Face-centered cubic nano-zinc sulfide, hexagonal nano-zinc sulfide and preparation method thereof

Abstract

The present application relates to the field of nanomaterial technology, and specifically discloses a face-centered cubic nano zinc sulfide, a hexagonal nano zinc sulfide and a preparation method thereof. The preparation method of the face-centered cubic nano zinc sulfide provided by the present application comprises the following steps: mixing an inorganic zinc salt and an inorganic sulfur salt, grinding them evenly to obtain a premix; adding a catalyst solution to the premix, reacting under grinding for 40-60 minutes to obtain a crude product; washing the crude product, filtering, filter pressing, and vacuum drying to obtain face-centered cubic nano zinc sulfide; and hexagonal nano zinc sulfide obtained by roasting the above-mentioned face-centered cubic nano zinc sulfide. The preparation method of the face-centered cubic nano zinc sulfide and hexagonal nano zinc sulfide provided by the present application uses less water and does not produce organic waste liquid, which has great practical significance.

Description

Technical Field

[0001] The present application relates to the technical field of nanomaterials, and in particular to face-centered cubic nano-zinc sulfide, hexagonal nano-zinc sulfide and a preparation method thereof. Background Art

[0002] Zinc sulfide (ZnS) is an important semiconductor material with unique electrical, optical, and catalytic properties. It is widely used in optoelectronics, bioassays, fluorescent labeling, immunoassays, catalysts, and polymer additives. Zinc sulfide has two crystalline structures: face-centered cubic (FCC), also known as sphalerite, and hexagonal (Wurtzite).

[0003] Zinc sulfide is typically prepared by liquid-phase reaction of low-concentration soluble zinc salts and sulfur-containing compounds. For example, related reports describe obtaining zinc sulfide using the following method: polyvinyl pyrrolidone of a certain molecular weight is dispersed in deionized water, stirred and heated to 50-80°C. A sulfur source such as thiourea is then added, along with concentrated nitric acid and zinc nitrate. After a reaction time, the mixture is centrifuged, washed with water, and dried to produce face-centered cubic zinc sulfide microspheres. Other reports suggest using low-concentration inorganic zinc and sulfur sources prepared in water as raw materials, using alkali metal chloride as a control and dispersant for the nanoparticles, and subjecting the mixture to ultrasonic treatment for a period of time. This is followed by centrifugation, washing with water, and vacuum drying to produce face-centered cubic nano-zinc sulfide. There are also documents that mention: using low-concentration inorganic zinc source and sulfur source prepared in water as raw materials, first prepare face-centered cubic nano zinc sulfide, then treat it with urea solution under ultrasonic treatment for a certain period of time, and then obtain hexagonal nano zinc sulfide through centrifugal separation, water washing, vacuum drying, and vacuum calcination.

[0004] However, the above methods all require the raw materials to be dissolved in water first, so a large amount of water is required in the preparation process, resulting in relatively high water consumption in the industrial preparation process. Summary of the Invention

[0005] In order to reduce the amount of water used in the preparation process of zinc sulfide, the present application provides a method for preparing zinc sulfide.

[0006] In the first aspect, the present application provides a method for preparing face-centered cubic nano-zinc sulfide, which adopts the following technical solution:

[0007] A method for preparing face-centered cubic nano-zinc sulfide comprises the following steps:

[0008] (1) Mixing and grinding the inorganic zinc salt and the inorganic sulfur salt to obtain a premix;

[0009] (2) adding a catalyst solution to the premix, reacting under grinding for 40-60 minutes to obtain a crude product;

[0010] (3) The crude product is washed, filtered, filter-pressed, and vacuum-dried to obtain face-centered cubic nano-zinc sulfide.

[0011] This application directly uses solid inorganic zinc salts and inorganic sulfur salts as raw materials, performs a grinding reaction under a catalyst, and undergoes a series of post-treatments to obtain face-centered cubic nano-zinc sulfide. This preparation method omits the raw material dissolution step in related technologies, significantly reducing water consumption and achieving a new, water-saving and energy-saving green process for the continuous production of nano-zinc sulfide. Furthermore, this preparation method has a simple process flow and is easy and convenient to operate, making it highly valuable for widespread use.

[0012] In a specific embodiment, the grinding reaction time is 40 min, or 50 min or 60 min.

[0013] Preferably, the inorganic zinc salt is selected from zinc nitrate hexahydrate, zinc sulfate heptahydrate and zinc chloride; and the inorganic sulfur salt is selected from barium sulfide, sodium sulfide nonahydrate and potassium sulfide.

