BETA-TYPE ACTIVE ZINC SULFIDE AND PREPARATION METHOD THEREFOR
20230271847 · 2023-08-31
Assignee
Inventors
Cpc classification
International classification
Abstract
Disclosed are beta-type active 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 beta-type active zinc sulfide. The zinc sulfide microspheres prepared by the present invention are beta-type, and have excellent photoelectric properties and broad application prospects.
Claims
1. A preparation method for beta-type active 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, an addition amount being 0.01 wt%-0.1 wt% of 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 beta-type ZnS nanospheres; and S5, washing the porous beta-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 beta-type active zinc sulfide, 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 Span-series and Tween-series nonionic surfactants.
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 15wt%-20wt%.
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. 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 Tween-80; 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. 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. 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. 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. The preparation method according to claim 1, wherein in S5, the silane coupling agent is selected from at least one of KH550, KH560, KH570, KH580, KH590, KH602, and KH792; 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-ethylamino-ethylamino) titanate; and a mass ratio of the porous beta-type ZnS nanospheres to the activating agent is 100: (2-5).
9. Beta-type active zinc sulfide prepared through the preparation method according to claim 1.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0027] In order to more clearly describe technical solutions in examples of the present invention or in the prior art, the accompanying drawings required for description of the examples or the prior art will be briefly introduced below. Obviously, the accompanying drawings in the following description are merely some examples of the present invention. Those of ordinary skill in the art would also derive other accompanying drawings from these accompanying drawings without making inventive efforts.
[0028]
[0029]
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0030] Technical solutions in examples of the present invention will be clearly and completely described below. Apparently, the described examples are merely some rather than all examples of the present invention. All other examples obtained by those of ordinary skill in the art based on the examples of the present invention without creative efforts shall fall within the protection scope of the present invention.
Example 1
[0031] The example provides a preparation method for beta-type active zinc sulfide. The method specifically includes the following steps: [0032] S1, 15 g of styrene monomers was dissolved in 100 mL of ethyl acetate, so as to obtain an oil phase; [0033] S2, 2 g of pore-forming agent, 1 g of sodium hexadecyl sulfate, 30 g of zinc chloride, 10 g of sodium citrate, 60 g of aluminum sulfide and 0.5 g of sodium persulfate were dissolved in 200 mL of water, so as to obtain a water phase, where the pore-forming agent was a mixture of polyoxyethylene sorbitan fatty acid ester and cetyltrimethyl ammonium bromide in a mass ratio of 5:2; [0034] S3, the oil phase was added into the water phase for mixing, emulsification and stirring were conducted at 12,000 r/min for 3 min, a pH value was adjusted to 8, platinum nitrate was added, an addition amount being 0.01 wt% of a total mass of a system, heating was conducted to 50° C., stirring and reaction were conducted for 2 h, centrifugation was conducted at 3,000 r/min for 15 min, and washing was conducted by using deionized water, so as to obtain porous ZnS/Ps nanospheres; [0035] S4, 10 g of porous ZnS/Ps nanospheres prepared in S3 were added into 50 mL of tetrahydrofuran solvent for reaction, centrifugation was conducted at 3,000 r/min for 15 min, washing was conducted by using deionized water, and calcination was conducted at 500° C. for 1 h, so as to obtain porous beta-type ZnS nanospheres; and [0036] S5, 100 g of porous beta-type ZnS nanospheres were washed by using acetic acid and then rinsed by using deionized water to become neutral, filtering was conducted, a filter cake was dried and ground into powder, and activation and modification were conducted by using 2 g of activating agent, so as to obtain the beta-type active zinc sulfide, where a yield was 92.5%, whiteness was 95, a particle size D97 was 1.8 .Math.m, and the activating agent was a compound mixture of sodium dodecyl benzene sulfonate and a silane coupling agent KH590 in a mass ratio of 2:2.
