Environment-friendly zinc sulfide nanoparticles, preparation method and application thereof

Abstract

The application relates to the technical field of semiconductor nanomaterials, and discloses an environment-friendly zinc sulfide nanoparticle as well as a preparation method and application of the zinc sulfide nanoparticle. The preparation method comprises the following steps: (1) activating Aspergillus oryzae spores, performing liquid fermentation, filtering the liquid fermentation product, washing, collecting solid substances, and obtaining biomass; (2) culturing the biomass in the step (1) in a ZnSO4.7H2O aqueous solution to obtain an Aspergillus oryzae liquid solution containing zinc sulfide nanoparticles; (3) drying the liquid solution obtained in the step (2) to obtain Aspergillus oryzae precipitate containing zinc sulfide nanoparticles; and (4) heating the precipitate in the step (3) at 400-450 DEG C for 4-6 h to obtain zinc sulfide nanoparticles. The application endows the zinc sulfide nanoparticles with excellent biocompatibility, expands the application of the zinc sulfide nanoparticles in the fields of biomedicine, chemical sensors, solar cells and light-emitting diodes, and provides a reference for the environment-friendly and batch production of the zinc sulfide nanoparticles.

Description

Technical Field

[0001] This invention relates to the field of semiconductor nanomaterials technology, specifically to an environmentally friendly zinc sulfide nanoparticle, its preparation method, and its application. Background Technology

[0002] Zinc sulfide nanoparticles, as a direct wide-bandgap semiconductor nanomaterial, boast a high room-temperature bandgap of 3.6–3.8 eV and an exciton binding energy as high as 40 meV. Because excitons with large binding energies are more likely to achieve high-efficiency excitation and emission at room temperature at relatively low excitation energies, zinc sulfide is also considered a short-wavelength luminescent material with great application potential. Furthermore, studies have shown that the emission wavelength range of zinc sulfide nanoparticles can extend from 350 nm to 750 nm. In addition, it contains no toxic elements, its preparation method is simple, and the raw materials are inexpensive and readily available, demonstrating great application potential in chemical sensors, biosensors, cell imaging, biofluorescent labeling, solar cells, and light-emitting diodes. Currently, numerous methods for synthesizing zinc sulfide nanoparticles have been reported, such as hydrothermal methods, sol-gel methods, precipitation methods, microemulsion methods, spray pyrolysis methods, and solid-phase methods. However, these physicochemical methods can cause environmental pollution, hindering large-scale industrial production.

[0003] One solution to this problem is biosynthesis, a method that has attracted considerable attention from researchers due to its safety, biofriendliness, and biocompatibility. Among various organisms, bacteria, being prokaryotes, are easily cultured autonomously in the laboratory and grow rapidly, making them an excellent carrier for synthesizing nanomaterials. Compared to bacteria, using fungi to prepare nanoparticles offers even greater convenience, such as the fact that the nanoparticles, precipitated outside the cells, do not contain cellular components and can be directly applied in various fields. Extensive research has demonstrated that biosynthesis is simple, inexpensive, and environmentally friendly compared to physical and chemical methods, making it widely applicable to the synthesis of zinc sulfide nanomaterials. However, there are no reports of using Aspergillus oryzae fungi to prepare zinc sulfide nanoparticles. Summary of the Invention

[0004] This invention provides an environmentally friendly zinc sulfide nanoparticle, its preparation method, and its application. It solves the problem that existing technologies do not use Aspergillus oryzae fungi to prepare zinc sulfide nanoparticles, expands the application of ZnS nanoparticles in biomedicine, chemical sensors, solar cells, and light-emitting diodes, and provides a reference for the environmental protection and mass production of zinc sulfide nanoparticles.

[0005] This invention discloses a method for preparing environmentally friendly zinc sulfide nanoparticles, the specific steps of which include:

[0006] (1) Activate Aspergillus oryzae strain, liquid ferment, filter the liquid fermentation product, wash, collect solid material to obtain biomass;

[0007] (2) The biomass in (1) was transferred to an aqueous solution of ZnSO4·7H2O and cultured at 30-40℃ for 90-100h to obtain a liquid solution of Aspergillus oryzae containing zinc sulfide nanoparticles.

