Preparation method of hollow self-assembled hollow InOOH nanosphere structure
By preparing hollow self-assembled hollow InOOH nanospheres, the problem of the difficulty in growing binary metal oxides was solved, and the photocatalytic activity and light energy conversion efficiency were improved, making it suitable for photocatalytic degradation of tetracycline.
Patent Information
- Application Number
- CN202411419318.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-12
- Publication Date
- 2025-01-14
AI Technical Summary
In the current field of photocatalysis, the growth kinetics of binary metal oxides are difficult to control, which makes it difficult to synthesize highly self-assembled single-crystal compounds and affects photocatalytic activity.
A method for preparing hollow self-assembled hollow InOOH nanospheres was adopted. Indium nitrate was dissolved by mixing ethylene glycol and pure water, heated in a hydrothermal high-pressure reactor, cooled, washed and dried to form pure-phase hollow InOOH nanospheres. The hollow structure and charge transfer characteristics were used to improve photocatalytic performance.
It improves the photocatalytic degradation activity of tetracycline, enhances the separation efficiency of photogenerated electron-hole pairs and the light energy conversion capability, and achieves efficient mass transport and photon capture.
Smart Images
Figure CN119306248A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of new materials, and in particular to a method for preparing a hollow self-assembled hollow InOOH nanosphere structure. Background Art
[0002] With the development of medicine, antibiotics are widely used as drugs to treat humans and animals, resulting in increasingly serious environmental pollution and a growing threat to human health and the balance of the ecosystem. Tetracycline is widely used as an antibiotic in the fields of medicine, hygiene, science, etc., but it is difficult to be degraded in nature, especially in water. Therefore, it is very meaningful to mineralize tetracycline from a polluted environment. Photocatalytic degradation of tetracycline can directly convert solar energy into chemical energy, degrade pollutants in water, thereby achieving a win-win situation for energy and the environment, and is an ideal way to achieve ecological civilization and sustainable development.
[0003] Photocatalytic technology has attracted extensive attention from scientists due to its advantages such as low cost, high efficiency and good stability. There are many factors that affect photocatalytic activity, such as the size, morphology, exposure sites and structure of the catalyst. Self-assembled single crystals are a new type of superstructure with potentially excellent photochemical properties. Thanks to the charge transfer between building blocks, they can be widely used in photocatalysis, electrocatalysis, energy conversion, optoelectronics and bio-labeling.
[0004] In the field of photocatalysis, an increasing number of binary metal oxides have been synthesized, but they usually exhibit common spherical, plate or rod-like morphologies, and since binary metal oxides increase the difficulty of kinetic control over growth, it is very difficult to synthesize highly self-assembled single crystalline compounds thereafter. Summary of the invention
[0005] In order to overcome the shortcomings of binary metal oxides in the existing photocatalytic field that increase the difficulty of kinetic control of growth and it is very difficult to synthesize highly self-assembled single crystal compounds thereafter, an embodiment of the present application provides a method for preparing a hollow self-assembled hollow InOOH nanosphere structure.
[0006] The technical solution adopted by the embodiment of the present application to solve the technical problem is:
[0007] A method for preparing a hollow self-assembled hollow InOOH nanosphere structure comprises the following steps: 1. fusing 10 ml of ethylene glycol and 5 ml of pure water to obtain a solution A;
[0008] Step 2: Add 0.3 mmol of indium nitrate tetrahydrate to the mixed solution A, then add 0.15 ml of acetic acid and stir for 10 min to obtain solution B after complete dissolution;
[0009] Step 3: Transfer solution B to a hydrothermal autoclave with an internal volume of 20 ml;
[0010] Step 4: Place the hydrothermal autoclave in an electric oven for heating, and then cool naturally to room temperature;
[0011] Step 5: The product is washed with deionized water and ethanol, centrifuged, and then dried in a freeze dryer to obtain a hollow self-assembled hollow InOOH nanosphere structure.
[0012] In a possible implementation, the concentration of ethylene glycol used in step 1 is 99%, and the fusion of ethylene glycol and pure water is carried out by ultrasonic stirring of deionized water.
[0013] In a possible implementation, the concentration of indium nitrate in step 2 is 99.99%, and indium nitrate, acetic acid and mixed solution A are mixed by ultrasonic and magnetic stirring.
[0014] In a possible implementation, in step 3, the hydrothermal autoclave is heated in an electric oven to a temperature of 180° C. and the heating is continued for 12 hours.
[0015] In a possible implementation, the products produced in steps 1 to 5 are measured using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and high-power scanning electron microscopy to observe the internal and external structural characteristics of the products.
