WO2023160008A1 - 一种β型活性硫化锌及其制备方法 - Google Patents

一种β型活性硫化锌及其制备方法 Download PDF

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WO2023160008A1
WO2023160008A1 PCT/CN2022/130206 CN2022130206W WO2023160008A1 WO 2023160008 A1 WO2023160008 A1 WO 2023160008A1 CN 2022130206 W CN2022130206 W CN 2022130206W WO 2023160008 A1 WO2023160008 A1 WO 2023160008A1
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sodium
preparation
zinc sulfide
porogen
zns
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French (fr)
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林泽鹏
林华雄
林俊
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广东鑫达新材料科技有限公司
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Priority to DE112022000663.3T priority Critical patent/DE112022000663T5/de
Priority to US18/303,477 priority patent/US20230271847A1/en
Publication of WO2023160008A1 publication Critical patent/WO2023160008A1/zh

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the invention relates to the technical field of zinc sulfide preparation, in particular to a ⁇ -type active zinc sulfide and a preparation method thereof.
  • Chinese patent CN107857292A discloses a zinc sulfide preparation production line, which uses zinc sulfate and hydrogen sulfide gas as reaction raw materials to prepare zinc sulfide.
  • the zinc sulfide preparation method uses toxic hydrogen sulfide gas in the reaction raw materials, which causes great harm to the environment.
  • the Chinese patent of Chinese patent CN102531040A proposes a process method for preparing multi-spectral ZnS.
  • the process method uses a hot isostatic pressing furnace to process native CVD ZnS to obtain a ZnS material with full-spectrum transmission.
  • the material has good optical properties, it loses the good mechanical properties of CVD ZnS materials, with a hardness of 156kg/mm 2 and a bending strength of 60MPa, which cannot meet the strength requirements of the high-speed flight weapon guidance system for the optical window.
  • the purpose of the present invention is to propose a kind of ⁇ -type active zinc sulfide and preparation method thereof, compared with the traditional method for synthesizing ZnS, the method steps are reduced, the synthesis conditions are mild, the method is simple and easy, the shape control of the synthetic material is stable, and the obtained
  • the product can be used in the fields of polymer resin processing, photovoltaic devices, photocatalysts, gas sensors, etc.
  • the prepared zinc sulfide microspheres are ⁇ -type, have excellent photoelectric properties, and have broad application prospects.
  • the invention provides a preparation method of ⁇ -type active zinc sulfide, adding oil containing styrene monomer to the water phase containing porogen, surfactant, Zn salt, complexing agent, sulfur source and water-soluble initiator phase, mixed and emulsified, metal elements are introduced, and the microspheres prepared by the reaction are dissolved in polystyrene by tetrahydrofuran, calcined, pickled, and activated to obtain ⁇ -type active zinc sulfide.
  • step S4 adding the porous ZnS/Ps nanospheres prepared in step S3 into a tetrahydrofuran solvent for reaction, centrifuging, washing, and calcining to obtain porous ⁇ -type ZnS nanospheres;
  • the organic solvent described in step S1 is at least one of benzene, toluene, xylene, ethylbenzene, ethyl acetate, methylene chloride, methyl acetate, chloroform, and carbon tetrachloride;
  • the content of the styrene monomer in the oil phase is 15-20wt%.
  • the porogen described in step S2 is a composite porogen, including a macroporous porogen and a mesoporous porogen, and the macroporous porogen is selected from polyoxyethylene sorbitan At least one of fatty acid esters, polyethylene glycol octylphenyl ether and polyoxyethylene sorbitan fatty acid esters; the mesoporous agent is selected from cetyltrimethylammonium bromide ( CTAB), oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 (P123), PEO106-PPO70-PEO106 (F127), preferably, the porogen is polyoxyethylene dehydration A mixture of sorbitol fatty acid ester and cetyltrimethylammonium bromide, the mass ratio is 5:(2-3).
  • CTAB cetyltrimethylammonium bromide
  • PEO20-PPO70-PEO20 P123
  • the surfactant described in step S2 is selected from sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium dodecylsulfate, sodium cetylbenzenesulfonate, One of sodium cetyl sulfonate, sodium cetyl sulfate, sodium octadecylbenzenesulfonate, sodium octadecylsulfonate, Tween-80;
  • the Zn salt is selected from zinc nitrate At least one of , zinc sulfate, zinc chloride;
  • the complexing agent is selected from at least one of citric acid, sodium citrate, polyethylene glycol, ammonia, tartaric acid, hydrazine;
  • the sulfur source is selected from At least one of sodium sulfide, potassium sulfide, aluminum sulfide, manganese sulfide, ammonium sulfide,
  • the mass ratio of porogen, surfactant, Zn salt, complexing agent, sulfur source, and water-soluble initiator described in step S2 is (2-5): (1-3): (30-50): (10-80): (60-100): (0.5-1).
  • the metal element described in step S3 is selected from at least one of nickel, lanthanum, cerium, cobalt, titanium, palladium, iridium, platinum, molybdenum, and strontium, and the addition amount is 0.01- 0.1 wt%; the pH value is adjusted to 8-9, the emulsification condition is 12000-15000r/min stirring for 3-5min; the heating temperature is 50-70°C, and the reaction is 2-5h.
  • the solid-to-liquid ratio of the ZnS/Ps nanospheres and THF solvent in step S4 is 1: (5-10) g/mL, the calcination conditions are 500-1000°C, and the calcination is 1- 6h.
