CN109942017B - Sulfide highly uniform microspheres with accurately controllable particle size and preparation method thereof - Google Patents

Sulfide highly uniform microspheres with accurately controllable particle size and preparation method thereof Download PDF

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CN109942017B
CN109942017B CN201910365130.8A CN201910365130A CN109942017B CN 109942017 B CN109942017 B CN 109942017B CN 201910365130 A CN201910365130 A CN 201910365130A CN 109942017 B CN109942017 B CN 109942017B
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microspheres
sulfide
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metal salt
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CN109942017A (en
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武素丽
吴越
常杰
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Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C01G11/02—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G13/00—Compounds of mercury
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/21—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/11—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/08—Sulfides

Abstract

The invention discloses a sulfide highly uniform microsphere with accurately controllable particle size and a preparation method thereof. The method is based on the idea of a core-shell structure and comprises two processes of primary growth to form a core and secondary layer-layer growth. Obtaining sulfide nano-microspheres with stable particle sizes through stable reaction conditions in the first-step growth; in the subsequent steps, the timing and the amount of the metal salt and the sulfur source are controlled, so that the particle size of the nano-microspheres can be accurately controlled. According to the synthesis method, the test steps can be accurately designed through the preset target grain size, so that the sulfide nano-microspheres with the target grain size can be obtained; meanwhile, the adjustable particle size range of the method is obviously enlarged and can be adjusted to be 100nm-1000 nm.

