CN1191193C - Synthesis of nano hollow balls of zinc selenide - Google Patents
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- CN1191193C CN1191193C CNB031002838A CN03100283A CN1191193C CN 1191193 C CN1191193 C CN 1191193C CN B031002838 A CNB031002838 A CN B031002838A CN 03100283 A CN03100283 A CN 03100283A CN 1191193 C CN1191193 C CN 1191193C
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Abstract
The present invention relates to a method for synthesizing a micrometer level zinc selenide hollow ball, which relates to preparation technology of synthesis of the micrometer level zinc selenide hollow ball and inner adulteration and surface coating thereof. The present invention is characterized in that under the condition of strong basicity, zincic acid radical ions and selenious acid or soluble selenite are used as raw material, and hydrazine hydrate is used as a reducing agent; in a sealed reactor, the raw material generates thermal reduction reaction in the temperature condition of 100 DEG C to 200 DEG C to synthesize the micrometer level zinc selenide hollow ball. If other kinds of metal ions are adulterated in a reaction system, a composite type zinc selenide micrometer hollow ball can be formed. A hollow ball is used as a core to carry out surface coating processing; thus, a coated zinc selenide hollow ball can be made. The present invention has the advantages of easy obtainment of the raw material, simple equipment, easy control, good technologic repeatability, stable product quality and safe and reliable operation; the present invention provides structural units which are necessary to assembly of functional material, such as photonic crystals. The present invention can be applied in fields of biological marks, fluorescence, electronics, etc.
Description
Technical Field
The invention relates to a synthesis method of micron-sized ZnSe hollow spheres and a process method for internal doping (comprising manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead and bismuth) and surface coating (comprising oxides, sulfides and selenides of manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead and bismuth) of the micron-sized ZnSe hollow spheres, and belongs to the technical field of preparation processes of inorganic materials.
Background
Zinc selenide is an important semiconductor material, has special optical and electrical properties, and has wide application in the fields of blue lasers, solar cells and the like. At present, the traditional synthesis method and the method reported by the literature can not synthesize the ZnSe hollow sphere with the micron order, so that the ZnSe hollow sphere can not be further assembled into structural materials such as photonic crystals and the like, and the application of the zinc selenide is limited. For example, the Netherlands, Material Chemistry and Physics, 1999, 60, 99, reported the synthesis of zinc selenide in the form of particles by the reaction of elemental selenium and elemental zinc in alkaline solution; british chemical communications, 2000, 14, 1243, page 14, reports the synthesis of nanoparticles of zinc selenide from organometallic compounds of zinc as precursors; U.S. Chemistry of Materials (2001), volume 13, page 913, also reports a method for synthesizing monodisperse zinc selenide nanoparticles using zinc organometallic compounds as precursors, which is expensive in raw Materials and complex in operation. Other methods are that nano particles of zinc selenide are synthesized in a micro emulsion system through reverse micelle, a film of zinc selenide grows by a molecular beam epitaxy method, but micron hollow spheres of zinc selenide cannot be synthesized.
Disclosure of Invention
The invention aims to provide a synthesis method of micron-sized zinc selenide hollow spheres and a process method for internal doping and surface coating of the micron-sized zinc selenide hollow spheres. The method is simple to operate, and can synthesize micron-scale zinc selenide (ZnSe) hollow spheres and a plurality of zinc selenide hollow spheres internally doped and surface-coated by using the same or basically the same process and adopting cheap and easily-obtained raw materials under the conditions of lower temperature and pressure, thereby providing a required series of structural units for the assembly of structural materials such as photonic crystals and the like.