Example 2
[0037] The example provides a preparation method for beta-type active zinc sulfide. The method specifically includes the following steps: [0038] S1, 20 g of styrene monomers was dissolved in 100 mL of dimethylbenzene, so as to obtain an oil phase; [0039] S2, 5 g of pore-forming agent, 3 g of Tween-80, 50 g of zinc sulfate, 80 g of tartaric acid, 100 g of thiourea and 1 g of ammonium persulfate were dissolved in 200 mL of water, so as to obtain a water phase, where the pore-forming agent was a mixture of polyoxyethylene sorbitan fatty acid ester and cetyltrimethyl ammonium bromide in a mass ratio of 5:3; [0040] S3, the oil phase was added into the water phase for mixing, emulsification and stirring were conducted at 15,000 r/min for 5 min, a pH value was adjusted to 9, cobalt nitrate was added, an addition amount being 0.1 wt% of a total mass of a system, heating was conducted to 70° C., stirring and reaction were conducted for 5 h, centrifugation was conducted at 3,000 r/min for 15 min, and washing was conducted by using deionized water, so as to obtain porous ZnS/Ps nanospheres; [0041] S4, 10 g of porous ZnS/Ps nanospheres prepared in S3 were added into 100 mL of tetrahydrofuran solvent for reaction, centrifugation was conducted at 3,000 r/min for 15 min, washing was conducted by using deionized water, and calcination was conducted at 1000° C. for 6 h, so as to obtain porous beta-type ZnS nanospheres; and [0042] S5, 100 g of porous beta-type ZnS nanospheres were washed by using phosphoric acid and then rinsed by using deionized water to become neutral, filtering was conducted, a filter cake was dried and ground into powder, and activation and modification were conducted by using 5 g of activating agent, so as to obtain the beta-type active zinc sulfide, where a yield was 93.7%, whiteness was 96, a particle size D97 was 1.7 .Math.m, and the activating agent was a compound mixture of sodium dodecyl benzene sulfonate and a silane coupling agent KH570 in a mass ratio of 2:5.
Example 3
[0043] The example provides a preparation method for beta-type active zinc sulfide. The method specifically includes the following steps: [0044] S1, 17 g of styrene monomers was dissolved in 100 mL of methylbenzene, so as to obtain an oil phase; [0045] S2, 3.5 g of pore-forming agent, 2 g of sodium dodecyl benzene sulfonate, 40 g of zinc nitrate, 50 g of citric acid, 80 g of sodium sulfide and 0.7 g of potassium persulfate were dissolved in 200 mL of water, so as to obtain a water phase, where the pore-forming agent was a mixture of polyoxyethylene sorbitan fatty acid ester and cetyltrimethyl ammonium bromide in a mass ratio of 5:2.5; [0046] S3, the oil phase was added into the water phase for mixing, emulsification and stirring were conducted at 13,500 r/min for 4 min, a pH value was adjusted to 8.5, platinum nitrate was added, an addition amount being 0.05 wt% of a total mass of a system, heating was conducted to 60° C., stirring and reaction were conducted for 3.5 h, centrifugation was conducted at 3,000 r/min for 15 min, and washing was conducted by using deionized water, so as to obtain porous ZnS/Ps nanospheres; [0047] S4, 10 g of porous ZnS/Ps nanospheres prepared in S3 were added into 70 mL of tetrahydrofuran solvent for reaction, centrifugation was conducted at 3,000 r/min for 15 min, washing was conducted by using deionized water, and calcination was conducted at 750° C. for 3 h, so as to obtain porous beta-type ZnS nanospheres; and [0048] S5, 100 g of porous beta-type ZnS nanospheres were washed by using sulfuric acid of 2 mol/L and then rinsed by using deionized water to become neutral, filtering was conducted, a filter cake was dried and ground into powder, and activation and modification were conducted by using 3.5 g of activating agent, so as to obtain the beta-type active zinc sulfide, where a yield was 94.2%, whiteness was 97, a particle size D97 was 1.5 .Math.m, and the activating agent was a compound mixture of sodium dodecyl benzene sulfonate and a silane coupling agent KH550 in a mass ratio of 2:3.
Example 4
[0049] Compared with Example 3, the example used sodium dodecyl benzene sulfonate as an activating agent, and did not change the other conditions. Obtained beta-type active zinc sulfide had a yield of 93.5%, whiteness of 92, and a particle size D97 of 2.0 .Math.m.
Example 5
[0050] Compared with Example 3, the example used a silane coupling agent KH550 as an activating agent, and did not change the other conditions. Obtained beta-type active zinc sulfide had a yield of 93.1%, whiteness of 91, and a particle size D97 of 2.1 .Math.m.
Example 6
[0051] Compared with Example 3, the example used polyoxyethylene sorbitan fatty acid ester as a pore-forming agent, and did not change the other conditions. Obtained beta-type active zinc sulfide had a yield of 92.9%, whiteness of 87, and a particle size D97 of 2.2 .Math.m.