[0014] In a specific embodiment, the inorganic zinc salt is zinc nitrate hexahydrate, zinc sulfate heptahydrate or zinc chloride; the inorganic sulfur salt is barium sulfide, sodium sulfide nonahydrate or potassium sulfide.

[0015] Preferably, the catalyst solution is a 0.3-0.8 wt % hydrogen peroxide solution.

[0016] In a specific embodiment, the concentration of the hydrogen peroxide solution may be 0.34 wt%, 0.41 wt% or 0.65 wt%.

[0017] Preferably, the molar ratio of the inorganic zinc salt to the inorganic sulfur salt is 1:(0.9-1.1).

[0018] In a specific embodiment, the molar ratio of the inorganic zinc salt to the inorganic sulfur salt is 1:1.

[0019] Preferably, the vacuum drying temperature is 70-90° C. and the time is 8-10 h.

[0020] In a specific embodiment, the vacuum drying temperature is 80° C. and the time is 8 hours.

[0021] In a second aspect, the present application provides a face-centered cubic nano zinc sulfide.

[0022] The invention discloses a face-centered cubic crystal nano zinc sulfide, which is prepared by utilizing a preparation method of the face-centered cubic crystal nano zinc sulfide.

[0023] In a third aspect, the present application provides a method for preparing hexagonal nano-zinc sulfide.

[0024] A method for preparing hexagonal nano zinc sulfide comprises the following steps:

[0025] The face-centered cubic nano-zinc sulfide is calcined at 500-600° C. for 1-2 hours under vacuum conditions to obtain hexagonal nano-zinc sulfide.

[0026] In the present application, since face-centered cubic nano-zinc sulfide is a high-temperature variant, it usually needs to be converted into hexagonal nano-zinc sulfide at 1020°C; however, in the present application, due to the use of a grinding production process, the obtained hexagonal nano-zinc sulfide has a smaller particle size, and the calcination is carried out under vacuum conditions, which greatly reduces the transformation temperature of the face-centered cubic nano-zinc sulfide, so that the face-centered cubic nano-zinc sulfide can be converted into hexagonal nano-zinc sulfide at 500~600°C.

[0027] In a specific embodiment, the calcination temperature may be 500°C, 550°C or 600°C.

[0028] In a specific embodiment, the calcination time can be 1 h or 2 h.

[0029] In a second aspect, the present application provides a hexagonal nano zinc sulfide.

[0030] The invention discloses hexagonal nano zinc sulfide, which is prepared by utilizing a preparation method of hexagonal nano zinc sulfide.

[0031] In summary, this application has the following beneficial effects:

[0032] 1. This application utilizes solid inorganic zinc salts and inorganic sulfur salts as raw materials, grinding and reacting them in the presence of hydrogen peroxide catalyst to produce face-centered cubic nano-zinc sulfide and hexagonal nano-zinc sulfide. This preparation method utilizes low water consumption and produces minimal wastewater, aligning with the industrial development philosophy of "water conservation and emission reduction." Furthermore, since this preparation method does not utilize organic solvents, the reaction process does not generate organic wastewater, minimizing environmental harm.

[0033] 2. In this application, due to the use of a grinding production process, the obtained hexagonal nano-zinc sulfide has a small particle size, and the calcination is carried out under vacuum conditions, which greatly reduces the transformation temperature of the face-centered cubic nano-zinc sulfide, so that the face-centered cubic nano-zinc sulfide can be transformed into hexagonal nano-zinc sulfide at 500~600℃. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is the X-ray diffraction (XRD) pattern of the face-centered cubic nano-zinc sulfide prepared in Example 1 of the present application.

[0035] Figure 2This is the X-ray diffraction (XRD) pattern of hexagonal nano-zinc sulfide prepared in Example 2 of the present application. DETAILED DESCRIPTION

[0036] In a first aspect, the present application provides a method for preparing face-centered cubic nano-zinc sulfide, comprising the following steps:

[0037] (1) Weigh a certain amount of inorganic zinc salt, put it into a ball mill, and grind it for 30 minutes to obtain inorganic zinc salt powder; weigh a certain amount of inorganic sulfur salt, put it into a ball mill, and grind it for 30 minutes to obtain inorganic sulfur salt powder; weigh a certain amount of 30% H2O2, dissolve it in deionized water to prepare a hydrogen peroxide solution with a H2O2 mass content of 0.3-0.8wt%.