The technical scheme provided by the invention is as follows:
a method for synthesizing micron-sized zinc selenide hollow spheres is characterized in that zincate ions are used as a zinc source, and selenious acid or soluble selenite is used as a selenium source, and the method comprises the following operation steps:
(1) dissolving a certain amount of metal zinc soluble salt in a sodium hydroxide, potassium hydroxide, ammonia water or lithium hydroxide aqueous solution with the molar weight of the metal zinc soluble salt being 1-10 times excessive to prepare a clear aqueous solution so as to form zincate ions;
(2) and (2) mixing selenious acid or soluble selenite and hydrazine hydrate reducing agent which is excessive by 1-10 times of the molar weight of zincate ions with the clear solution prepared in the step (1) according to the stoichiometric ratio of the zincate ions, putting the mixture into a closed reactor, and carrying out hydrothermal reduction reaction for 2-48 hours at the temperature of 100-200 ℃ to synthesize the micron-sized zinc selenide hollow spheres.
The metal zinc soluble salt in the invention adopts any one of zinc nitrate, zinc sulfate, zinc chloride or zinc acetate. The soluble selenite adopts sodium selenite or ammonium selenite.
The hydrazine hydrate reducing agent in the invention can be replaced by any one of sodium borohydride, potassium borohydride, hydroxylamine or hydrazine sulfate.
The invention also provides a method for synthesizing the composite micron-sized zinc selenide hollow spheres, which is characterized in that zincate ions are used as a zinc source, and selenious acid or soluble selenite is used as a selenium source, and the method comprises the following operation steps:
(1) dissolving a certain amount of metal zinc soluble salt in a sodium hydroxide, potassium hydroxide, ammonia water or lithium hydroxide aqueous solution with the molar weight of the metal zinc soluble salt being 1-10 times excessive to prepare a clear aqueous solution so as to form zincate ions;
(2) then adding a certain amount of one or more other kinds of metal soluble salts into the reaction system, and fully and uniformly stirring; wherein: the metal is manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead and bismuth;
(3) and (2) mixing selenious acid or soluble selenite and hydrazine hydrate reducing agent with the molar excess of 1-10 times of zincate ions according to the stoichiometric ratio of the zincate ions with the clear solution prepared in the step (1), putting the mixture into a closed reactor, and carrying out hydrothermal reduction reaction for 2-48 hours at the temperature of 100-200 ℃ to synthesize the composite micron-sized zinc selenide hollow spheres.
The invention also provides a method for coating selenide micron-sized zinc selenide hollow spheres, which is characterized in that zincate ions are used as a zinc source, and selenious acid or soluble selenite is used as a selenium source, and the method comprises the following operation steps:
(1) dissolving a certain amount of metal zinc soluble salt in a sodium hydroxide, potassium hydroxide, ammonia water or lithium hydroxide aqueous solution with the molar weight of the metal zinc soluble salt being 1-10 times excessive to prepare a clear aqueous solution so as to form zincate ions;
(2) according to the stoichiometric ratio of zincate ions, selenious acid or soluble selenite and hydrazine hydrate reducing agent which is excessive by 1-10 times of the molar weight of the zincate ions are mixed with the clear solution prepared in the step (1), the mixture is placed into a closed reactor, and hydrothermal reduction reaction is carried out for 2-48 hours at the temperature of 100-200 ℃, so that micron-sized zinc selenide hollow spheres can be synthesized;
(3) putting a certain amount of zinc selenide micron hollow spheres in water or ethylenediamine, stirring to form a suspension, adding soluble salt of another metal, then adding a selenium source with the same mole as the soluble salt of the metal, and finally adding a hydrazine hydrate reducing agent with the excess of 1-10 times of the mole of the selenium sourceto prepare a mixed solution, wherein: the selenium source is elemental selenium, selenious acid, sodium selenite or ammonium selenite; the other metal is manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead or bismuth;
(4) and (3) putting the mixed solution into a closed reactor, and carrying out reduction reaction for 2-48 hours at the temperature of 100-200 ℃ to synthesize the micron-sized zinc selenide hollow spheres coated with the selenide on the surfaces.
