and a solution part is removed in a centrifugation mode, so that a second intermediate product is obtained. The first intermediate product comprises byproducts of reduced glutathione decomposition and anions replaced by S in the hydrothermal reaction, and the impurities are all in solution, so the impurities are removed by centrifuging to remove the solution. Reduced glutathione is decomposed in a high-temperature environment, and by-products such as hydrogen sulfide are decomposed.
Because the elements replaced by S exist in the solution in an ion form in the hydrothermal reaction process, no solid impurities exist in the solution, and the impurities can be removed by removing the solution in a centrifugal mode. And because no solid impurities exist, the metal compound composite material prepared by the method has the characteristic of high purity, and the requirement of separating and removing the solid impurities is not needed, so that the preparation process of the method is simpler and quicker.
After the impurities are removed, a washing step is further included, the second intermediate product is repeatedly washed by adopting absolute ethyl alcohol and/or deionized water, and the washed precipitate is taken as a third intermediate product. The purpose of the repeated washing with absolute ethanol and/or deionized water is to clean the second intermediate product from residual impurities.
And drying, namely drying the third intermediate product for more than 24 hours at 60 ℃ to obtain the MS @ MX composite material.
The structure of the composite material is MS @ MX, in the structure, MS is a shell material formed by chemical combination reaction of a sulfur group and a metal cation, and MX is a core material of the composite material.
The invention has the following beneficial effects:
the invention utilizes the complexation of the reduced glutathione and the metal cations to connect the sulfur groups in the reduced glutathione with the metal cations, so that the sulfur groups react with the surfaces of various metal compounds MX in a hydrothermal reaction to form a shell of MS, a preparation method with strong universality and simple preparation process is obtained, and the preparation difficulty of preparing the metal compound composite material is reduced.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray detection diagram according to a first embodiment of the present invention;
FIG. 2 is an X-ray detection diagram of a second embodiment of the present invention.
Detailed Description
The technical solution of the present invention is clearly and completely described below with reference to the accompanying drawings by way of specific implementation manners of the embodiments of the present invention.
The invention relates to a surface-vulcanized metal compound composite material MS @ MX and a preparation method thereof. The metal compound reacts with the sulfur group on the glutathione, so that an MS shell is formed on the surface of the metal compound MX, and the composite material MS @ MX is finally prepared.
In the composite material ms @ mx, M refers to one or more metal cations; x is single Se element anion, single Te element anion or anion containing Se element and Te element; s in MS denotes a sulfur group.
The following examples are given to illustrate the technical solutions of the present invention. In the following examples, LGTA is referred to as reduced glutathione.
Example one
Preparing a metal compound matrix:
the proportion of the materials is Bi: te: se = 2: 2.7: 0.3, and the proportion is a molar ratio, namely an atomic ratio.
The preparation method is high-energy ball milling. Specifically, the raw materials are elementary substances of Bi, te and Se, and the purity is not lower than 99.99%. The ball mill is a SPEX 8000M type. In an argon-protected glove box, raw materials prepared according to the chemical formula and stainless steel grinding balls are put into a stainless steel ball grinding tank matched with the ball mill according to the mass ratio of 1.
Preparing a composite heterostructure material taking a metal compound as a matrix:
Bi 2 S 3 @Bi 2 Te 2.7 Se 0.3 the heterostructure powders are obtained by hydrothermal treatment.
Specifically, 1gBi after ball milling 2 Te 2.7 Se 0.3 The powder and 0.2g of LGTA were added to 20mL of deionized water and mixed thoroughly. Placing the mixture into a polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 24h, washing the final product with deionized water and absolute ethyl alcohol for a plurality of times under centrifugation, finally drying the precipitated powder at 60 ℃ for 24 hours, and repeatedly collecting the powder for a plurality of times to obtain Bi 2 S 3 @Bi 2 Te 2.7 Se 0.3 A composite heterostructure powder material.
The hydrothermal reaction can adopt a polytetrafluoroethylene reaction kettle with the volume of 50 ml.
Experimental test analysis:
detection of Bi after hydrothermal treatment Using X-ray 2 S 3 @Bi 2 Te 2.7 Se 0.3 Crystal structure of core-shell heterostructure powder material samples. As shown in FIG. 1, the comparison using standard card PDF #75-1306 shows that the sample after hydrothermal reaction has bismuth sulfide peak, and the coexistence of two-phase peak shows that Bi is successfully obtained after hydrothermal reaction 2 S 3 @Bi 2 Te 2.7 Se 0.3 A composite heterostructure powder material.
Example two
Preparing a metal compound matrix:
the ratio of Pb to Se =1.1:1, the proportion is a molar ratio, namely an atomic ratio.
The preparation method is high-energy ball milling. Specifically, the raw materials are simple substances of Pb and Se, and the purity is not lower than 99.99%. The ball mill is a SPEX 8000M type. In an argon-protected glove box, raw materials prepared according to the chemical formula and stainless steel grinding balls are put into a stainless steel ball grinding tank matched with the ball mill according to the mass ratio of 1.
Preparing a composite heterostructure material taking a metal compound as a matrix:
PbS@Pb 1.1 the Se composite heterostructure powder is obtained by hydrothermal treatment.
Specifically, 1gPb after ball milling is treated 1.1 Se powder and 0.2g of LGTA were added to 20mL of deionized water and mixed well. Placing in a polytetrafluoroethylene reaction kettle, reacting at 180 deg.C for 24 hr, washing the final product with deionized water and anhydrous ethanol under centrifugation for several times, drying the precipitated powder at 60 deg.C for 24 hr, and collecting repeatedly for several times to obtain PbS @ Pb 1.1 Se composite heterostructure powder material.