Description

Sulfide highly uniform microspheres with accurately controllable particle size and preparation method thereof
Technical Field
The invention relates to a sulfide highly uniform microsphere with accurately controllable particle size and a preparation method thereof, belonging to the field of preparation of photonic crystal materials.
Background
Semiconductor materials are widely used in the fields of solar cells, lasers, photocatalysis, etc., wherein various metal sulfides are the main species of the semiconductor materials, such as ZnS, CdS, CuS, PbS, SnS, HgS, MnS, FeS, NiS, CoS, etc. Further research finds that the semiconductor material with the micro-nano size level shows a plurality of unique physical and chemical phenomena, such as quantum effect, nonlinear optical effect and the like. These phenomena are mainly determined by the size, shape and structure of the material. The monodisperse microspheres eliminate the influence of the shape on the properties of the material, and the controllable particle size of the microspheres can further study the influence of the size of the material on the properties. Therefore, the preparation of the monodisperse metal sulfide microsphere with the accurately controllable particle size has important significance for further research of semiconductor materials.
In the current research on synthesizing sulfide microspheres, the particle size of the synthesized microspheres can be controlled by various factors, for example, the reaction time (see X.Wang, Z.Wang, &lTtTtranslation = L "&gTtL &lTt/T &gTt. Bai, H.Wang, &lTtTtranslation = L" &gTtL &lTt/T &gTt &. Kang, D.H.Werner, M.Xu, B. L i, J. L i and X-F.Yu, Opt.express,2018,26,27001. 27013.), the reaction temperature (see M.G.Han, C.G.shin, S. -J.Jeon, H.Shim, C.J.Heo, H.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.H.Shim, C.H.H.J.J.Heo, H.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.J.EP, S.J.J.J.EP, S.J.J.J.J.EP, S.J.EP, S.No. 3, S.10.
Disclosure of Invention
The invention aims to provide a sulfide highly uniform microsphere with accurately controllable particle size and a preparation method thereof. A preparation method of sulfide highly uniform microspheres with accurately controllable particle size is based on the idea of a core-shell structure and comprises two processes of primary growth to form a core and secondary layer-layer growth, and sulfide nano microspheres with stable particle size are obtained through stable reaction conditions in the first step of growth; in the subsequent steps, the timing and the amount of the metal salt and the sulfur source are controlled, so that the particle size of the nano-microspheres can be accurately controlled. According to the synthesis method, the test steps can be accurately designed through the preset target grain size, so that the sulfide nano-microspheres with the target grain size can be obtained; meanwhile, the adjustable particle size range of the method is obviously enlarged, the adjustable particle size range is 100nm-1000nm, the particle size of the microsphere is highly uniform and is of a polycrystalline structure, and the particle size distribution coefficient is less than 5%.
The invention is realized by the following process steps:
1) according to the concentration of (0.25-1.25) mmol/L, a certain amount of polyvinylpyrrolidone (average molecular weight: 10000-;
2) according to the concentration of (0.1-0.3) mol/L, adding a certain amount of sulfur source into the aqueous solution of polyvinylpyrrolidone heated to a stable temperature, and adding a certain amount of concentrated nitric acid into the solution;
3) according to M2+(M2+＝Zn2+、Cd2+、Pb2+、Cu2+、Sn2+、Hg2+、Mn2+、Fe2+、Ni2+Or Co2+)：S2-Taking a certain amount of metal salt, dispersing the metal salt into deionized water with a certain volume in advance, adding a metal salt aqueous solution into the solution, and stirring for 0.5-5min according to the molar ratio of (0.5-1.5) to 3;
4) adjusting the stirring speed to be lower, and stirring and reacting for 1-5h in a water bath at 50-80 ℃ according to the amount of the added metal salt;
5) according to M2+：S2-Adding a certain amount of zinc source pre-dispersed in deionized water into the system obtained in the step 4) according to the molar ratio of (0.5-1.5) to 3, and reacting for 1-5 hours according to the amount of the added metal source;
6) repeating the step 5) until M is added into the system2+：S2-In a molar ratio of 1: 1;
7) adding a certain amount of sulfur source into a reaction system according to the concentration of (0.1-0.3) mol/L;
8) repeating the step of 5-7) for 0-10 times, and stopping the reaction when the particle size of the microspheres reaches 100-1000 nm;
9) the obtained sulfide nano-microspheres are washed by water for three times or more, centrifuged, dried and ground to obtain the solid sulfide nano-microspheres.
Further, in the scheme, the concentration of the concentrated nitric acid in the step 2) is 0.011-0.044 mol/L.
Further, in the above scheme, the stirring speed in the step 3) is 1000-1200 rpm.
Further, in the above scheme, the stirring speed in the step 4) is 300-500 rpm.
In the above scheme, the sulfur source used comprises thiourea, thioacetamide and ammonium sulfide, preferably, the sulfur source used is thioacetamide; the metal salt includes inorganic salts of zinc such as nitrate, acetate, sulfate, etc., and preferably, the metal salt is hydrated nitrate.
Advantageous effects of the invention
The invention discloses a sulfide highly uniform microsphere with accurately controllable particle size and a preparation method thereof. According to the synthesis method, the sulfide nano-microspheres with target particle sizes can be obtained by accurately designing test steps through preset target particle sizes; meanwhile, the adjustable particle size range of the method is obviously enlarged and can be adjusted to be 100nm-1000 nm. The microsphere has uniform grain size, is of a polycrystalline structure, and has a grain size distribution coefficient of less than 5 percent.