  • the pickling agent in step S5 is selected from at least one of sulfuric acid, nitric acid, phosphoric acid, and acetic acid;
  • the activator is selected from sodium dodecylbenzenesulfonate, dodecylsulfuric acid Sodium, sodium dodecyl sulfonate, silane coupling agent, titanate coupling agent, triethanolamine, epoxidized soybean oil, isooctyl alcohol, isooctyl acid, castor oil, glyceryl monostearate, Span series , at least one of Tween series nonionic surfactants,
  • the silane coupling agent is selected from at least one of KH550, KH560, KH570, KH580, KH590, KH602, KH792;
  • the titanate coupling agent Selected from isopropyl tris (isostearyl) titanate, isopropyl tris (dioctyl
  • the activator is a complex mixture of sodium dodecylbenzenesulfonate and a silane coupling agent, with a mass ratio of 2:(2-5).
  • silane coupling agent e.g., sodium dodecylbenzenesulfonate
  • surfactant e.g., sodium dodecylbenzenesulfonate
  • the dispersion and compatibility of ⁇ -type zinc sulfide can be greatly improved.
  • the present invention further protects a ⁇ -type active zinc sulfide prepared by the above-mentioned preparation method.
  • the present invention uses the sol-gel method to combine the oil phase containing styrene monomer with the water containing porogen, surfactant, Zn salt, complexing agent, sulfur source, and water-soluble initiator. Phase mixing and emulsification, the oil phase is added to the water phase to form an oil-in-water emulsion.
  • the water phase uses Zn salt and sulfur source as precursors, and then adds complexing agents, surfactants and other additives, and mixes evenly to form a stable sol system , a sol-gel reaction occurs to form a ZnS shell.
  • polystyrene is generated simultaneously as an intermediate template.
  • nanoporous microspheres with a ZnS/Ps two-layer structure are easily generated in the solution. (under the condition that the porogen exists), and then wash away the polystyrene with tetrahydrofuran, and then calcined at 500-1000 ° C to obtain porous ⁇ -type ZnS nanospheres, which are hollow porous microspheres;
  • the present invention catalyzes the accelerated reaction between the sulfur source and the Zn salt to proceed forward, so that the prepared ⁇ -type zinc sulfide has a complete crystal form and a stable structure, and improves the stability of the ⁇ -type zinc sulfide in the application of modified plastics. , dispersion and product coverage.
  • metal sulfide instead of hydrogen sulfide allows the zinc salt to fully react, while reducing safety hazards in production and reducing environmental pollution.
  • Porous ⁇ -type ZnS nanospheres are prepared by introducing porogens, which are porous hollow microspheres.
  • this method has fewer steps, mild synthesis conditions, simple and easy method, stable shape control of the synthesized material, and the obtained product can be applied in electrocatalysis, infrared fluorescence, semiconductor, polymer material, new energy
  • the prepared zinc sulfide microspheres are ⁇ -type, have excellent photoelectric properties, and have broad application prospects.
  • Fig. 1 is the SEM figure of the ⁇ type active zinc sulfide that the embodiment of the present invention 1 makes;
  • Figure 2 is a TEM image of the ⁇ -type active zinc sulfide prepared in Example 1 of the present invention.
  • This embodiment provides a preparation method of ⁇ -type active zinc sulfide, which specifically includes the following steps:
  • porogen Dissolve 2g of porogen, 1g of sodium cetyl sulfate, 30g of zinc chloride, 10g of sodium citrate, 60g of aluminum sulfide, and 0.5g of sodium persulfate in 200mL of water to obtain an aqueous phase;
  • the porogen is polyoxygen A mixture of ethylene sorbitan fatty acid ester and cetyltrimethylammonium bromide, the mass ratio is 5:2;
  • step S4 Add 10 g of porous ZnS/Ps nanospheres prepared in step S3 into 50 mL of tetrahydrofuran solvent for reaction, centrifuge at 3000 r/min for 15 minutes, wash with deionized water, and calcinate at 500° C. for 1 hour to obtain porous ⁇ -type ZnS nanospheres;
  • Fig. 1 is the SEM figure of the ⁇ type active zinc sulfide that makes, and as can be seen from the figure, a large amount of macropores and mesopores are formed on the surface of this nanometer microsphere;
  • Fig. 2 is the TEM figure of the ⁇ type active zinc sulfide that makes, by It can be seen from the figure that the nano-microsphere is a hollow structure.
  • This embodiment provides a preparation method of ⁇ -type active zinc sulfide, which specifically includes the following steps:
  • step S4 Add 10 g of the porous ZnS/Ps nanospheres prepared in step S3 into 100 mL of tetrahydrofuran solvent for reaction, centrifuge at 3000 r/min for 15 minutes, wash with deionized water, and calcinate at 1000° C. for 6 hours to obtain porous ⁇ -type ZnS nanospheres;
  • This embodiment provides a preparation method of ⁇ -type active zinc sulfide, which specifically includes the following steps:
  • porogen 2g sodium dodecylbenzenesulfonate, 40g zinc nitrate, 50g citric acid, 80g sodium sulfide, 0.7g potassium persulfate are dissolved in 200mL water to obtain the water phase;
  • the porogen is poly A mixture of oxyethylene sorbitan fatty acid ester and cetyltrimethylammonium bromide, the mass ratio is 5:2.5;
  • step S4 Add 10 g of the porous ZnS/Ps nanospheres prepared in step S3 into 70 mL of tetrahydrofuran solvent for reaction, centrifuge at 3000 r/min for 15 minutes, wash with deionized water, and calcinate at 750° C. for 3 hours to obtain porous ⁇ -type ZnS nanospheres;
  • the activator is sodium dodecylbenzenesulfonate, and other conditions are not changed.
  • the yield of the obtained ⁇ -type active zinc sulfide is 93.5%, the whiteness is 92, and the particle diameter D97 is 2.0 ⁇ m.
  • the activator is the silane coupling agent KH550, and other conditions are not changed.
  • the yield of the obtained ⁇ -type active zinc sulfide was 93.1%, the whiteness was 91, and the particle size D97 was 2.1 ⁇ m.
  • the porogen is polyoxyethylene sorbitan fatty acid ester, and other conditions are not changed.