The invention also provides a method for coating the oxide or sulfide micron-sized zinc selenide hollow spheres, which is characterized in that zincate ions are used as a zinc source, and selenious acid or soluble selenite is used as a selenium source, and the method comprises the following operation steps:
(1) dissolving a certain amount of metal zinc soluble salt in a sodium hydroxide, potassium hydroxide, ammonia water or lithium hydroxide aqueous solution with the molar weight of the metal zinc soluble salt being 1-10 times excessive to prepare a clear aqueous solution so as to form zincate ions;
(2) according to the stoichiometric ratio of zincate ions, selenious acid or soluble selenite and hydrazine hydrate reducing agent which is excessive by 1-10 times of the molar weight of the zincate ions are mixed with the clear aqueous solution prepared in the step (1), the mixture is placed into a closed reactor, and hydrothermal reduction reaction is carried out for 2-48 hours at the temperature of 100-200 ℃, so that micron-sized zinc selenide hollow spheres can be synthesized;
(3) putting a certain amount of zinc selenide micron hollow spheres in water or ethylenediamine, stirring to form a suspension, adding soluble salt of another metal, and then adding an oxygen source or a sulfur source with the same mole as the soluble salt of the metal to prepare a mixedsolution, wherein: the oxygen source is sodium hydroxide, potassium hydroxide or lithium hydroxide; the sulfur source is element sulfur, thiourea, sodium sulfide and ammonium sulfide, and the other metal is manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead or bismuth;
(4) and (3) putting the mixed solution into a closed reactor, and carrying out reduction reaction for 2-48 hours at the temperature of 100-200 ℃ to synthesize the micron-sized zinc selenide hollow spheres coated with oxides and sulfides on the surfaces.
Compared with the prior art, the invention has the following advantages and beneficial effects: the invention reports a method for synthesizing micron-scale zinc selenide hollow spheres for the first time, and solves the problems of high temperature, virulent raw materials, complex process and the like in the conventional method for synthesizing the zinc selenide semiconductor material; the synthesis method has the advantages of low reaction temperature, simple equipment, cheap and easily-obtained raw materials, easy realization of control, good process repeatability, stable product quality and safe and reliable operation; through internal doping and surface coating treatment, a large number of zinc selenide micron hollow spheres with various composite and coating structures can be synthesized.
Drawings
FIG. 1 is a powder X-ray diffraction diagram of micron level hollow spheres of zinc selenide prepared at a series of different reaction temperatures.
FIG. 2 is a scanning electron micrograph of a ZnSe hollow microsphere prepared at 100 ℃.
FIG. 3 is a scanning electron micrograph of hollow spheres of ZnSe micro spheres prepared at 180 ℃.
Fig. 4 is a scanning electron microscope photograph of the zinc selenide hollow microspheres prepared at the temperature of 100 ℃ after grinding, which shows that the zinc selenide hollow microspheres are hollow structures, and the inner picture is a partially enlarged zinc selenide hollow microsphere wall.
FIG. 5 is a scanning electron microscope photograph of a Ni-doped composite ZnSe hollow microsphere with Zn: Ni of 100: 10 prepared at 160 ℃.
Fig. 6 is a scanning electron microscope photograph of the surface-coated copper selenide micron hollow sphere prepared at the temperature of 180 ℃.
Detailed Description
Under the condition of strong alkalinity, zincate ions are used as a zinc source, selenious acid or soluble selenite is used as a selenium source, micron-sized ZnSe hollow spheres are synthesized in an aqueous solution, and internal doping and surface coating of the hollow spheres can be realized through different pre-treatment and post-treatment means, and the reaction mechanism and the embodiment of the invention are further explained in detail below.
The micron-sized ZnSe hollow sphere is synthesized by taking zincate ions as a zinc source and selenious acid or soluble selenite as a selenium source through a reduction reaction under a strong alkaline condition.
The reaction can be expressed as:
secondly, under the condition of strong alkalinity, taking zincate ions as a zinc source and selenious acid or soluble selenite as a selenium source, adding soluble salts of other types of metals (including manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead and bismuth) before reaction, and synthesizing the composite zinc selenide micron hollow sphere through reduction reaction.
