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US-12623916-B2 - β-type zinc sulfide and preparation method therefor

US12623916B2US 12623916 B2US12623916 B2US 12623916B2US-12623916-B2

Abstract

Disclosed are β-type zinc sulfide and a preparation method therefor. The method includes: adding an oil phase containing styrene monomers into a water phase containing a pore-forming agent, a surfactant, a Zn salt, a complexing agent, a sulfur source and a water-soluble initiator, conducting mixing and emulsification, introducing metal elements, dissolving polystyrene of microspheres prepared through reaction in tetrahydrofuran, and then conducting calcination, pickling and activation to obtain the β-type zinc sulfide. The zinc sulfide microspheres prepared by the present invention are β-type, and have excellent photoelectric properties and broad application prospects.

Inventors

  • Lin Ze-Peng
  • Lin Hua-Xiong
  • Lin Jun

Assignees

  • GUANGDONG XINDA ADVANCED MATERIALS TECHNOLOGY CO., LTD

Dates

Publication Date
20260512
Application Date
20230419
Priority Date
20220225

Claims (8)

  1. 1 . A preparation method for β-type zinc sulfide, comprising the following steps: S1, dissolving styrene monomers in an organic solvent, so as to obtain an oil phase; S2, dissolving a pore-forming agent, a surfactant, a Zn salt, a complexing agent, a sulfur source and a water-soluble initiator in water, so as to obtain a water phase, wherein the pore-forming agent is a composite pore-forming agent, the composite pore-forming agent comprises a macropore-forming agent and a mesopore-forming agent, the macropore-forming agent is selected from at least one of polyoxyethylene sorbitan fatty acid ester, polyethylene glycol octyl phenyl ether, and polyoxyethylene sorbitan fatty acid ester, and the mesopore-forming agent is cetyltrimethyl ammonium bromide (CTAB); S3, adding the oil phase into the water phase, conducting mixing and emulsification, adjusting a pH value to 8-9, introducing metal elements, heating to 50° C.-70° C., stirring and conducting reaction for 2 h-5 h, and conducting centrifugation and washing, so as to obtain porous ZnS/PS nanospheres, wherein the metal elements are selected from at least one of nickel, lanthanum, cerium, cobalt, titanium, palladium, iridium, platinum, molybdenum, and strontium, and wherein the total amount of the metal elements added is 0.01 wt % to 0.1 wt % based on a total mass of a system; S4, adding the porous ZnS/PS nanospheres prepared in S3 into a tetrahydrofuran solvent for reaction, and conducting centrifugation, washing and calcination, so as to obtain porous β-type ZnS nanospheres; and S5, washing the porous β-type ZnS nanospheres by using an acid pickling agent, rinsing the nanospheres by using water to become neutral after washing, and conducting activation and modification by using an activating agent, so as to obtain the β-type zinc sulfide that has been activated and modified with the activating agent, wherein the acid pickling agent is selected from at least one of sulfuric acid, nitric acid, phosphoric acid, and acetic acid, and the activating agent is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, a silane coupling agent, a titanate coupling agent, triethanolamine, epoxidized soybean oil, isooctanol, isooctanoic acid, castor oil, glyceryl monostearate, and a sorbitan fatty acid ester nonionic surfactant and a polyoxyethylene sorbitan fatty acid ester nonionic surfactant.
  2. 2 . The preparation method according to claim 1 , wherein in S1, the organic solvent is at least one of benzene, methylbenzene, dimethylbenzene, ethylbenzene, ethyl acetate, dichloromethane, methyl acetate, chloroform and carbon tetrachloride; and a content of the styrene monomers in the oil phase is 15 wt %-20 wt %.
  3. 3 . The preparation method according to claim 1 , wherein in S2, the pore-forming agent is a mixture of the polyoxyethylene sorbitan fatty acid ester and the cetyltrimethyl ammonium bromide in a mass ratio of 5:(2-3).
  4. 4 . The preparation method according to claim 1 , wherein in S2, the surfactant is selected from at least one of the sodium dodecyl benzene sulfonate, the sodium dodecyl sulfonate, the sodium dodecyl sulfate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfonate, sodium hexadecyl sulfate, sodium octadecyl benzene sulfonate, sodium octadecyl sulfonate, and polyoxyethylene (20) sorbitan monooleate; the Zn salt is selected from at least one of zinc nitrate, zinc sulfate, and zinc chloride; the complexing agent is selected from at least one of citric acid, sodium citrate, polyethylene glycol, ammonia water, tartaric acid, and hydrazine; the sulfur source is selected from at least one of sodium sulfide, potassium sulfide, aluminum sulfide, manganese sulfide, ammonium sulfide, thiourea, and L-cysteine; and the water-soluble initiator is selected from at least one of sodium persulfate, potassium persulfate, and ammonium persulfate.
  5. 5 . The preparation method according to claim 1 , wherein in S2, a mass ratio of the pore-forming agent to the surfactant to the Zn salt to the complexing agent to the sulfur source to the water-soluble initiator is (2-5):(1-3):(30-50):(10-80):(60-100):(0.5-1).
  6. 6 . The preparation method according to claim 1 , wherein in S3, an emulsification condition is stirring at 12,000 r/min-15,000 r/min for 3 min-5 min.
  7. 7 . The preparation method according to claim 1 , wherein in S4, a solid-liquid ratio of the ZnS/PS nanospheres to the tetrahydrofuran solvent is 1:(5-10) g/ml, and a calcination condition is calcination at 500° C.-1000° C. for 1 h-6 h.
  8. 8 . The preparation method according to claim 1 , wherein in S5, the silane coupling is selected from at least one of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-(2-aminoethylamino) propyl-dimethoxymethylsilane, and N-[3-(trimethoxysilyl) propyl]ethylenediamine; the titanate coupling agent is selected from at least one of isopropyl tri(isostearoyl) titanate, isopropyl tri(dioctylphosphonyl) titanate, di(dioctylphosphonyl)oxyacetate titanium, di(dioctylphosphonyl)ethylene titanate, isopropyl di(methacryloyl) isostearoyl titanate, isopropyl tri(dioctylphosphonyl) titanate, isopropyl tri (dodecylbenzenesulfonyl) titanate, and isopropyl tri(n-ethylanino-ethylamino) titanate; and a mass ratio of the porous p-type ZnS nanospheres to the activating agent is 100:(2-5).