  • the yield of the ⁇ -type active zinc sulfide was 92.9%, the whiteness was 87, and the particle size D97 was 2.2 ⁇ m.
  • the porogen is cetyltrimethylammonium bromide, and other conditions are not changed.
  • the yield of the obtained ⁇ -type active zinc sulfide was 92.7%, the whiteness was 88, and the particle size D97 was 2.1 ⁇ m.
  • Example 3 Compared with Example 3, no porogen was added, and other conditions were not changed.
  • step S4 Add 10 g of the ZnS/Ps nanospheres prepared in step S3 into 70 mL of tetrahydrofuran solvent for reaction, centrifuge at 3000 r/min for 15 minutes, wash with deionized water, and calcinate at 750° C. for 3 hours to obtain ⁇ -type ZnS nanospheres;
  • Example 3 Compared with Example 3, no platinum nitrate was added, and other conditions remained unchanged.
  • porogen 2g sodium dodecylbenzenesulfonate, 40g zinc nitrate, 50g citric acid, 80g sodium sulfide, 0.7g potassium persulfate are dissolved in 200mL water to obtain the water phase;
  • the porogen is poly A mixture of oxyethylene sorbitan fatty acid ester and cetyltrimethylammonium bromide, the mass ratio is 5:2.5;
  • step S4 Add 10 g of the porous ZnS/Ps nanospheres prepared in step S3 into 70 mL of tetrahydrofuran solvent for reaction, centrifuge at 3000 r/min for 15 minutes, wash with deionized water, and calcinate at 750° C. for 3 hours to obtain porous ⁇ -type ZnS nanospheres;
  • Example 3 Compared with Example 3, no activator was added, and other conditions were not changed.
  • porogen 2g sodium dodecylbenzenesulfonate, 40g zinc nitrate, 50g citric acid, 80g sodium sulfide, 0.7g potassium persulfate are dissolved in 200mL water to obtain the water phase;
  • the porogen is poly A mixture of oxyethylene sorbitan fatty acid ester and cetyltrimethylammonium bromide, the mass ratio is 5:2.5;
  • step S4 Add 10 g of the porous ZnS/Ps nanospheres prepared in step S3 into 70 mL of tetrahydrofuran solvent for reaction, centrifuge at 3000 r/min for 15 minutes, wash with deionized water, and calcinate at 750° C. for 3 hours to obtain porous ⁇ -type ZnS nanospheres;
  • the activator is a compound mixture of sodium dodecylbenzenesulfonate and silane coupling agent KH550, with a mass ratio of 2:3.
  • the porogen is a mixture of polyoxyethylene sorbitan fatty acid ester and cetyltrimethylammonium bromide with a mass ratio of 5:2.5.
  • Degradation rate (%) (A 0 -A 1 )/A 0 ⁇ 100%.
  • a 0 is the absorbance value of the initial methylene blue solution
  • a 1 is the absorbance value of the treated methylene blue solution.
  • the activator is sodium dodecylbenzenesulfonate or silane coupling agent KH550, and the mechanical properties of the material after adding PP resin to modify it, compared with Example 3 and Example 3 Compared with the absence of an activator, the mechanical properties are significantly reduced.
  • the activation of the activator greatly improves the dispersion of ⁇ -type zinc sulfide, increases the compatibility with the resin, and reduces the occurrence of agglomeration.
  • the silane coupling agent and The complex activation of surfactants can greatly improve the dispersion and compatibility of ⁇ -type zinc sulfide, thus having little effect on the mechanical properties of the resin.
  • the porogen is polyoxyethylene sorbitan fatty acid ester or cetyltrimethylammonium bromide, and its whiteness decreases.
  • the photocatalytic degradation performance declines
  • comparative example 1 compares with embodiment 3, does not add porogen, its whiteness declines obviously, mechanical properties declines significantly, photocatalytic degradation performance declines obviously, by introducing porogen Prepare porous ⁇ -type ZnS nano-microspheres, which are porous hollow microspheres.
  • resin macromolecules can easily penetrate through the pores, so that the addition of inorganic ⁇ -type active zinc sulfide has little effect on the mechanical properties of organic plastics. .
  • porogens especially mesoporous porogens
  • the specific surface area of nano-microspheres can be significantly increased, and their photocatalytic reactivity can be improved, thereby improving the active function of nano- ⁇ -type active zinc sulfide.
  • Example 3 in Comparative Example 2 without adding platinum nitrate, the product yield decreased, the whiteness decreased, the particle size increased, the photocatalytic performance and the mechanical properties of the material modified by adding PP resin decreased.
  • the present invention introduces metal elements, catalyzes the accelerated reaction between the sulfur source and the Zn salt, and makes the prepared ⁇ -type zinc sulfide crystal form complete and stable in structure, and improves the stability and dispersion of the ⁇ -type zinc sulfide in the application of modified plastics. performance and product coverage.
  • nano-microsphere-type ⁇ -type active zinc sulfide with hollow structure was not prepared, and the mechanical properties of the material were greatly reduced after adding PP resin modification, and the photocatalytic activity decreased, and porous ⁇ -type ZnS nano-microspheres were prepared, which were porous Hollow microspheres, when added to plastics for modification, resin macromolecules are easy to penetrate through the pores, so that the addition of inorganic ⁇ -type active zinc sulfide has little effect on the mechanical properties of organic plastics, thereby avoiding nanoparticle agglomeration and improving ⁇ The specific surface area of the type active ZnS, thereby improving its photocatalytic activity.