Example 7
[0052] Compared with Example 3, the example used cetyltrimethyl ammonium bromide as a pore-forming agent, and did not change the other conditions. Obtained beta-type active zinc sulfide had a yield of 92.7%, whiteness of 88, and a particle size D97 of 2.1 .Math.m.
Comparative Example 1
[0053] Compared with Example 3, the example added no pore-forming agent, and did not change the other conditions.
[0054] Specifically, the example included the following steps: [0055] S1, 17 g of styrene monomers was dissolved in 100 mL of methylbenzene, so as to obtain an oil phase; [0056] S2, 5.5 g of sodium dodecyl benzene sulfonate, 40 g of zinc nitrate, 50 g of citric acid, 80 g of sodium sulfide and 0.7 g of potassium persulfate were dissolved in 200 mL of water, so as to obtain a water phase; [0057] S3, the oil phase was added into the water phase for mixing, emulsification and stirring were conducted at 13,500 r/min for 4 min, a pH value was adjusted to 8.5, platinum nitrate was added, an addition amount being 0.05 wt% of a total mass of a system, heating was conducted to 60° C., stirring and reaction were conducted for 3.5 h, centrifugation was conducted at 3,000 r/min for 15 min, and washing was conducted by using deionized water, so as to obtain ZnS/Ps nanospheres; [0058] S4, 10 g of ZnS/Ps nanospheres prepared in S3 were added into 70 mL of tetrahydrofuran solvent for reaction, centrifugation was conducted at 3,000 r/min for 15 min, washing was conducted by using deionized water, and calcination was conducted at 750° C. for 3 h, so as to obtain beta-type ZnS nanospheres; and [0059] S5, 100 g of beta-type ZnS nanospheres were washed by using sulfuric acid of 2 mol/L and then rinsed by using deionized water to become neutral, filtering was conducted, a filter cake was dried and ground into powder, and activation and modification were conducted by using 3.5 g of activating agent, so as to obtain the beta-type active zinc sulfide, where a yield was 92.4%, whiteness was 85, a particle size D97 was 2.0 .Math.m, and the activating agent was a compound mixture of sodium dodecyl benzene sulfonate and a silane coupling agent KH550 in a mass ratio of 2:3.
Comparative Example 2
[0060] Compared with Example 3, the example added no platinum nitrate, and did not change the other conditions.
[0061] Specifically, the example included the following steps: [0062] S1, 17 g of styrene monomers was dissolved in 100 mL of methylbenzene, so as to obtain an oil phase; [0063] S2, 3.5 g of pore-forming agent, 2 g of sodium dodecyl benzene sulfonate, 40 g of zinc nitrate, 50 g of citric acid, 80 g of sodium sulfide and 0.7 g of potassium persulfate were dissolved in 200 mL of water, so as to obtain a water phase, where the pore-forming agent was a mixture of polyoxyethylene sorbitan fatty acid ester and cetyltrimethyl ammonium bromide in a mass ratio of 5:2.5; [0064] S3, the oil phase was added into the water phase for mixing, emulsification and stirring were conducted at 13,500 r/min for 4 min, a pH value was adjusted to 8.5, heating was conducted to 60° C., stirring and reaction were conducted for 3.5 h, centrifugation was conducted at 3,000 r/min for 15 min, and washing was conducted by using deionized water, so as to obtain porous ZnS/Ps nanospheres; [0065] S4, 10 g of porous ZnS/Ps nanospheres prepared in S3 were added into 70 mL of tetrahydrofuran solvent for reaction, centrifugation was conducted at 3,000 r/min for 15 min, washing was conducted by using deionized water, and calcination was conducted at 750° C. for 3 h, so as to obtain porous beta-type ZnS nanospheres; and [0066] S5, 100 g of porous beta-type ZnS nanospheres were washed by using sulfuric acid of 2 mol/L and then rinsed by using deionized water to become neutral, filtering was conducted, a filter cake was dried and ground into powder, and activation and modification were conducted by using 3.5 g of activating agent, so as to obtain the beta-type active zinc sulfide, where a yield was 67.2%, whiteness was 86, a particle size D97 was 3.0 .Math.m, and the activating agent was a compound mixture of sodium dodecyl benzene sulfonate and a silane coupling agent KH550 in a mass ratio of 2:3.
Comparative Example 3
[0067] Compared with Example 3, the example added no activating agent, and did not change the other conditions.