Description

CROSS-REFERENCE TO RELATED APPLICATIONS The application claims priority to Chinese patent application No. 202210182378.2, filed on Feb. 25, 2022, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD The present invention relates to the technical field of zinc sulfide preparation, and particularly relates to β-type zinc sulfide and a preparation method therefor. BACKGROUND Zinc sulfide is a group II-IV sulfide semiconductor material with a direct broadband system. At 300 K, it has a forbidden band width Eg=3.647 eV and a corresponding ultraviolet absorption band edge of 340.6 nm. Its effective mass μ is 0.176 me and its dielectric constant ε is 8.3 in the Brus formula. With high electroluminescence and photoluminescence efficiency, it is an important matrix material of multi-color fluorescent toner at present. Because of nonlinear optical properties, luminescent properties, quantum size effects and other important physical and chemical properties, the zinc sulfide is widely used in fields, such as various light-emitting apparatuses, laser and infrared detectors, infrared windows and nonlinear optical materials, ceramics, and thermoplastics. An existing production technology is to produce zinc sulfide generally by using purified sphalerite or hydrogen sulfide to react with a Zn salt solution. This kind of production processes are complex, insufficient in reaction, and incomplete in purification and separation, which leads to coarse zinc sulfide particles with an uneven particle size. In practical application, they are low in activity, poor in dispersibility, and likely to agglomerate. In addition, the hydrogen sulfide is highly toxic, and thus causing a huge safety hazard to production and much harm to the environment. CN107857292A discloses a production line for preparing zinc sulfide, which uses zinc sulfate and hydrogen sulfide gas as reaction raw materials to prepare the zinc sulfide. A preparation method for zinc sulfide uses toxic hydrogen sulfide gas as a reaction raw material, which is very harmful to the environment. CN102531040A puts forward a process method for preparing multi-spectral ZnS. The process method uses a hot isostatic pressing furnace to process original chemical vapor deposition (CVD) ZnS, so as to obtain a ZnS material with full spectrum transmission. The material has desirable optical properties, but loses desirable mechanical properties of the CVD ZnS material. It has hardness of 156 kg/mm2 and bending strength of 60 MPa, which cannot satisfy strength requirements of guidance systems of high-speed flying weapons for optical windows. SUMMARY An objective of the present invention is to provide β-type zinc sulfide and a preparation method therefor. Compared with a traditional method for synthesizing ZnS, the method has fewer steps, mild synthesis conditions, simple and easy operations, and stable morphology control of a synthesized material. An obtained product may be used in polymer resin processing, photovoltaic devices, photocatalysts, gas sensors or other fields. Zinc sulfide microspheres prepared are β-type, and have excellent photoelectric properties and broad application prospects. A technical solution of the present invention is achieved as follows: The present invention provides a preparation method for β-type zinc sulfide. The method includes: adding an oil phase containing styrene monomers into a water phase containing a pore-forming agent, a surfactant, a Zn salt, a complexing agent, a sulfur source and a water-soluble initiator, conducting mixing and emulsification, introducing metal elements, dissolving polystyrene of microspheres prepared through reaction in tetrahydrofuran, and then conducting calcination, pickling and activation to obtain the β-type zinc sulfide. For further improvement to the present invention, the method includes the following steps: S1. dissolving styrene monomers in an organic solvent, so as to obtain an oil phase;S2, dissolving a pore-forming agent, a surfactant, a Zn salt, a complexing agent, a sulfur source and a water-soluble initiator in water, so as to obtain a water phase;S3, adding the oil phase into the water phase, conducting mixing and emulsification, adjusting a pH value, introducing metal elements, conducting heating, stirring and reaction, and conducting centrifugation and washing, so as to obtain porous ZnS/Ps nanospheres;S4, adding the porous ZnS/Ps nanospheres prepared in S3 into a tetrahydrofuran solvent for reaction, and conducting centrifugation, washing and calcination, so as to obtain porous β-type ZnS nanospheres; andS5, washing the porous β-type ZnS nanospheres by using an acid pickling agent, rinsing the nanospheres by using water to become neutral after washing, and conducting activation and modification by using an activating agent, so as to obtain the β-type zinc sulfide. For further improvement to the present invention, in S1, the organic solvent is at least one of benzene, methylbenzene, d