Experimental test analysis:
detection of PbS @ Pb after hydrothermal reaction Using X-ray 1.1 Crystal structure of Se composite heterostructure powder material samples. As shown in FIG. 2, comparison using standard card PDF #99-0053 shows that significant Pb is present in the hydrothermal reaction sample 1.1 The coexistence of two-phase peaks of Se and PbS shows that PbS @ Pb is successfully obtained after hydrothermal synthesis 1.1 Se composite heterostructure powder material.
In the two embodiments, the raw material simple substance is processed by ball milling to prepare the composite heterostructure material. In the ball milling process, the elementary substances of the raw materials are subjected to combination reaction to form a metal compound MX. When the metal compound MX is prepared, the proportion of various elements is strictly controlled, so that the metal compound MX can not remain after complete reaction.
The purpose of selecting simple substances as raw materials is to facilitate the calculation of the proportion of each element in the raw materials. Therefore, the compound can be selected as a raw material in the preparation process.
Ball milling is one way of preparing the metal compound MX in an oxygen-free environment, and one skilled in the art can also prepare the metal compound MX by all possible methods, such as solid phase sintering, arc melting, chemical synthesis, etc.
In summary, the embodiments of the present invention provide a class of composite materials prepared by vulcanizing ms @ mx on the surface of a metal compound, and a preparation method thereof.
It should be noted that the metal compound composite material and the composite material mentioned in the technical solution of the present invention are both ms @ mx (X = Se, te) composite materials.
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A preparation method of a surface-vulcanized metal compound composite material MS @ MX is characterized by comprising the following steps: mixing a reduced glutathione solution containing sulfur groups with a certain concentration and a metal compound MX with a certain mass, carrying out hydrothermal reaction, forming vulcanized MS on the surface of the metal compound MX, and preparing an MS @ MX composite material, wherein M in the metal compound MX and the vulcanized MS is a metal cation.
2. The method for preparing the surface-vulcanized metal compound composite material MS @ MX according to claim 1, characterized in that: x in MX is anion of Se element and/or Te element.
3. The method for preparing the surface-sulfurized metal compound composite material MS @ MX as claimed in claim 1, wherein: the metal cation is one metal element or a combination of multiple metal elements.
4. The method for preparing the surface-vulcanized metal compound composite material MS @ MX according to claim 1, characterized in that: deionized water is also added when the reduced glutathione is mixed with the metal compound MX.
5. The method for preparing the surface-sulfurized metal compound composite material MS @ MX as claimed in claim 1, wherein: the reaction temperature of the hydrothermal reaction is 100-180 ℃, and the reaction time is more than 3 h.
6. The method for preparing the surface-sulfurized metal compound composite material MS @ MX as claimed in claim 1, wherein: the preparation method further comprises a step of preparing a metal compound MX, wherein the simple substance M and the simple substance X are ground in an oxygen-isolated environment to obtain a powdery composite heterostructure material taking the metal compound MX as a matrix, and the powdery composite heterostructure material is subjected to hydrothermal reaction with a reduced glutathione solution.
7. The method for preparing the surface-vulcanized metal compound composite material MS @ MX according to claim 5, characterized in that: and the method also comprises a centrifugation step, wherein after the hydrothermal reaction is finished, a first intermediate product is obtained, the first intermediate product is taken out, and a solution part is removed by adopting a centrifugation mode, so that a second intermediate product is obtained.
8. The method for preparing the surface-sulfurized metal compound composite material MS @ MX as claimed in claim 7, wherein: and a washing step, namely repeatedly washing the second intermediate product by adopting absolute ethyl alcohol and/or deionized water, and taking the washed precipitate as a third intermediate product.
9. The method for preparing the surface-sulfurized metal compound composite material MS @ MX according to claim 8, wherein: and further comprising a drying step, namely drying the third intermediate product for more than 24 hours at the temperature of 60 ℃ to obtain the MS @ MX composite material.
10. A surface vulcanization metal compound composite material MS @ MX is characterized in that: the composite material is prepared by the preparation method of any one of claims 1 to 9, the structure of the composite material is MS @ MX, the MS in the structure is a shell material formed by chemical combination reaction of a sulfur group and a metal cation, and the MX is a core material of the composite material.
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| US20080226917A1 (en) * | 2007-02-20 | 2008-09-18 | Research Foundation Of State University Of New York | Core-shell nanoparticles with multiple cores and a method for fabricating them |
| CN102127446A (en) * | 2011-01-13 | 2011-07-20 | 武汉大学 | Aqueous phase preparation method of ZnSe/ZnS core-shell structure quantum dots |
| US20160178596A1 (en) * | 2014-12-22 | 2016-06-23 | Industrial Technology Research Institute | Probe and method for detecting metal ions and chemical/biochemical molecules |
| CN107055587A (en) * | 2017-06-02 | 2017-08-18 | 南京工程学院 | A kind of preparation method of the nano composite sulfide of core shell structure |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080226917A1 (en) * | 2007-02-20 | 2008-09-18 | Research Foundation Of State University Of New York | Core-shell nanoparticles with multiple cores and a method for fabricating them |
| CN102127446A (en) * | 2011-01-13 | 2011-07-20 | 武汉大学 | Aqueous phase preparation method of ZnSe/ZnS core-shell structure quantum dots |
| US20160178596A1 (en) * | 2014-12-22 | 2016-06-23 | Industrial Technology Research Institute | Probe and method for detecting metal ions and chemical/biochemical molecules |
| CN107055587A (en) * | 2017-06-02 | 2017-08-18 | 南京工程学院 | A kind of preparation method of the nano composite sulfide of core shell structure |
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