Drawings
FIG. 1 is an X-ray diffraction pattern of ZnS microspheres obtained in example 1;
FIG. 2(a, b) is a transmission electron micrograph at different magnifications of ZnS microspheres obtained in example 1; (c) is a high-resolution transmission electron microscope picture; (d) is a SAED graph;
FIG. 3 is a scanning electron micrograph of ZnS microspheres obtained in example 1;
FIG. 4 is a graph showing the particle size distribution of ZnS microspheres obtained in example 1;
FIG. 5 is a scanning electron micrograph of ZnS microspheres obtained in example 2;
FIG. 6 is a scanning electron micrograph of ZnS microspheres obtained in example 3.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available or may be prepared by conventional methods.
Example 1
The method comprises the steps of preparing monodisperse ZnS nano microspheres with the particle size of 235 +/-5 nm by a multi-step growth method for accurately regulating and controlling the particle size, and constructing the three-dimensional photonic crystal by utilizing the ZnS nano microspheres with the particle size. The preparation method comprises the following steps:
1) weighing 3.00g of polyvinylpyrrolidone and 100m L deionized water, fully dissolving the polyvinylpyrrolidone in the deionized water to obtain a uniform solution, stirring and heating to 75 ℃, weighing 2.25g of thioacetamide, adding the thioacetamide to a reaction system, weighing 0.07m L concentrated nitric acid, adding the concentrated nitric acid to the reaction system, weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, quickly adding the zinc nitrate hexahydrate to the reaction system, stirring vigorously at the speed of 1000rpm for 3min, reducing the stirring speed to 500rpm, and stirring and reacting for 2h at the temperature of 75 ℃;
2) weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, then quickly adding the zinc nitrate hexahydrate into a three-neck flask, stirring in a water bath for reaction for 2 hours, weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, then quickly adding the zinc nitrate hexahydrate into the three-neck flask, stirring in a water bath for reaction for 2 hours, weighing 2.25g of thioacetamide, adding the thioacetamide into the three-neck flask, stirring magnetically for 30 minutes, weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, then quickly adding the zinc nitrate into the three-neck flask, stirring in;
3) repeating the step 2) twice;
4) centrifuging the reaction system while the reaction system is hot, washing for 3 times, drying and grinding to obtain solid ZnS nano microspheres;
XRD test is carried out on the obtained monodisperse ZnS nano microsphere, the crystal structure of the ZnS nano microsphere is analyzed, as shown in figure 1, the diffraction peak position and the relative intensity of the obtained product are consistent with the standard cubic phase ZnS atlas, and the standard card is JCPDSNO.05-0566. In addition, other impurity peaks do not exist in the figure, and the fact that the product has high crystalline phase purity is proved.
Observing the transmission electron microscope image in FIG. 2, it can be found that the prepared microspheres have good spherical morphology and uniform particle size. In addition, the orientations of the lattice stripes in the microspheres are different, and the concentric ring patterns are obtained by selective electron diffraction, and the results show that the prepared ZnS microspheres are of polycrystalline structures. The lattice fringe spacing measured in an HR-TEM image obtained by a high-resolution transmission electron microscope is about 0.315nm and is matched with a (111) plane in cubic phase ZnS, and the product is proved to be the cubic phase ZnS. In addition, the ZnS nano microsphere obtained by multi-step growth is proved to be uniform in the interior and not to have a layered structure.
The scanning electron microscope image of fig. 3 shows that the prepared microspheres have excellent monodispersity, the particle size distribution data of the finished microspheres are shown in fig. 4, and the particle size distribution coefficient is calculated to be less than 5%, and the particle size distribution is narrow.
Example 2
The method comprises the steps of preparing monodisperse ZnS nano microspheres with the particle size of 150 +/-5 nm by a multi-step growth method for accurately regulating and controlling the particle size, and constructing the three-dimensional photonic crystal by utilizing the ZnS nano microspheres with the particle size. The preparation method comprises the following steps:
1) weighing 3.00g of polyvinylpyrrolidone and 100m L deionized water, fully dissolving the polyvinylpyrrolidone in the deionized water to obtain a uniform solution, stirring and heating to 75 ℃, weighing 2.25g of thioacetamide, adding the thioacetamide to a reaction system, weighing 0.07m L concentrated nitric acid, adding the concentrated nitric acid to the reaction system, weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, quickly adding the zinc nitrate hexahydrate to the reaction system, stirring vigorously at the speed of 1000rpm for 3min, reducing the stirring speed to 500rpm, and stirring and reacting for 2h at the temperature of 75 ℃;
2) weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, then quickly adding the zinc nitrate hexahydrate into a three-neck flask, and stirring in a water bath for reacting for 2 hours;
3) centrifuging the reaction system while the reaction system is hot, washing for 3 times, drying and grinding to obtain solid ZnS nano microspheres;