[0008] (3) The liquid solution obtained in (2) is dried at 70-75°C for 24-28 hours to obtain Aspergillus oryzae precipitate containing zinc sulfide nanoparticles;

[0009] (4) Heat the precipitate from (3) at 400-450℃ for 4-6 hours to obtain zinc sulfide nanoparticles.

[0010] Preferably, the Aspergillus oryzae is Aspergillus oryzae strain 3.042.

[0011] Preferably, step (1) specifically involves inoculating Aspergillus oryzae into a liquid culture medium and culturing it for 4 to 5 days under stirring and at 30 to 40°C. Then, the liquid culture medium is filtered, washed, and the solid material is collected to obtain biomass.

[0012] Preferably, the liquid culture medium described in (1) is prepared by mixing potatoes, glucose and deionized water together and sterilizing them at 113-116℃ and 103.4kPa for 20-30 minutes to obtain the liquid culture medium; the raw material ratio of the liquid culture medium is potato: glucose: deionized water = 10g: 1g: 50mL.

[0013] Preferably, the stirring speed described in (1) is 150 to 200 rpm.

[0014] Preferably, the washing process described in (1) involves washing with distilled water or deionized water 2-3 times.

[0015] Preferably, in (2), the ZnSO4·7H2O aqueous solution is made by mixing ZnSO4·7H2O powder with water at a ratio of 0.08627g:100mL.

[0016] Preferably, in (2), the material-to-liquid ratio is biomass:ZnSO4·7H2O aqueous solution = 10g:100.08627g.

[0017] The second objective of this invention is to provide an environmentally friendly zinc sulfide nanoparticle.

[0018] The third objective of this invention is to apply the prepared environmentally friendly zinc sulfide nanoparticles to the fields of biomedicine, chemical sensors, solar cells, and light-emitting diodes.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] Zinc sulfide nanoparticles were prepared using *Aspergillus oryzae*. The method involves the absorption of zinc ions by *Aspergillus oryzae* cells, followed by bioreduction and assembly to obtain zinc sulfide nanoparticles. This method offers advantages such as being environmentally friendly, resource-saving, easy to operate, and producing products with excellent biocompatibility, thus broadening the application of zinc sulfide nanoparticles in the biomedical field. Therefore, using the green and pollution-free *Aspergillus oryzae* to synthesize zinc sulfide nanoparticles not only solves the environmental pollution problems associated with physical and chemical synthesis methods but also endows zinc sulfide nanoparticles with excellent biocompatibility, expanding the applications of ZnS nanoparticles in biomedicine, chemical sensors, solar cells, and light-emitting diodes. This provides a reference and model for the environmentally friendly and mass production of zinc sulfide nanoparticles. Attached Figure Description

[0021] Figure 1 X-ray diffraction pattern of ZnS nanoparticles prepared in this invention;

[0022] Figure 2 Transmission microscope image (a) and high-resolution transmission microscope image (b) of ZnS nanoparticles prepared in Example 1 of the present invention;

[0023] Figure 3 Transmission microscope image (a) and high-resolution transmission microscope image (b) of ZnS nanoparticles prepared in Example 2 of the present invention;

[0024] Figure 4 Transmission microscope image (a) and high-resolution transmission microscope image (b) of ZnS nanoparticles prepared in Example 3 of the present invention;

[0025] Figure 5 The infrared spectrum of the ZnS nanoparticles prepared in this invention. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Unless otherwise specified, the experimental methods described in the various embodiments of this invention are conventional methods. Unless otherwise specified, the materials and reagents used are commercially available.

[0028] Example 1

[0029] A method for preparing environmentally friendly zinc sulfide nanoparticles, wherein the raw material dosage conditions are as follows:

[0030] 80g potatoes, 8g glucose, 500mL deionized water, Aspergillus oryzae, 0.08627g ZnSO4·7H2O.

[0031] The preparation steps and conditions are as follows:

[0032] (1) Peel and cut the potatoes into pieces, mix them with glucose and 400 mL of deionized water, and autoclave them at 113℃ and 103.4 kPa for 20 min to obtain liquid culture medium;

[0033] (2) Aspergillus oryzae (3.042) was inoculated into 1L of liquid culture medium in (1) and cultured at 150 rpm and 30°C for 4 days. The liquid culture medium was then filtered and washed twice with deionized water to obtain biomass.