Abstract

本发明提出了一种β型活性硫化锌及其制备方法，属于硫化锌制备技术领域，向含有致孔剂、表面活性剂、Zn盐、络合剂、硫源、水溶性引发剂的水相中加入含有苯乙烯单体的油相，混合乳化，引入金属元素，反应制得的微球经四氢呋喃溶解聚苯乙烯后，煅烧，酸洗，并活化得到β型活性硫化锌。与传统合成ZnS的方法相比，该方法步骤减少，合成条件温和，方法简便易行，合成材料的形貌控制稳定，所得产物可应用于电催化、红外荧光、半导体、高分子材料、新能源材料等领域，制得的硫化锌微球为β型，具有极好的光电性能，具有广阔的应用前景。

Description

一种β型活性硫化锌及其制备方法 技术领域
本发明涉及硫化锌制备技术领域，具体涉及一种β型活性硫化锌及其制备方法。
背景技术
硫化锌是Ⅱ-Ⅳ族硫化物半导体材料，是具有直接宽带系的半导体材料，在300K时，其禁带宽度Eg＝3.647eV，相应的紫外吸收带边为340.6nm。在Brus公式中，其有效质量μ＝0.176me，介电常数ε＝8.3。其电致发光和光致发光效率很高，是目前多荧光色粉的重要基质材料。由于硫化锌具有的非线性光学性质、发光性质、量子尺寸效应及其它重要的物理化学性质，其应用范围十分广泛，如各种发光装置、激光与红外探测器件、红外窗口与非线性光学材料、陶瓷及热塑塑料等领域。现有生产技术中，硫化锌的生产通常采用提纯闪锌矿或硫化氢与锌盐溶液反应，此类生产工艺复杂，反应不充分，提纯、分离不完全导致硫化锌颗粒粗大，粒径不均一，在实际应用中，其活性低、分散性差易团聚。同时，硫化氢有剧毒，对于生产存在巨大安全隐患，对于环境危害也十分严重。
中国专利CN107857292A公开了一种硫化锌的制备生产线，以硫酸锌和硫化氢气体为反应原料制备硫化锌。该硫化锌制备方法在反应原料中使用了有毒的硫化氢气体，对环境造成较大危害。
中国专利CN102531040A的中国专利中提出了制备多光谱ZnS的工艺方法，该工艺方法使用热等静压炉对原生CVD ZnS进行处理，获得了具有全谱段透过ZnS材料。该材料虽然具有良好的光学性能，却损失了CVD ZnS材料所具备的良好机械性能，硬度156kg/mm 2，抗弯强度60MPa，无法满足高速飞行武器制导系统对光学窗口的强度使用要求。
发明内容
本发明的目的在于提出一种β型活性硫化锌及其制备方法，与传统合成ZnS的方法相比，该方法步骤减少，合成条件温和，方法简便易行，合成材料的形貌控制稳定，所得产物可应用于高分子树脂加工、光伏器件、光催化剂、气敏传感器等领域，制得的硫化锌微球为β型，具有极好的光电性能，具有广阔的应用前景。
本发明的技术方案是这样实现的：
本发明提供一种β型活性硫化锌的制备方法，向含有致孔剂、表面活性剂、Zn盐、络合剂、硫源、水溶性引发剂的水相中加入含有苯乙烯单体的油相，混合乳化，引入金属元素，反应制得的微球经四氢呋喃溶解聚苯乙烯后，煅烧，酸洗，并活化得到β型活性硫化锌。
作为本发明的进一步改进，包括以下步骤：
S1.将苯乙烯单体溶于有机溶剂中，得到油相；
S2.将致孔剂、表面活性剂、Zn盐、络合剂、硫源、水溶性引发剂溶于水中，得到水相；
S3.将油相加入水相中混合，乳化，调节pH值，引入金属元素，加热搅拌反应，离心，洗涤，得到多孔ZnS/Ps纳米微球；
S4.将步骤S3制得的多孔ZnS/Ps纳米微球加入四氢呋喃溶剂中反应，离心，洗涤，煅烧，得到多孔β型ZnS纳米微球；
S5.用酸洗剂洗涤多孔β型ZnS纳米微球，洗涤后用水漂洗至中性，使用活化剂活化改性，得到β型活性硫化锌。
作为本发明的进一步改进，步骤S1中所述有机溶剂为苯、甲苯、二甲苯、乙苯、乙酸乙酯、二氯甲烷、乙酸甲酯、氯仿、四氯化碳中的至少一种；所述苯乙烯单体在油相中的含量为15-20wt％。
作为本发明的进一步改进，步骤S2中所述致孔剂为复合致孔剂，包括大孔致孔剂和介孔致孔剂，所述大孔致孔剂选自聚氧乙烯失水山梨醇脂肪酸酯、聚乙二醇辛基苯基醚和聚氧乙烯失水山梨醇脂肪酸酯中的至少一种；所述介孔致孔剂选自十六烷基三甲基溴化铵(CTAB)、氧乙烯-氧丙烯三嵌段共聚物PEO20-PPO70-PEO20(P123)、PEO106-PPO70-PEO106(F127)中的至一种，优选地，所述致孔剂为聚氧乙烯失水山梨醇脂肪酸酯和十六烷基三甲基溴化铵的混合物，质量比为5：(2-3)。
作为本发明的进一步改进，步骤S2中所述表面活性剂选自十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠、十六烷基苯磺酸钠、十六烷基磺酸钠、十六烷基硫酸钠、十八烷基苯磺酸钠、十八烷基磺酸钠、吐温-80中的至一种；所述Zn盐选自硝酸锌、硫酸锌、氯化锌中的至少一种；所述络合剂选自柠檬酸、柠檬酸钠、聚乙二醇、氨水、酒石酸、联氨中的至少一种；所述硫源选自硫化钠、硫化钾、硫化铝、硫化锰、硫化铵、硫脲、L-半胱氨酸中的至少一种；所述水溶性引发剂选自过硫酸钠、过硫酸钾、过硫酸铵中的至少一种。
作为本发明的进一步改进，步骤S2中所述致孔剂、表面活性剂、Zn盐、络合剂、硫源、水溶性引发剂的质量比为(2-5)：(1-3)：(30-50)：(10-80)：(60-100)：(0.5-1)。