by the characterization of a scanning electron microscope and the statistics of particle size distribution, the particle size distribution coefficient is calculated to be less than 4%, and the particle size distribution is narrow.
Example 3
The ZnS nano microsphere with the monodisperse particle size of 1000 +/-5 nm is prepared by a multi-step growth method for accurately regulating and controlling the particle size. The preparation method comprises the following steps:
1) weighing 3.00g of polyvinylpyrrolidone and 100m L deionized water, fully dissolving the polyvinylpyrrolidone in the deionized water to obtain a uniform solution, stirring and heating to 75 ℃, weighing 2.25g of thioacetamide, adding the thioacetamide to the reaction system, weighing 0.07m L concentrated nitric acid, adding the concentrated nitric acid to the reaction system, weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, quickly adding the zinc nitrate hexahydrate to the reaction system, stirring vigorously at the speed of 1000rpm for 3min, reducing the stirring speed to 500rpm, and stirring and reacting for 2h at the temperature of 75 ℃;
2) weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, then quickly adding the zinc nitrate hexahydrate into a three-neck flask, stirring in a water bath for reaction for 2 hours, weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, then quickly adding the zinc nitrate hexahydrate into the three-neck flask, stirring in a water bath for reaction for 2 hours, weighing 2.25g of thioacetamide, adding the thioacetamide into the three-neck flask, stirring magnetically for 30 minutes, weighing 2.97g of zinc nitrate hexahydrate, dissolving the zinc nitrate hexahydrate in 5m L deionized water in advance, then quickly adding the zinc nitrate into the three-neck flask, stirring in;
3) repeating the step 2) for ten times;
4) centrifuging the reaction system while the reaction system is hot, washing for 3 times, drying and grinding to obtain solid ZnS nano microspheres;
by the characterization of a scanning electron microscope and the statistics of particle size distribution, the particle size distribution coefficient is calculated to be less than 5%, and the particle size distribution is narrow.
Examples 4 to 6
The metal salts used in example 1 were replaced with copper nitrate trihydrate, lead nitrate, and cadmium nitrate tetrahydrate, and the molar weights of the corresponding compounds were unchanged, so that CuS microspheres having a particle size of about 240nm and a particle size distribution coefficient of less than 3%, PbS microspheres having a particle size distribution coefficient of less than 3% of about 210nm, and CdS microspheres having a particle size distribution coefficient of less than 2% of about 250nm were prepared.
Examples 7 to 9
The metal salts used in example 2 were replaced with copper nitrate trihydrate, lead nitrate, and cadmium nitrate tetrahydrate, and the molar weights of the corresponding materials were unchanged, so that CuS microspheres having a particle size of about 140nm and a particle size distribution coefficient of less than 3%, PbS microspheres having a particle size distribution coefficient of less than 3% of about 140nm, and CdS microspheres having a particle size distribution coefficient of less than 2% of about 150nm were prepared, respectively.
Examples 10 to 18
The metal salts used in example 3 were replaced with copper nitrate trihydrate, lead nitrate, cadmium nitrate tetrahydrate, stannous chloride, mercury acetate, manganese acetate, ferrous sulfate, nickel sulfate, and cobalt nitrate, and the corresponding molar amounts were weighed unchanged, thus CuS microspheres, PbS microspheres, SnS microspheres, HgS microspheres, MnS microspheres, FeS microspheres, NiS microspheres, and CoS microspheres, and CoS microspheres, all having particle size distribution coefficients of less than 5%, were prepared, respectively, with particle sizes of about 970nm, about 950nm, about 1010nm, about 960nm, and about 1000 nm.
Examples 19 to 21
In example 1, the mass of polyvinylpyrrolidone obtained in step 1 is replaced by 1.00g, 2.00g and 3.00g, so as to prepare ZnS microspheres with particle diameters of about 160nm, 240nm and 230nm respectively, and the particle diameter distribution coefficients of the ZnS microspheres are less than 3%.
Examples 22 to 24
In example 1, the mass of thioacetamide taken in step 3 is replaced by 1.00g, 2.00g and 5.00g respectively, so that ZnS microspheres with particle sizes of about 220nm, 260nm and 180nm can be prepared respectively, and the particle size distribution coefficients are all less than 3%.
Examples 25 to 27
In example 1, the volumes of the concentrated nitric acid obtained in step 4 are respectively replaced by 0.05m L, 0.10m L and 0.20m L, so that ZnS microspheres with particle sizes of about 230nm, 250nm and 190nm can be respectively prepared, and the particle size distribution coefficients of the ZnS microspheres are all less than 4%.
Examples 28 to 30
In example 1, the mass of zinc nitrate hexahydrate obtained in step 5 is replaced by 1.19g, 2.38g and 4.16g respectively, so that ZnS microspheres with particle sizes of 230nm, 250nm and 210nm can be prepared respectively, and the particle size distribution coefficients of the ZnS microspheres are less than 4%.
Examples 31 to 33
In example 1, the vigorous stirring time in step 5 is replaced by 0.5min, 1.5min and 5min, so as to prepare ZnS microspheres with particle sizes of 230nm, 280nm and 170nm respectively, wherein the particle size distribution coefficients are all less than 4%. Examples 34 to 36
In example 1, the reaction temperature was replaced by 60 ℃, 70 ℃ and 80 ℃ respectively, so as to prepare ZnS microspheres having particle diameters of 270nm, 260nm and 220nm respectively, wherein the particle diameter distribution coefficients thereof are less than 5%.