[0068] Specifically, the example included the following steps: [0069] S1, 17 g of styrene monomers was dissolved in 100 mL of methylbenzene, so as to obtain an oil phase; [0070] S2, 3.5 g of pore-forming agent, 2 g of sodium dodecyl benzene sulfonate, 40 g of zinc nitrate, 50 g of citric acid, 80 g of sodium sulfide and 0.7 g of potassium persulfate were dissolved in 200 mL of water, so as to obtain a water phase, where the pore-forming agent was a mixture of polyoxyethylene sorbitan fatty acid ester and cetyltrimethyl ammonium bromide in a mass ratio of 5:2.5; [0071] S3, the oil phase was added into the water phase for mixing, emulsification and stirring were conducted at 13,500 r/min for 4 min, a pH value was adjusted to 8.5, platinum nitrate was added, an addition amount being 0.05 wt% of a total mass of a system, heating was conducted to 60° C., stirring and reaction were conducted for 3.5 h, centrifugation was conducted at 3,000 r/min for 15 min, and washing was conducted by using deionized water, so as to obtain porous ZnS/Ps nanospheres; [0072] S4, 10 g of porous ZnS/Ps nanospheres prepared in S3 were added into 70 mL of tetrahydrofuran solvent for reaction, centrifugation was conducted at 3,000 r/min for 15 min, washing was conducted by using deionized water, and calcination was conducted at 750° C. for 3 h, so as to obtain porous beta-type ZnS nanospheres; and [0073] S5, 100 g of porous beta-type ZnS nanospheres were washed by using sulfuric acid of 2 mol/L and then rinsed by using deionized water to become neutral, filtering was conducted, and a filter cake was dried and ground into powder, so as to obtain beta-type zinc sulfide, where a yield was 91.7%, whiteness was 89, and a particle size D97 was 2.0 .Math.m.
Comparative Example 4
[0074] Specifically, the example included the following steps:
[0075] 3.5 g of pore-forming agent, 2 g of sodium dodecyl benzene sulfonate, 40 g of zinc nitrate, 50 g of citric acid and 80 g of sodium sulfide were dissolved in 200 mL of water, a pH value was adjusted to 8.5, platinum nitrate was added, an addition amount being 0.05 wt% of a total mass of a system, heating was conducted to 60° C., stirring and reaction were conducted for 3.5 h, centrifugation was conducted at 3,000 r/min for 15 min, and washing was conducted by using deionized water, so as to obtain a porous ZnS material; and 100 g of porous ZnS material was washed by using sulfuric acid of 2 mol/L and then rinsed by using deionized water to become neutral, filtering was conducted, a filter cake was dried and ground into powder, and activation and modification were conducted by using 3.5 g of activating agent, so as to obtain the beta-type active zinc sulfide, where a yield was 88.5%, whiteness was 92, and a particle size D97 was 4.0 .Math.m.
[0076] The activating agent was a compound mixture of the sodium dodecyl benzene sulfonate and a silane coupling agent KH550 in a mass ratio of 2:3. The pore-forming agent was a mixture of polyoxyethylene sorbitan fatty acid ester and cetyltrimethyl ammonium bromide in a mass ratio of 5:2.5.
Test Example 1
[0077] Photocatalytic properties of beta-type active zinc sulfide prepared in Examples 1-7 and beta-type active zinc sulfide prepared in Comparative Examples 1-4 were tested, and results were shown in Table 1.
[0078] A methylene blue solution with an initial concentration of 1×10.sup.-4 mol/L was prepared by using a volumetric flask, 10 mg of prepared beta-type active zinc sulfide was added into 50 mL of methylene blue solution, conducting ultrasonic processing for 3 min so as to enable ZnS samples to be evenly dispersed in the methylene blue solution and form a stable suspension, stirring was conducted for 15 min so as to enable methylene blue to reach adsorption equilibrium on a surface of beta-type active zinc sulfide, irradiation was conducted by using an ultraviolet lamp so as to make a photocatalytic reaction for 30 min, 5 mL of mixed solution was taken in a centrifuge tube by using a syringe, absorbance of the solution was tested, and a degradation rate of the solution was computed according to a computation formula as follows:
[0079] A.sub.0 was an absorbance value of an initial methylene blue solution; and A.sub.1 was an absorbance value of the processed methylene blue solution.
TABLE-US-00001 Group Degradation rate (%) Example 1 94.5 Example 2 95.2 Example 3 96.4 Example 4 93.5 Example 5 93.1 Example 6 88.9 Example 7 89.1 Comparative Example 1 85.3 Comparative Example 2 87.5 Comparative Example 3 93.0 Comparative Example 4 86.4
[0080] It may be seen from the above table, the beta-type active zinc sulfide prepared in Examples 1-3 of the present invention had high photocatalytic efficiency, such that a degradation rate of methylene blue was high within 30 min.