作为本发明的进一步改进，步骤S3中所述金属元素选自镍、镧、铈、钴、钛、钯、铱、铂、钼、锶中的至少一种，添加量为体系总质量的0.01-0.1wt％；所述pH值调节至8-9，所述乳化条件为12000-15000r/min搅拌3-5min；所述加热温度为50-70℃，反应2-5h。
作为本发明的进一步改进，步骤S4中所述ZnS/Ps纳米微球和四氢呋喃溶剂的固液比为1：(5-10)g/mL，所述煅烧条件为500-1000℃，煅烧1-6h。
作为本发明的进一步改进，步骤S5中所述酸洗剂选自硫酸、硝酸、磷酸、醋酸中的至少一种；所述活化剂选自十二烷基苯磺酸钠、十二烷基硫酸钠、十二烷基磺酸钠、硅烷偶联剂、钛酸酯偶联剂、三乙醇胺、环氧大豆油、异辛醇、异辛酸、蓖麻油、单硬脂酸甘油酯、司盘系列、吐温系列非离子表面活性剂中的至少一种，所述硅烷偶联剂选自KH550、KH560、KH570、KH580、KH590、KH602、KH792中的至少一种；所述钛酸酯偶联剂选自异丙基三(异硬脂酰基)钛酸酯、异丙基三(二辛基焦磷酰基)钛酸酯、二(二辛基焦磷酰基)合氧乙酸酯钛、二(二辛基焦磷酰基)乙撑钛酸酯、异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯、异丙基三(二辛基磷酰基)钛酸酯、异丙基三(十二烷基苯磺酰基)钛酸酯、异丙基三(正乙氨基—乙氨基)钛酸酯中的至少一种；所述多孔β型ZnS纳米微球与活化剂的质量比为100：(2-5)。
优选地，活化剂为十二烷基苯磺酸钠和硅烷偶联剂的复配混合物，质量比为2：(2-5)。经过硅烷偶联剂和表面活性剂的复合活化，能大大提高β型硫化锌的分散性和相容性。
本发明进一步保护一种上述的制备方法制得的β型活性硫化锌。
本发明具有如下有益效果：本发明通过溶胶凝胶法，将含有苯乙烯单体的油相与含有致孔剂、表面活性剂、Zn盐、络合剂、硫源、水溶性引发剂的水相混合乳化，油相加入水相中，形成水包油乳液，水相中以Zn盐和硫源为前驱体，然后加入络合剂、表面活性剂等添加剂，均匀混合，形成稳定的溶胶体系，发生溶胶凝胶反应，形成ZnS壳层，同时，同步生成聚苯乙烯为中间模板，由于ZnS与聚苯乙烯模板形成的速率差异在溶液中容易生成ZnS/Ps两层结构的纳米多孔微球(在致孔剂存在的条件下)，然后用四氢呋喃洗去聚苯乙烯后，在500-1000℃下煅烧，得到多孔β型ZnS纳米微球，为中空多孔微球；
另外，本发明通过引入金属元素，催化硫源与Zn盐加速反应正向进行，使制备的β型硫化锌晶型完整、结构稳定，提高了β型硫化锌在改性塑料应用中的稳定性、分散性及产品遮盖 率。使用金属硫化物代替硫化氢，使得锌盐充分反应，同时减少生产中的安全隐患、减少环境污染。通过引入致孔剂制备多孔β型ZnS纳米微球，为多孔中空微球，加入塑料中改性处理时，树脂大分子容易从孔中贯穿从而使得无机β型活性硫化锌的添加对有机塑料的力学性能影响不大；通过活化剂活化，极大的提高了β型硫化锌的分散性，增加了与树脂的相容性，减少团聚现象。
与传统合成ZnS的方法相比，该方法步骤减少，合成条件温和，方法简便易行，合成材料的形貌控制稳定，所得产物可应用于电催化、红外荧光、半导体、高分子材料、新能源材料等领域，制得的硫化锌微球为β型，具有极好的光电性能，具有广阔的应用前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例1制得的β型活性硫化锌的SEM图；
图2为本发明实施例1制得的β型活性硫化锌的TEM图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例提供一种β型活性硫化锌的制备方法，具体包括以下步骤：
S1.将15g苯乙烯单体溶于100mL乙酸乙酯中，得到油相；
S2.将2g致孔剂、1g十六烷基硫酸钠、30g氯化锌、10g柠檬酸钠、60g硫化铝、0.5g过硫酸钠溶于200mL水中，得到水相；致孔剂为聚氧乙烯失水山梨醇脂肪酸酯和十六烷基三甲基溴化铵的混合物，质量比为5：2；
S3.将油相加入水相中混合，12000r/min乳化搅拌3min，调节pH值至8，加入硝酸铂，添加量为体系总质量的0.01wt％，加热至50℃，搅拌反应2h，3000r/min离心15min，去离子 水洗涤，得到多孔ZnS/Ps纳米微球；
S4.将10g步骤S3制得的多孔ZnS/Ps纳米微球加入50mL四氢呋喃溶剂中反应，3000r/min离心15min，去离子水洗涤，500℃煅烧1h，得到多孔β型ZnS纳米微球；
S5.用醋酸洗涤100g多孔β型ZnS纳米微球，洗涤后用去离子水漂洗至中性，过滤，滤饼干燥、磨粉，使用2g活化剂活化改性，得到β型活性硫化锌，产率为92.5％，白度为95，粒径D97为1.8μm，活化剂为十二烷基苯磺酸钠和硅烷偶联剂KH590的复配混合物，质量比为2：2。图1为制得的β型活性硫化锌的SEM图，由图可知，该纳米微球表面形成了大量的大孔及介孔；图2为制得的β型活性硫化锌的TEM图，由图可知，该纳米微球为中空结构。
实施例2
本实施例提供一种β型活性硫化锌的制备方法，具体包括以下步骤：
S1.将20g苯乙烯单体溶于100mL二甲苯中，得到油相；
S2.将5g致孔剂、3g吐温-80、50g硫酸锌、80g酒石酸、100g硫脲、1g过硫酸铵溶于200mL水中，得到水相；致孔剂为聚氧乙烯失水山梨醇脂肪酸酯和十六烷基三甲基溴化铵的混合物，质量比为5：3；