[0038] Wherein, the inorganic zinc salt is zinc nitrate hexahydrate, zinc sulfate heptahydrate or zinc chloride, and the inorganic sulfur salt is barium sulfide, sodium sulfide nonahydrate or potassium sulfide.

[0039] (2) At room temperature, inorganic zinc salt powder and inorganic sulfur salt powder at a molar ratio of 1: (0.9-1.1) are added to a ball mill, and the mixture is thoroughly ground and mixed to obtain a premix;

[0040] (3) Add hydrogen peroxide solution to the premix and react under grinding for 40-60 minutes until the reaction is complete to obtain a crude product;

[0041] (4) The crude product is washed with deionized water and filtered, repeated 3-5 times, and then filtered to obtain a filter cake; and the filter cake is vacuum dried at 70-90°C for 8-10 hours to obtain face-centered cubic nano-zinc sulfide.

[0042] In a second aspect, the present application also provides a method for preparing hexagonal nano-zinc sulfide, comprising the following steps:

[0043] The face-centered cubic nano-zinc sulfide prepared above is calcined at 500-600° C. under vacuum conditions for 1-2 hours to obtain hexagonal nano-zinc sulfide.

[0044] In this application, the reagents and materials, unless otherwise specified, can be obtained from commercial sources or prepared by conventional methods.

[0045] The present application is further described in detail below with reference to the embodiments, performance testing and accompanying drawings.

[0046] Example 1

[0047] Example 1 provides a face-centered cubic nano-zinc sulfide.

[0048] The above-mentioned method for preparing face-centered cubic nano zinc sulfide is prepared by the following steps:

[0049] (1) Weigh 29.75 g of Zn(NO3)2·6H2O, put it into a ball mill, and grind it for 30 min to obtain Zn(NO3)2·6H2O powder; weigh 16.94 g of BaS, put it into a ball mill, and grind it for 30 min to obtain BaS powder; weigh 1.13 g of 30% H2O2, dissolve it in 98.07 g of deionized water to prepare a hydrogen peroxide solution with a H2O2 mass content of 0.34 wt% and a concentration of 0.34 wt%.

[0050] (2) Add the Zn(NO3)2·6H2O powder and BaS powder into a ball mill at room temperature, grind for 30 min, and mix thoroughly to obtain a premix;

[0051] (3) Add the above hydrogen peroxide solution to the premix and react for 60 minutes under grinding. The reaction is completed to obtain a crude product;

[0052] (4) The crude product was washed with deionized water and filtered three times, and then filtered to obtain a filter cake; and the filter cake was vacuum dried at 80°C for 8 hours to obtain face-centered cubic nano-zinc sulfide.

[0053] The X-ray diffraction (XRD) pattern of the face-centered cubic nano-zinc sulfide prepared in Example 1 is as follows: Figure 1 As shown, after comparison with the standard spectrum of face-centered cubic nano-zinc sulfide (sphalerite) JCPDS NO. 05-0566, the characteristic peaks of XRD are consistent.

[0054] Example 2

[0055] Example 2 provides a hexagonal nano-zinc sulfide.

[0056] The above-mentioned preparation method of hexagonal nano zinc sulfide is prepared by the following steps:

[0057] The face-centered cubic nano-zinc sulfide prepared in Example 1 was calcined at 600° C. for 1 h under vacuum conditions to obtain hexagonal nano-zinc sulfide.

[0058] The X-ray diffraction (XRD) pattern of the hexagonal nano-zinc sulfide prepared in Example 2 is as follows: Figure 1 As shown, after comparison with the standard spectrum of hexagonal nano-zinc sulfide (wurtzite) JCPDS NO. 36-1450, the characteristic peaks of XRD are consistent.

[0059] Example 3

[0060] Example 3 provides a face-centered cubic nano-zinc sulfide.

[0061] The above-mentioned method for preparing face-centered cubic nano zinc sulfide is prepared by the following steps:

[0062] (1) Weigh 34.50 g of ZnSO4·7H2O, place it in a ball mill, and grind it for 30 min to obtain ZnSO4·7H2O powder; weigh 28.82 g of Na2S·9H2O, place it in a ball mill, and grind it for 30 min to obtain Na2S·9H2O powder; weigh 1.16 g of 30% H2O2, dissolve it in 98.64 g of deionized water to prepare a hydrogen peroxide solution with a H2O2 mass content of 0.41 wt%.