The reaction can be expressed as:
under the condition of strong alkalinity, zincate ions are used as a zinc source, selenious acid or soluble selenite is used as a selenium source, soluble salts of other metals (including manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead and bismuth) and oxygen sources (including sodium hydroxide, potassium hydroxide and lithium hydroxide), sulfur sources (including elemental sulfur, thiourea, sodium sulfide and ammonium sulfide) or selenium sources (including elemental selenium, selenious acid, sodium selenite and ammonium selenite) are added after the formation of the zinc selenide hollow spheres, and the zinc selenide hollow spheres with surfaces coated with oxides, sulfides or selenides can be respectively synthesized through reaction.
The reaction can be expressed as:
SeO in the above formulae3 2-Is selenious acid or soluble selenite (such as sodium selenite, ammonium selenite), reducing agent is hydrazine hydrate or sodium borohydride, potassium borohydride, hydroxylamine or hydrazine sulfate, and M2+Represents soluble salts (nitrates, sulfates or chlorides) of divalent metals such as manganese, cobalt, nickel, copper, cadmium, tin, lead, M3+Represents a soluble salt (nitrate, sulphate or chloride) of the trivalent metal iron, antimony or bismuth.
The invention will be further understood by reference to the following examples.
Example 1:
0.002 molar analytically pure ZnSO was weighed4·7H2And (3) placing O into a 40 ml reaction kettle, adding 20 ml of 1M NaOH solution for dissolving, adding equimolar sodium selenite and hydrazine hydrate with the molar excess of 1 time into the reaction kettle, adding deionized water to 70% of the total volume, sealing the reaction kettle, and reacting for 2 hours at 100 ℃. Then cooling to room temperature, opening the reaction kettle, performing suction filtration by using a cloth type funnel, and washing by using deionized water to obtain yellow powder. The product was identified as zinc selenide by X-ray powder diffraction and as micron-sized spheres of zinc selenide by scanning electron microscopy, approximately 3 microns in diameter (fig. 2). After being ground, the zinc selenide spheres were identified by a scanning electron microscope, and as a result, the spheres were found to have a hollow structure (fig. 4).
Under the same condition, hydrazine hydrate is replaced by sodium borohydride, potassium borohydride, hydroxylamine or hydrazine sulfate with the molar weight excess of 5 times, the reaction temperature is controlled at 100, 150 and 200 ℃, the reaction time is adjusted to 48, 32, 16, 8 and 4 hours, and the micron-sized zinc selenide hollow spheres can be obtained.
Example 2:
0.003 molar of analytically pure ZnCl is weighed2Placing the mixture into a 40 ml reaction kettle, adding 20 ml of 2M NaOH solution for dissolving, and adding AgNO3In the ratio of Zn to Ag being 100 to 5Example to the solution, with ZnCl2And 1/2 times AgNO3Ammonium selenite with the sum of molar weight and hydrazine sulfate with the excess of 2 times are added, deionized water is added till the total volume is 70 percent, the reaction kettle is sealed, and the reaction is carried out for 4 hours at 120 ℃, so that the Ag doped composite type zinc selenide micron hollow sphere with Zn and Ag of 100: 5 can be prepared.
Under the same condition, hydrazine hydrate is changed into sodium borohydride, potassium borohydride, hydroxylamine or hydrazine sulfate, the reaction temperature is controlled at 100, 150 and 200 ℃, the reaction time is adjusted to 48, 32, 16, 8 and 2 hours, and the micron-sized Ag doped zinc selenide hollow spheres can be obtained.
Example 3:
0.002 molar analytically pure Zn (NO) was weighed3)2Placing the mixture into a 40 ml reaction kettle, adding 20 ml of 1M KOH solution for dissolving, and adding MnSO4Adding Zn and Ni into the solution at a ratio of 100: 10, and adding Zn (NO)3)2And NiSO4Selenious acid with the sum of molar weight and sodium borohydride with the excess of 4 times, finally adding deionized water to 70 percent of the total volume, sealing the reaction kettle,reacting at 160 deg.C for 32 hr to obtain Ni-doped composite ZnSe hollow micron spheres (FIG. 5) with Zn/Ni ratio of 100: 10.