S3.将油相加入水相中混合，15000r/min乳化搅拌5min，调节pH值至9，加入硝酸钴，添加量为体系总质量的0.1wt％，加热至70℃，搅拌反应5h，3000r/min离心15min，去离子水洗涤，得到多孔ZnS/Ps纳米微球；
S4.将10g步骤S3制得的多孔ZnS/Ps纳米微球加入100mL四氢呋喃溶剂中反应，3000r/min离心15min，去离子水洗涤，1000℃煅烧6h，得到多孔β型ZnS纳米微球；
S5.用磷酸洗涤100g多孔β型ZnS纳米微球，洗涤后用去离子水漂洗至中性，过滤，滤饼干燥、磨粉，使用5g活化剂活化改性，得到β型活性硫化锌，产率为93.7％，白度为96，粒径D97为1.7μm，活化剂为十二烷基苯磺酸钠和硅烷偶联剂KH570的复配混合物，质量比为2：5。
实施例3
本实施例提供一种β型活性硫化锌的制备方法，具体包括以下步骤：
S1.将17g苯乙烯单体溶于100mL甲苯中，得到油相；
S2.将3.5g致孔剂、2g十二烷基苯磺酸钠、40g硝酸锌、50g柠檬酸、80g硫化钠、0.7g过硫酸钾溶于200mL水中，得到水相；致孔剂为聚氧乙烯失水山梨醇脂肪酸酯和十六烷基三甲基溴化铵的混合物，质量比为5：2.5；
S3.将油相加入水相中混合，13500r/min乳化搅拌4min，调节pH值至8.5，加入硝酸铂，添加量为体系总质量的0.05wt％，加热至60℃，搅拌反应3.5h，3000r/min离心15min，去离子水洗涤，得到多孔ZnS/Ps纳米微球；
S4.将10g步骤S3制得的多孔ZnS/Ps纳米微球加入70mL四氢呋喃溶剂中反应，3000r/min离心15min，去离子水洗涤，750℃煅烧3h，得到多孔β型ZnS纳米微球；
S5.用2mol/L的硫酸洗涤100g多孔β型ZnS纳米微球，洗涤后用去离子水漂洗至中性，过滤，滤饼干燥、磨粉，使用3.5g活化剂活化改性，得到β型活性硫化锌，产率为94.2％，白度为97，粒径D97为1.5μm，活化剂为十二烷基苯磺酸钠和硅烷偶联剂KH550的复配混合物，质量比为2：3。
实施例4
与实施例3相比，活化剂为十二烷基苯磺酸钠，其他条件均不改变。得到β型活性硫化锌的产率为93.5％，白度为92，粒径D97为2.0μm。
实施例5
与实施例3相比，活化剂为硅烷偶联剂KH550，其他条件均不改变。得到β型活性硫化锌的产率为93.1％，白度为91，粒径D97为2.1μm。
实施例6
与实施例3相比，致孔剂为聚氧乙烯失水山梨醇脂肪酸酯，其他条件均不改变。得到β型活性硫化锌的产率为92.9％，白度为87，粒径D97为2.2μm。
实施例7
与实施例3相比，致孔剂为十六烷基三甲基溴化铵，其他条件均不改变。得到β型活性硫化锌的产率为92.7％，白度为88，粒径D97为2.1μm。
对比例1
与实施例3相比，未添加致孔剂，其他条件均不改变。
具体包括以下步骤：
S1.将17g苯乙烯单体溶于100mL甲苯中，得到油相；
S2.将5.5g十二烷基苯磺酸钠、40g硝酸锌、50g柠檬酸、80g硫化钠、0.7g过硫酸钾溶于200mL水中，得到水相；
S3.将油相加入水相中混合，13500r/min乳化搅拌4min，调节pH值至8.5，加入硝酸铂，添加量为体系总质量的0.05wt％，加热至60℃，搅拌反应3.5h，3000r/min离心15min，去离子水洗涤，得到ZnS/Ps纳米微球；
S4.将10g步骤S3制得的ZnS/Ps纳米微球加入70mL四氢呋喃溶剂中反应，3000r/min离心15min，去离子水洗涤，750℃煅烧3h，得到β型ZnS纳米微球；
S5.用2mol/L的硫酸洗涤100gβ型ZnS纳米微球，洗涤后用去离子水漂洗至中性，过滤，滤饼干燥、磨粉，使用3.5g活化剂活化改性，得到β型活性硫化锌，产率为92.4％，白度为85，粒径D97为2.0μm，活化剂为十二烷基苯磺酸钠和硅烷偶联剂KH550的复配混合物，质量比为2：3。
对比例2
与实施例3相比，未添加硝酸铂，其他条件均不改变。
具体包括以下步骤：
S1.将17g苯乙烯单体溶于100mL甲苯中，得到油相；
S2.将3.5g致孔剂、2g十二烷基苯磺酸钠、40g硝酸锌、50g柠檬酸、80g硫化钠、0.7g 过硫酸钾溶于200mL水中，得到水相；致孔剂为聚氧乙烯失水山梨醇脂肪酸酯和十六烷基三甲基溴化铵的混合物，质量比为5：2.5；
S3.将油相加入水相中混合，13500r/min乳化搅拌4min，调节pH值至8.5，加热至60℃，搅拌反应3.5h，3000r/min离心15min，去离子水洗涤，得到多孔ZnS/Ps纳米微球；
S4.将10g步骤S3制得的多孔ZnS/Ps纳米微球加入70mL四氢呋喃溶剂中反应，3000r/min离心15min，去离子水洗涤，750℃煅烧3h，得到多孔β型ZnS纳米微球；
S5.用2mol/L的硫酸洗涤100g多孔β型ZnS纳米微球，洗涤后用去离子水漂洗至中性，过滤，滤饼干燥、磨粉，使用3.5g活化剂活化改性，得到β型活性硫化锌，产率为67.2％，白度为86，粒径D97为3.0μm，活化剂为十二烷基苯磺酸钠和硅烷偶联剂KH550的复配混合物，质量比为2：3。
对比例3