[0063] (2) At room temperature, the ZnSO4·7H2O powder and the Na2S·9H2O powder were added to a ball mill and ground for 30 min. The mixture was thoroughly mixed to obtain a premix.

[0064] (3) Add the above hydrogen peroxide solution to the premix and react for 40 minutes under grinding. The reaction is completed to obtain a crude product;

[0065] (4) The crude product was washed with deionized water and filtered three times, and then filtered to obtain a filter cake; and the filter cake was vacuum dried at 80°C for 8 hours to obtain face-centered cubic nano-zinc sulfide.

[0066] Example 4

[0067] Example 4 provides a hexagonal nano-zinc sulfide.

[0068] The above-mentioned preparation method of hexagonal nano zinc sulfide is prepared by the following steps:

[0069] The face-centered cubic nano-zinc sulfide prepared in Example 3 was calcined at 500° C. for 2 h under vacuum conditions to obtain hexagonal nano-zinc sulfide.

[0070] Example 5

[0071] Example 5 provides a face-centered cubic nano-zinc sulfide.

[0072] The above-mentioned method for preparing face-centered cubic nano zinc sulfide is prepared by the following steps:

[0073] (1) Weigh 25.90 g of ZnCl2, place it in a ball mill, and grind it for 30 min to obtain ZnCl2 powder; weigh 20.95 g of K2S, place it in a ball mill, and grind it for 30 min to obtain K2S powder; weigh 2.15 g of 30% H2O2, dissolve it in 97.85 g of deionized water to prepare a hydrogen peroxide solution with a H2O2 mass content of 0.65 wt%.

[0074] (2) Add the ZnCl2 powder and K2S powder into a ball mill at room temperature, grind for 30 min, and mix thoroughly to obtain a premix;

[0075] (3) Add the above hydrogen peroxide solution to the premix and react for 50 minutes under grinding. The reaction is completed to obtain a crude product;

[0076] (4) The crude product was washed with deionized water and filtered three times, and then filtered to obtain a filter cake; and the filter cake was vacuum dried at 80°C for 8 hours to obtain face-centered cubic nano-zinc sulfide.

[0077] Example 6

[0078] Example 6 provides a hexagonal nano-zinc sulfide.

[0079] The above-mentioned preparation method of hexagonal nano zinc sulfide is prepared by the following steps:

[0080] The face-centered cubic nano-zinc sulfide prepared in Example 5 was calcined at 550° C. for 2 h under vacuum conditions to obtain hexagonal nano-zinc sulfide.

[0081] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention. Therefore, such modifications and improvements, which do not depart from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A method for preparing face-centered cubic nano zinc sulfide, characterized in that: The following steps are involved: (1) Mixing and grinding the inorganic zinc salt and the inorganic sulfur salt to obtain a premix; (2) adding a catalyst solution to the premix, reacting under grinding for 40-60 minutes to obtain a crude product; The catalyst solution is a 0.3-0.8 wt% hydrogen peroxide solution; (3) The crude product is washed, filtered, filter-pressed, and vacuum-dried to obtain face-centered cubic nano-zinc sulfide.

2. The method for preparing face-centered cubic nano zinc sulfide according to claim 1, wherein: The inorganic zinc salt is selected from zinc nitrate hexahydrate, zinc sulfate heptahydrate and zinc chloride; the inorganic sulfur salt is selected from barium sulfide, sodium sulfide nonahydrate and potassium sulfide.

3. The method for preparing face-centered cubic nano zinc sulfide according to claim 1, wherein: The molar ratio of the inorganic zinc salt to the inorganic sulfur salt is 1:(0.9-1.1).

4. The method for preparing face-centered cubic nano zinc sulfide according to claim 1, wherein: The vacuum drying temperature is 70-90° C. and the time is 8-10 h.

5. A face-centered cubic nano zinc sulfide, characterized in that: The nano zinc sulfide is prepared by the method for preparing the face-centered cubic crystal according to any one of claims 1 to 4.

6. A method for preparing hexagonal nano zinc sulfide, characterized in that: The following steps are involved: The face-centered cubic nano-zinc sulfide according to claim 5 is calcined at 500-600° C. for 1-2 hours under vacuum conditions to obtain hexagonal nano-zinc sulfide.

7. A hexagonal nano zinc sulfide, characterized in that: The nano zinc sulfide is prepared by the method for preparing hexagonal crystal nano zinc sulfide according to claim 6.

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