Test Example 2
[0081] 5 g of beta-type active zinc sulfide prepared in Examples 1-7 and Comparative Examples 1-4 and 100 g of polypropylene (PP) resin (purchased from the Nan Ya Company in Taiwan, with a model PP 3317) were added into a double-screw extruder, heating was conducted to 170° C., melting, stirring and mixing were conducted for 2 h, then extrusion and granulation were conducted, modified PP was obtained and cut into dumbbell-shaped tensile samples, the dumbbell-shaped tensile samples were stretched at a constant speed of 50 mm/min according to GB/T1040.2-2006, properties of the modified PP were tested, and results were shown in Table 2.
TABLE-US-00002 Group Tensile strength (MPa) Elongation at break (%) Example 1 26.2 470 Example 2 26.4 474 Example 3 27.2 482 Example 4 23.5 457 Example 5 23.1 452 Example 6 22.9 435 Example 7 23.0 432 Comparative Example 1 21.5 412 Comparative Example 2 23.4 450 Comparative Example 3 22.5 445 Comparative Example 4 20.7 402
[0082] It may be seen from the above table that the beta-type active zinc sulfide prepared in Examples 1-3 of the present invention had less influence on mechanical properties of PP resin after being added into the PP resin for modification.
[0083] Compared with Example 3, Examples 4 and 5 used sodium dodecyl benzene sulfonate or a silane coupling agent KH550 as an activating agent, and mechanical properties of the material were decreased after the beta-type active zinc sulfide was added into the PP resin for modification. Compared with Example 3, Comparative Example 3 added no activating agent, and mechanical properties were obviously decreased. Through activation with the activating agent, dispersibility of beta-type zinc sulfide was greatly improved, compatibility with resin was enhanced, and agglomeration was reduced. Through combination and activation of the silane coupling agent and a surfactant, dispersibility and compatibility of the beta-type zinc sulfide may be greatly improved, resulting in less influence on the mechanical properties of the resin.
[0084] Compared with Example 3, Examples 6 and 7 used polyoxyethylene sorbitan fatty acid ester or cetyltrimethyl ammonium bromide as a pore-forming agent, whiteness was decreased, and after the beta-type active zinc sulfide was added into PP resin for modification, mechanical properties and photocatalytic degradation properties of the material were decreased. Compared with Example 3, Comparative Example 1 added no pore-forming agent, whiteness was obviously decreased, mechanical properties and photocatalytic degradation properties were obviously decreased, porous beta-type ZnS nanospheres were prepared by introducing the pore-forming agent, which were porous hollow microspheres, when the nanospheres were added into plastics for modification, resin macromolecules were likely to penetrate pores, and further addition of inorganic beta-type active zinc sulfide had less influence on mechanical properties of organic plastics. In addition, the pore-forming agent, especially a mesopore-forming agent, was introduced, such that a specific surface area of nanospheres was obviously increased, photocatalytic activity was improved, and further an active function of nano-beta-type active zinc sulfide was enhanced.
[0085] Compared with Example 3, Comparative Example 2 added no platinum nitrate, such that a yield was decreased, whiteness was decreased, a particle size was increased, and photocatalytic properties and mechanical properties of the material added into PP resin for modification were decreased. The present invention introduced the metal elements, so as to catalyze forward reaction between the sulfur source and the Zn salt, such that the prepared beta-type zinc sulfide had a complete crystal form and a stable structure, and stability, dispersibility and product coverage of the beta-type zinc sulfide in application of modified plastics were improved.
[0086] Comparative Example 4 did not prepare beta-type active zinc sulfide nanospheres of a hollow structure, and mechanical properties and photocatalytic degradation properties of the material were decreased after beta-type active zinc sulfide was added into PP resin for modification. The porous beta-type ZnS nanospheres were prepared, which were porous hollow microspheres, when the nanospheres were added into plastics for modification, the resin macromolecules were likely to penetrate pores, and further addition of inorganic beta-type active zinc sulfide had less influence on mechanical properties of organic plastics. In this way, agglomeration of nano particles was avoided, the specific surface area of beta-type active zinc sulfide was increased, and further photocatalytic activity was improved.
[0087] The above description is merely the preferred examples of the present invention, and not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention should fall within the protection scope of the present invention.