与实施例3相比，未添加活化剂，其他条件均不改变。
具体包括以下步骤：
S1.将17g苯乙烯单体溶于100mL甲苯中，得到油相；
S2.将3.5g致孔剂、2g十二烷基苯磺酸钠、40g硝酸锌、50g柠檬酸、80g硫化钠、0.7g过硫酸钾溶于200mL水中，得到水相；致孔剂为聚氧乙烯失水山梨醇脂肪酸酯和十六烷基三甲基溴化铵的混合物，质量比为5：2.5；
S3.将油相加入水相中混合，13500r/min乳化搅拌4min，调节pH值至8.5，加入硝酸铂，添加量为体系总质量的0.05wt％，加热至60℃，搅拌反应3.5h，3000r/min离心15min，去离子水洗涤，得到多孔ZnS/Ps纳米微球；
S4.将10g步骤S3制得的多孔ZnS/Ps纳米微球加入70mL四氢呋喃溶剂中反应，3000r/min离心15min，去离子水洗涤，750℃煅烧3h，得到多孔β型ZnS纳米微球；
S5.用2mol/L的硫酸洗涤100g多孔β型ZnS纳米微球，洗涤后用去离子水漂洗至中性，过滤，滤饼干燥、磨粉，得到β型硫化锌，产率为91.7％，白度为89，粒径D97为2.0μm。
对比例4
具体包括以下步骤：
将3.5g致孔剂、2g十二烷基苯磺酸钠、40g硝酸锌、50g柠檬酸、80g硫化钠溶于200mL水中，调节pH值至8.5，加入硝酸铂，添加量为体系总质量的0.05wt％，加热至60℃，搅拌反应3.5h，3000r/min离心15min，去离子水洗涤，得到多孔ZnS材料；用2mol/L的硫酸洗涤100g多孔ZnS材料，洗涤后用去离子水漂洗至中性，过滤，滤饼干燥、磨粉，使用3.5g活化剂活化改性，得到β型活性硫化锌，产率为88.5％，白度为92，粒径D97为4.0μm。
活化剂为十二烷基苯磺酸钠和硅烷偶联剂KH550的复配混合物，质量比为2：3。致孔剂为聚氧乙烯失水山梨醇脂肪酸酯和十六烷基三甲基溴化铵的混合物，质量比为5：2.5。
测试例1
将实施例1-7和对比例1-4制得的β型活性硫化锌进行光催化性能测试，结果见表1。
用容量瓶配制初始浓度为1×10 -4mol/L的亚甲基蓝溶液，量取50mL后，加入10mg制备好的β型活性硫化锌，超声3min使ZnS样品均匀地分散在亚甲基蓝溶液中形成稳定的悬浮液，搅拌15min使亚甲基蓝在β型活性硫化锌表面达到吸附平衡，紫外灯照射使光催化反应进行，30min用注射器取5mL该混合溶液与离心管中，测试其吸光度，计算其降解率，计算公式如下：
降解率(％)＝(A 0-A 1)/A 0×100％。
其中，A 0为初始亚甲基蓝溶液的吸光度值；A 1为经过处理后的亚甲基蓝溶液的吸光度值。
表1
组别 降解率(％)
实施例1 94.5
实施例2 95.2
实施例3 96.4
实施例4 93.5
实施例5 93.1
实施例6 88.9
实施例7 89.1
对比例1 85.3
对比例2 87.5
对比例3 93.0
对比例4 86.4
由上表可知，本发明实施例1-3制得的β型活性硫化锌光催化效率高，使得30min内亚甲基蓝降解率高。
测试例2
[根据细则26改正 21.12.2022]
将5g实施例1-7和对比例1-4制得的β型活性硫化锌和100g PP树脂(购于中国台湾省南亚，型号PP 3317)加入双螺杆挤出机，加热至170℃熔融搅拌混合2h后，挤出，制粒，得到改性PP，剪裁成哑铃型拉伸试样，根据GB/T1040.2-2006对哑铃型拉伸试样进行定速拉伸，速率为50mm/min，测试改性PP的性能，结果如表2。
表2
组别 拉伸强度(MPa) 断裂伸长率(％)
实施例1 26.2 470
实施例2 26.4 474
实施例3 27.2 482
实施例4 23.5 457
实施例5 23.1 452
实施例6 22.9 435
实施例7 23.0 432
对比例1 21.5 412
对比例2 23.4 450
对比例3 22.5 445
对比例4 20.7 402
由上表可知，本发明实施例1-3制得的β型活性硫化锌加入PP树脂中改性后，对PP树脂的力学性能影响不大。
实施例4、5与实施例3相比，活化剂为十二烷基苯磺酸钠或硅烷偶联剂KH550，其加入PP树脂改性后材料的力学性能下降，对比例3与实施例3相比，未添加活化剂，力学性能显著下降，通过活化剂活化，极大的提高了β型硫化锌的分散性，增加了与树脂的相容性，减少团聚现，经过硅烷偶联剂和表面活性剂的复合活化，能大大提高β型硫化锌的分散性和相容性，从而对树脂的力学性能影响不大。
实施例6、7与实施例3相比，致孔剂为聚氧乙烯失水山梨醇脂肪酸酯或十六烷基三甲基溴化铵，其白度下降，加入PP树脂改性后材料的力学性能下降，光催化降解性能下降，对比例1与实施例3相比，未添加致孔剂，其白度明显下降，力学性能显著下降，光催化降解性能明显下降，通过引入致孔剂制备多孔β型ZnS纳米微球，为多孔中空微球，加入塑料中改性处理时，树脂大分子容易从孔中贯穿从而使得无机β型活性硫化锌的添加对有机塑料的力学性能影响不大。另一方面，通过引入致孔剂，特别是介孔致孔剂，能明显增大纳米微球的比表面积，提高其光催化反应活性，从而提高纳米β型活性硫化锌的活性功能。
对比例2与实施例3相比，未添加硝酸铂，其产物得率下降，白度下降，粒径增大，光催化性能以及加入PP树脂改性后材料的力学性能下降。本发明通过引入金属元素，催化硫源与 Zn盐加速反应正向进行，使制备的β型硫化锌晶型完整、结构稳定，提高了β型硫化锌在改性塑料应用中的稳定性、分散性及产品遮盖率。