Under the same condition, the hydrazine hydrate is changed into sodium borohydride, potassium borohydride, hydroxylamine or hydrazine sulfate, the reaction temperature is controlled at 100, 140 and 200 ℃, the reaction time is adjusted to 48, 32, 16, 8 and 4 hours, and the micron-sized Ni-doped zinc selenide hollow spheres can be obtained.
Example 4:
weighing 0.001 mol analytically pure ZnSO4·7H2O is put into a 40 ml reaction kettle, 20 ml of 0.5M LiOH solution is added for dissolution, and BiCl is added3Adding the mixture into the solution according to the proportion of Zn to Bi of 100 to 15, and adding the mixture and ZnSO4·7H2O and 3/2 times of BiCl3Selenious acid with the sum of molar weight and hydroxylamine with the excess of 4 times are added, finally deionized water is added to 70 percent of the total volume, the reaction kettle is sealed, and the reaction is carried out for 16 hours at 180 ℃, so as to prepare the Bi doped composite zinc selenide micron hollow sphere with Zn and Bi of 100: 15.
Under the same condition, hydrazine hydrate is changed into sodium borohydride, potassium borohydride, hydroxylamine or hydrazine sulfate, the reaction temperature is controlled at 100, 160 and 200 ℃, the reaction time is adjusted to 48, 32, 16, 8 and 4 hours, and the micron-sized Bi doped zinc selenide hollow spheres can be obtained.
Example 5:
and (3) putting 0.01 mol of the zinc selenide micron hollow sphere obtained by the method I in a 40 ml reaction kettle, adding 20 ml of 0.1M silver nitrate solution and 20 ml of 0.1M sodium hydroxide solution, sealing the reaction kettle, and reacting for 8 hours at 100 ℃. And opening the reaction kettle, performing suction filtration by using a distributed funnel, and washing by using deionized water to prepare the zinc selenide micron hollow sphere with the surface coated with the silver oxide.
Example 6:
and (3) putting 0.02 mol of the zinc selenide micron hollow sphere obtained by the method I in a 40 ml reaction kettle, adding 0.002 mol of analytically pure cadmium nitrate and 0.002 mol of analytically pure sulfur powder, adding 40 ml of analytically pure ethylenediamine, sealing the reaction kettle, and reacting at 120 ℃ for 12 hours. And opening the reaction kettle, performing suction filtration by using a distributed funnel, and washing by using deionized water to prepare the zinc selenide micron hollow sphere with the surface coated with the cadmium sulfide.
Example 7:
0.015 mol of the zinc selenide micron hollow sphere obtained by the method of the first embodiment is placed in a 40 ml reaction kettle, 0.003 mol of analytically pure copper sulfate and 0.003 mol of analytically pure sodium selenite are added, 10 ml of water and 0.01 mol of hydroxylamine are added, the reaction kettle is sealed, and the reaction is carried out for 24 hours at 180 ℃. And opening the reaction kettle, performing suction filtration by using a distributed funnel, and washing by using deionized water to prepare the zinc selenide micron hollow sphere with the surface coated with copper selenide. (FIG. 6)
Claims (7)
1. A method for synthesizing micron-sized zinc selenide hollow spheres is characterized in that zincate ions are used as a zinc source, and selenious acid or soluble selenite is used as a selenium source, and the method comprises the following operation steps:
(1) dissolving a certain amount of metal zinc soluble salt in a sodium hydroxide, potassium hydroxide, ammonia water or lithium hydroxide aqueous solution with the molar weight of the metal zinc soluble salt being 1-10 times excessive to prepare a clear aqueous solution so as to form zincate ions;
(2) and (2) mixing selenious acid or soluble selenite and hydrazine hydrate reducing agent which is excessive by 1-10 times of the molar weight of zincate ions with the clear solution prepared in the step (1) according to the stoichiometric ratio of the zincate ions, putting the mixture into a closed reactor, and carrying out hydrothermal reduction reaction for 2-48 hours at the temperature of 100-200 ℃ to synthesize the micron-sized zinc selenide hollow spheres.