[0034] (3) Dissolve ZnSO4·7H2O in 100mL of deionized water to obtain an aqueous solution of ZnSO4·7H2O with a concentration of 3mmol / L;

[0035] (4) Weigh 10g of the biomass obtained in (2) and transfer it to the ZnSO4·7H2O aqueous solution obtained in (3). Cultivate at 30℃ for 90h to obtain Aspergillus oryzae liquid solution containing zinc sulfide nanoparticles.

[0036] (5) The liquid solution obtained in (4) was dried at 70°C for 24 hours to obtain Aspergillus oryzae precipitate containing zinc sulfide nanoparticles;

[0037] (6) Place the black powder from (5) in a muffle furnace and heat at 400°C for 4 hours to obtain white powdered zinc sulfide nanoparticles.

[0038] Example 2

[0039] A method for preparing environmentally friendly zinc sulfide nanoparticles, wherein the raw material dosage conditions are as follows:

[0040] 40g potato, 4g glucose, 300mL deionized water, Aspergillus oryzae, 0.08627g ZnSO4·7H2O.

[0041] The preparation steps and conditions are as follows:

[0042] (1) Peel and cut the potatoes into pieces, mix them with glucose and 200 mL of distilled water, and autoclave them at 115℃ and 103.4 kPa for 25 min to obtain liquid culture medium;

[0043] (2) Inoculate Aspergillus oryzae (3.042) into 1L of liquid culture medium in (1) and culture at 180 rpm and 35°C for 5 days. Filter the liquid culture medium and wash it twice with distilled water to obtain biomass.

[0044] (3) Dissolve ZnSO4·7H2O in 100mL of deionized water to obtain an aqueous solution of ZnSO4·7H2O with a concentration of 3mmol / L;

[0045] (4) Weigh 10g of the biomass obtained in (2) and transfer it to the ZnSO4·7H2O aqueous solution obtained in (3). Cultivate at 35℃ for 96h to obtain Aspergillus oryzae liquid solution containing zinc sulfide nanoparticles.

[0046] (5) The liquid solution obtained in (4) was dried at 73°C for 26 h to obtain Aspergillus oryzae precipitate containing zinc sulfide nanoparticles;

[0047] (6) Place the precipitate from (5) in a muffle furnace and heat it at 430°C for 5 hours to obtain white powdered zinc sulfide nanoparticles.

[0048] Example 3

[0049] A method for preparing environmentally friendly zinc sulfide nanoparticles, wherein the raw material dosage conditions are as follows:

[0050] 60g potato, 6g glucose, 400mL deionized water, Aspergillus oryzae, 0.08627g ZnSO4·7H2O.

[0051] The preparation steps and conditions are as follows:

[0052] (1) Peel and cut the potatoes into pieces, mix them with glucose and 300 mL of deionized water, and autoclave them at 116 °C and 103.4 kPa for 30 min to obtain liquid culture medium.

[0053] (2) Aspergillus oryzae (3.042) was inoculated into 1L of liquid culture medium in (1) and cultured at 200 rpm and 40°C for 5 days. The liquid culture medium was then filtered and washed 3 times with deionized water to obtain biomass.

[0054] (3) Dissolve ZnSO4·7H2O in 100mL of deionized water to obtain an aqueous solution of ZnSO4·7H2O with a concentration of 3mmol / L;

[0055] (4) Weigh 10g of the biomass obtained in (2) and transfer it to the ZnSO4·7H2O aqueous solution obtained in (3). Cultivate at 40℃ for 100h to obtain Aspergillus oryzae liquid solution containing zinc sulfide nanoparticles.

[0056] (5) The liquid solution obtained in (4) was dried at 75°C for 28 hours to obtain Aspergillus oryzae precipitate containing zinc sulfide nanoparticles;

[0057] (6) The precipitate in (5) was placed in a muffle furnace and heated at 450°C for 6 hours to obtain white powdered zinc sulfide nanoparticles.