对比例4未制备中空结构的纳米微球型β型活性硫化锌，其加入PP树脂改性后材料的力学性能大幅度下降，且光催化活性下降，制备多孔β型ZnS纳米微球，为多孔中空微球，加入塑料中改性处理时，树脂大分子容易从孔中贯穿从而使得无机β型活性硫化锌的添加对有机塑料的力学性能影响不大，从而避免纳米粒子团聚，且能提高β型活性硫化锌的比表面积，从而提高其光催化活性。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种β型活性硫化锌的制备方法，其特征在于，包括以下步骤：
    S1.将苯乙烯单体溶于有机溶剂中，得到油相；
    S2.将致孔剂、表面活性剂、Zn盐、络合剂、硫源、水溶性引发剂溶于水中，得到水相；所述致孔剂为复合致孔剂，包括大孔致孔剂和介孔致孔剂，所述大孔致孔剂选自聚氧乙烯失水山梨醇脂肪酸酯、聚乙二醇辛基苯基醚和聚氧乙烯失水山梨醇脂肪酸酯中的至少一种；所述介孔致孔剂为十六烷基三甲基溴化铵(CTAB)；
    S3.将油相加入水相中混合，乳化，调节pH值至8-9，引入金属元素，加热至50-70℃搅拌反应2-5h，离心，洗涤，得到多孔ZnS/PS纳米微球；所述金属元素选自镍、镧、铈、钴、钛、钯、铱、铂、钼、锶中的至少一种，添加量为体系总质量的0.01-0.1wt％；
    S4.将步骤S3制得的多孔ZnS/PS纳米微球加入四氢呋喃溶剂中反应，离心，洗涤，煅烧，得到多孔β型ZnS纳米微球；
    S5.用酸洗剂洗涤多孔β型ZnS纳米微球，洗涤后用水漂洗至中性，使用活化剂活化改性，得到β型活性硫化锌；所述酸洗剂选自硫酸、硝酸、磷酸、醋酸中的至少一种；所述活化剂选自十二烷基苯磺酸钠、十二烷基硫酸钠、十二烷基磺酸钠、硅烷偶联剂、钛酸酯偶联剂、三乙醇胺、环氧大豆油、异辛醇、异辛酸、蓖麻油、单硬脂酸甘油酯、司盘系列、吐温系列非离子表面活性剂中的至少一种。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤S1中所述有机溶剂为苯、甲苯、二甲苯、乙苯、乙酸乙酯、二氯甲烷、乙酸甲酯、氯仿、四氯化碳中的至少一种；所述苯乙烯单体在油相中的含量为15-20wt％。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤S2中所述致孔剂为聚氧乙烯失水山梨醇脂肪酸酯和十六烷基三甲基溴化铵的混合物，质量比为5：(2-3)。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S2中所述表面活性剂选自十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠、十六烷基苯磺酸钠、十六烷基磺酸钠、十六烷基硫酸钠、十八烷基苯磺酸钠、十八烷基磺酸钠、吐温-80中的至一种；所述Zn盐选自硝酸锌、硫酸锌、氯化锌中的至少一种；所述络合剂选自柠檬酸、柠檬酸钠、聚乙二醇、氨水、酒石酸、联氨中的至少一种；所述硫源选自硫化钠、硫化钾、硫化铝、硫化锰、硫化铵、硫脲、L-半胱氨酸中的至少一种；所述水溶性引发剂选自过硫酸钠、过硫酸钾、过硫酸铵中的至少一种。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤S2中所述致孔剂、表面活性剂、Zn盐、络合剂、硫源、水溶性引发剂的质量比为(2-5)：(1-3)：(30-50)：(10-80)： (60-100)：(0.5-1)。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤S3中所述乳化条件为12000-15000r/min搅拌3-5min。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S4中所述ZnS/PS纳米微球和四氢呋喃溶剂的固液比为1：(5-10)g/mL，所述煅烧条件为500-1000℃，煅烧1-6h。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤S5中所述硅烷偶联剂选自KH550、KH560、KH570、KH580、KH590、KH602、KH792中的至少一种；所述钛酸酯偶联剂选自异丙基三(异硬脂酰基)钛酸酯、异丙基三(二辛基焦磷酰基)钛酸酯、二(二辛基焦磷酰基)合氧乙酸酯钛、二(二辛基焦磷酰基)乙撑钛酸酯、异丙基二(甲基丙烯酰基)异硬脂酰基钛酸酯、异丙基三(二辛基磷酰基)钛酸酯、异丙基三(十二烷基苯磺酰基)钛酸酯、异丙基三(正乙氨基—乙氨基)钛酸酯中的至少一种；所述多孔β型ZnS纳米微球与活化剂的质量比为100：(2-5)。
  9. 一种如权利要求1-8任一项所述的制备方法制得的β型活性硫化锌。
PCT/CN2022/130206 2022-02-25 2022-11-07 一种β型活性硫化锌及其制备方法 WO2023160008A1 (zh)

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