Claims (6)

1. A preparation method of sulfide highly uniform microspheres with accurately controllable particle sizes is characterized by comprising the following process steps:
1) according to the concentration of 0.25-1.25 mmol/L, polyvinylpyrrolidone with the average molecular weight of 10000-58000 is dispersed in deionized water to obtain a uniform solution, and the uniform solution is stirred and heated to 50-80 ℃;
2) adding a sulfur source with the concentration of 0.1-0.3 mol/L into the solution in the step 1), and then adding concentrated nitric acid into the solution;
3) according to M2+：S2-0.5-1.5: 3, said M2+Is Zn2+、Cd2+、Pb2+、Cu2+、Sn2+、Hg2+、Mn2+、Fe2 +、Ni2+Or Co2+Taking metal salt, dispersing the metal salt into deionized water in advance, then adding a metal salt aqueous solution into the solution obtained in the step 2), and stirring for 0.5-5 min;
4) the stirring speed is reduced, and the reaction is carried out for 1 to 5 hours in a water bath at the temperature of between 50 and 80 ℃;
5) according to M2+：S2-0.5-1.5: 3, adding metal salt pre-dispersed in deionized water into the system obtained in the step 4), and reacting for 1-5 h;
6) repeating the step 5) until M is added into the system2+：S2-In a molar ratio of 1: 1;
7) adding a sulfur source with the concentration of 0.1-0.3 mol/L into the reaction system in the step 6);
8) repeating the steps 5) -7) for 0-10 times, and stopping the reaction when the particle size of the microspheres reaches 100-1000 nm;
9) the obtained sulfide nano-microspheres are washed by water for three times or more, centrifuged, dried and ground to obtain the solid sulfide nano-microspheres.
2. The method for preparing the highly uniform sulfide microspheres with precisely controlled particle diameters according to claim 1, wherein the concentration of the concentrated nitric acid in the step 2) is 0.011-0.044 mol/L.
3. The method for preparing highly uniform sulfide microspheres with precisely controlled particle sizes as claimed in claim 1, wherein the stirring speed in step 3) is 1000-1200 rpm.
4. The method for preparing highly uniform sulfide microspheres with precisely controlled particle sizes as claimed in claim 1, wherein the stirring speed in step 4) is 300-500 rpm.
5. The method for preparing highly uniform sulfide microspheres with precisely controlled particle sizes according to claim 1, wherein the sulfur source is thiourea, thioacetamide or ammonium sulfide.
6. The method for preparing highly uniform sulfide microspheres with precisely controlled particle sizes according to claim 1, wherein the metal salt is nitrate, acetate, nitrate hydrate or sulfate.
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CN109942017B (en) * 2019-04-30 2020-07-14 大连理工大学 Sulfide highly uniform microspheres with accurately controllable particle size and preparation method thereof
CN110467225A (en) * 2019-09-03 2019-11-19 大连理工大学 A kind of preparation method of the hollow sandwich microballoon of monodisperse cobalt sulfide
CN112158880B (en) * 2020-08-28 2022-12-13 昆明理工大学 Preparation method of beta-mercuric sulfide nano particles
CN112194172B (en) * 2020-10-21 2022-01-04 中国科学院南京土壤研究所 Method for rapidly preparing spherical mercury sulfide nanoparticles
CN114835154B (en) * 2022-03-31 2024-01-26 宁波大学 Preparation method of monodisperse ZnS colloidal microspheres with adjustable particle size

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