[0058] Identification of zinc sulfide nanoparticles synthesized using the methods described in the embodiments of this invention

[0059] like Figure 1 As shown, by Figure 1 The X-ray diffraction (XRD) pattern clearly shows that 13 characteristic diffraction peaks of ZnS nanoparticles correspond to the diffraction planes (0033), (0036), (0042), (1013), (1025), (1028), (1034), (1043), (1046), (0159), (2011), (2017), and (1097), respectively. The corresponding diffraction peak positions are 18.200°, 21.940°, 24.580°, 28.360°, 30.739°, 31.778°, 33.820°, 37.302°, 38.960°, 44.760°, 55.958°, 56.638°, and 66.456°, which are in good agreement with the standard JCPDS card (No. 89-2425). According to the Debey-Scherrer formula, the average grain size of the obtained sample is approximately 18.2 nm, indicating that the obtained sample is a hexagonal wurtzite structure ZnS nanoparticle.

[0060] like Figures 2-4 As shown, Figures 2-4 The images shown are transmission microscopy (TEM) and high-resolution TEM images of the ZnS nanoparticles prepared in Examples 1-3, respectively. Due to the small size of the samples and their high surface energy, aggregation occurs. The size of the ZnS nanoparticles is 10.1–16.5 nm, which is consistent with... Figure 1 The test results were consistent.

[0061] like Figure 5 As shown, at a wavenumber of 698 cm⁻¹ -1 The characteristic peak at 1436 cm⁻¹ represents the disulfide bonds in ZnS nanoparticles, while the peak at 1436 cm⁻¹ represents the disulfide bonds in ZnS nanoparticles. -1 1558cm -1 and 1731cm -1 The strong peak at 2925 cm⁻¹ corresponds to the vibrational bands of amide I and II. -1 and 3390cm -1The absorption peaks at these locations correspond to the stretching vibrations of CH and OH, respectively. This indicates that small organic molecules exist on the surface of the ZnS nanoparticles synthesized using Aspergillus oryzae, and these small organic molecules can improve the biocompatibility of ZnS nanoparticles to meet the application requirements in the field of biolabeling.

[0062] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention.

[0063] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A method for preparing environmentally friendly zinc sulfide nanoparticles, characterized in that, The specific steps include: (1) Activate the Aspergillus oryzae strain, perform liquid fermentation, filter the liquid fermentation product, wash it, collect the solid material, and obtain biomass; the Aspergillus oryzae strain is Aspergillus oryzae 3.042; (2) The biomass in (1) was transferred to an aqueous solution of ZnSO4·7H2O and cultured at 30~40°C for 90~100h to obtain a liquid solution of Aspergillus oryzae containing zinc sulfide nanoparticles; (3) The liquid solution obtained in (2) is dried at 70~75°C for 24~28h to obtain Aspergillus oryzae precipitate containing zinc sulfide nanoparticles; (4) Heat the precipitate in (3) at 400~450°C for 4~6h to obtain zinc sulfide nanoparticles.

2. The method for preparing environmentally friendly zinc sulfide nanoparticles as described in claim 1, characterized in that, (1) The specific steps are as follows: inoculate Aspergillus oryzae into liquid culture medium, and after stirring and culturing at 30-40°C for 4-5 days, filter the liquid culture medium, wash it, collect the solid material, and obtain biomass.

3. The method for preparing environmentally friendly zinc sulfide nanoparticles as described in claim 2, characterized in that, The preparation method of the liquid culture medium described in (1) is as follows: mix potatoes, glucose and deionized water together and sterilize them at 113~116℃ and 103.4kPa for 20~30min to obtain liquid culture medium; the raw material ratio of liquid culture medium is potato: glucose: deionized water = 10g: 1g: 50mL.

4. The method for preparing environmentally friendly zinc sulfide nanoparticles as described in claim 2, characterized in that, The stirring speed mentioned in (1) is 150~200 rpm.

5. The method for preparing environmentally friendly zinc sulfide nanoparticles as described in claim 1, characterized in that, (1) Wash with distilled water or deionized water 2-3 times during the washing process.

6. The method for preparing environmentally friendly zinc sulfide nanoparticles as described in claim 1, characterized in that, (2) The ZnSO4·7H2O aqueous solution is made by mixing ZnSO4·7H2O powder with water at a ratio of 0.08627g:100mL.

7. The method for preparing environmentally friendly zinc sulfide nanoparticles as described in claim 1, characterized in that, (2) The ratio of biomass to ZnSO4·7H2O aqueous solution is 10g: 100.08627g.

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