2. The method for synthesizing the zinc selenide hollow sphere according to claim 1, which is characterized in that: the metal zinc soluble salt is any one of zinc nitrate, zinc sulfate, zinc chloride or zinc acetate.
3. The method for synthesizing the zinc selenide hollow sphere according to claim 1, which is characterized in that: the soluble selenite in the step (2) is sodium selenite or ammonium selenite.
4. The method for synthesizing the zinc selenide hollow sphere according to claim 1, which is characterized in that: and (3) replacing the hydrazine hydrate reducing agent in the step (2) with any one of sodium borohydride, potassium borohydride, hydroxylamine or hydrazine sulfate.
5. A synthetic method of composite micron-sized zinc selenide hollow spheres is characterized in that zincate ions are used as a zinc source, and selenious acid or soluble selenite is used as a selenium source, and the method comprises the following operation steps:
(1) dissolving a certain amount of metal zinc soluble salt in a sodium hydroxide, potassium hydroxide, ammonia water or lithium hydroxide aqueous solution with the molar weight excess of 1-10 times to prepare a clear aqueous solution so as to form zincate ions;
(2) adding a certain amount of one or more other kinds of metal soluble salts into the reaction system, and fully and uniformly stirring; wherein: the metal is manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead or bismuth;
(3) and (2) mixing selenious acid or soluble selenite and hydrazine hydrate reducing agent with the molar excess of 1-10 times of zincate ions with the clear solution prepared in the step (1) according to the stoichiometric ratio of the zincate ions, putting the mixture into a closed reactor, and carrying out hydrothermal reduction reaction for 2-48 hours at the temperature of 100-200 ℃ to synthesize the composite micron-sized zinc selenide hollow spheres.
6. A method for coating selenide micron-sized zinc selenide hollow spheres is characterized in that zincate ions are used as a zinc source, and selenious acid or soluble selenite is used as a selenium source, and the method comprises the following operation steps:
(1) dissolving a certain amount of metal zinc soluble salt in a sodium hydroxide, potassium hydroxide, ammonia water or lithium hydroxide aqueous solution with the molar weight excess of 1-10 times to prepare a clear aqueous solution so as to form zincate ions;
(2) mixing selenious acid or soluble selenite and hydrazine hydrate reducing agent with the molar excess of 1-10 times of zincate ions in the stoichiometric ratio of zincate ions with the clear solution prepared in the step (1), putting the mixture into a closed reactor, and carrying out hydrothermal reduction reaction for 2-48 hoursat the temperature of 100-200 ℃ to synthesize micron-sized zinc selenide hollow spheres;
(3) putting a certain amount of zinc selenide micron hollow spheres in water or ethylenediamine, stirring to form a suspension, adding soluble salts of manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead or bismuth, then adding a selenium source with the same mole as the soluble salts of the metals, and finally adding a hydrazine hydrate reducing agent with the excess of 1-10 times of the mole of the selenium source to prepare a mixed solution, wherein: the selenium source is elemental selenium, selenious acid, sodium selenite or ammonium selenite:
(4) and (3) putting the mixed solution into a closed reactor, and carrying out reduction reaction for 2-48 hours at the temperature of 100-200 ℃ to synthesize the micron-sized zinc selenide hollow spheres coated with the selenide on the surfaces.
7. A method for coating oxide or sulfide micron-sized zinc selenide hollow spheres is characterized in that zincate ions are used as a zinc source, and selenious acid or soluble selenite is used as a selenium source, and the method comprises the following operation steps:
(1) dissolving a certain amount of metal zinc soluble salt in a sodium hydroxide, potassium hydroxide, ammonia water or lithium hydroxide aqueous solution with the molar weight of the metal zinc soluble salt being 1-10 times excessive to prepare a clear aqueous solution so as to form zincate ions;
(2) according to the stoichiometric ratio of zincate ions, selenious acid or soluble selenite and hydrazine hydrate reducing agent with the molar excess of 1-10 times of the zincate ions are mixed with the clear solution prepared in the step (1), the mixture is placed into a closed reactor, and hydrothermalreduction reaction is carried out for 2-48 hours at the temperature of 100-200 ℃, so as to synthesize micron-sized zinc selenide hollow spheres;
(3) putting a certain amount of zinc selenide micron-sized hollow spheres into water or ethylenediamine, stirring to form a suspension, adding soluble salts of manganese, iron, cobalt, nickel, copper, silver, cadmium, tin, antimony, lead or bismuth metal, and then adding an oxygen source or a sulfur source which is equimolar with the soluble salts of the metal to prepare a mixed solution, wherein: the oxygen source is sodium hydroxide, potassium hydroxide or lithium hydroxide; the sulfur source is elemental sulfur, thiourea, sodium sulfide and ammonium sulfide;
(4) and (3) putting the mixed solution into a closed reactor, and carrying out reduction reaction for 2-48 hours at the temperature of 100-200 ℃ to synthesize the micron-sized zinc selenide hollow spheres coated with oxides or sulfides on the surfaces.
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| CN1305803C (en) * | 2005-05-13 | 2007-03-21 | 中国科学院上海硅酸盐研究所 | Prepn process of hollow zinc oxide balls with zinc powder as material |
| CN100344531C (en) * | 2005-10-19 | 2007-10-24 | 清华大学 | Process of preparing monodisperse nanometer semiconductor selenide particle |
| CN101025416B (en) * | 2007-01-04 | 2011-11-23 | 山东师范大学 | Luminescent zinc selenide nano rod synthesizing method and its use |
| CN102897723A (en) * | 2012-08-29 | 2013-01-30 | 江苏大学 | Hydrothermal method for preparing selenium-copper-based nano-crystals |
| CN103084583B (en) * | 2013-01-17 | 2014-09-10 | 东南大学 | Method for preparing compound of zinc oxides and silver nano |
| CN103159189A (en) * | 2013-04-03 | 2013-06-19 | 南京理工大学 | Synthesis method of ZnSe hollow microspheres by alcohol thermal reduction |
| CN106057480B (en) * | 2016-08-11 | 2018-06-01 | 浙江大学 | Three-dimensional porous selenides nanocomposite for ultracapacitor and preparation method thereof |
| CN107452951B (en) * | 2017-08-11 | 2019-11-26 | 青岛九环新越新能源科技股份有限公司 | XS2@YSe2The preparation method of the anode material of lithium-ion battery of core-shell structure |
| CN109778339A (en) * | 2017-11-13 | 2019-05-21 | 太极石股份有限公司 | A kind of method for producing yarn covered with antibacterial and anti-dye |
| CN107917993B (en) * | 2017-12-11 | 2020-07-17 | 品粹新材料科技(南京)有限公司 | Vehicle-mounted gas detection device |
| CN110133764B (en) * | 2018-02-08 | 2020-08-21 | 天津大学 | Preparation method of zinc selenide nano hollow sphere double-layer graded-refractive-index antireflection film |
| CN109650353A (en) * | 2019-01-14 | 2019-04-19 | 成都中建材光电材料有限公司 | A kind of preparation method of high-purity selenium disulfide |
| CN111604064A (en) * | 2020-05-12 | 2020-09-01 | 河南大学 | Pollution-free hydrothermal synthesis method of zinc selenide microspheres and synthesis method of composite material thereof |
| CN114506824B (en) * | 2021-12-02 | 2023-09-05 | 佛山市铁人环保科技有限公司 | Zinc selenide sol and preparation method and application thereof |
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