[0016] In a possible implementation, the products produced in step 1 to step 5 are compared with a comparative example, and the comparative example includes star-shaped InOOH nanospheres and linear InOOH nanospheres.
[0017] In a possible implementation, the synthesis of the comparative example of star-shaped InOOH nanospheres comprises: S1, 0.88 ml of InCl 3 aqueous solution, 5 ml of water and 0.367 g of NaAc·3H 2 O is put into a beaker and stirred to form a clear solution with a pH of about 6, and 24.0 ml of ethylene glycol is added during the stirring process; S2, after waiting for 10 minutes, the mixed solution is transferred to a hydrothermal autoclave with a capacity of 50 mL, and the hydrothermal autoclave is heated at 180°C for 12 hours.
[0018] In a possible implementation, the synthesis of the linear InOOH nanosphere comparative example comprises: S1, 0.1 g of InCl 3 ·4H 2 O is dispersed in a mixture of 6 ml oleylamine and 10 ml ethanol; S2, the mixture is placed in a 25 ml hydrothermal kettle and heated at 150°C for 10 hours.
[0019] The beneficial effects of this application are:
[0020] 1. The method of preparing hollow self-assembled hollow InOOH nanospheres in this scheme is simple and easy, and the reaction conditions are mild. The self-assembled hollow InOOH nanospheres can improve the activity of photocatalytic degradation of tetracycline. The empty pore structure in the nanospheres is conducive to light penetration and carrier diffusion, thereby achieving efficient material transport.
[0021] 2. In this scheme, charge transfer between adjacent building blocks in the preparation of hollow self-assembled InOOH nanospheres is adopted to improve the separation efficiency of photogenerated electron-hole pairs, thereby extending the lifetime of photoexcited carriers. In addition, the hollow structure can act as a photon capture trap, capturing more incident photons through multiple scattering to generate more electron-hole pairs, thereby enhancing light energy conversion. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 is an X-ray diffraction (XRD) diagram of the product in the embodiment of the present invention;
[0023] Figure 2 This is a scanning electron microscope (SEM) image of the product in the embodiment of the present invention;
[0024] Figure 3 (a) and (b) are transmission electron microscopy (TEM) images of the product in the embodiment of the present invention, and (c) is a high resolution transmission electron microscopy (HRTEM) image of the product in the embodiment;
[0025] Figure 4 This is a scanning electron microscope (SEM) image of the present invention at a high magnification;
[0026] Figure 5 It is a line graph of the degradation performance of the three catalysts of the present invention. DETAILED DESCRIPTION
[0027] The technical solution in the embodiment of the present application is to solve the problems of the above-mentioned background technology, and the overall idea is as follows:
[0028] 1) Embodiment:
[0029] This embodiment introduces a specific structure of a method for preparing a hollow self-assembled hollow InOOH nanosphere structure. Figure 1-Figure 4 As shown, including:
[0030] S1. Mix 10 ml of ethylene glycol and 5 ml of pure water, and use ultrasound to completely dissolve the ethanol and pure water to obtain solution A.
[0031] S2, 0.3mmol indium nitrate (InCl 3) tetrahydrate was added to the mixed solution A, and then 0.15 ml of acetic acid (CH 3 COOH), and stirred and mixed by magnetic stirring for 10 min until completely dissolved, thereby obtaining solution B;
[0032] S3, transfer solution B to a hydrothermal autoclave with an internal volume of 20 ml;
[0033] S4, placing the hydrothermal autoclave in an electric oven, heating at 180° C. for 12 hours, and cooling naturally to room temperature;
[0034] S5. The product is washed with deionized water and ethanol, centrifuged, and finally dried in a freeze dryer to obtain hollow self-assembled hollow InOOH nanospheres.
[0035] Among them, for the product in this embodiment, X-ray powder diffraction (XRD) (X-ray diffraction abbreviation), the details are as follows: patterns of the samples were obtained using a BrukerD8 Advance Diffractometer (USA) with Cu Kα radiation (λ=0.15406nm) and measurement at angles(angle) of 20–70°at a step size(step length) of 0.02°) to determine the crystal structure of the synthesized self-assembled hollow InOOH nanospheres, which are as follows Figure 1 As shown, all X-ray diffraction peaks are consistent with the orthorhombic InOOH standard card (JCPDS NO.71-2283). When no diffraction peaks of impurities are detected, it can be shown that the InOOH product is pure phase;
[0036] Secondly, for the product in this example, the morphologies of the prepared samples were studied via field emissionscanning electron microscopy(Tescan MIRA LMS,Czech)and transmission electron microscopy(JEOL,JEM-F200,Japan)) to determine the crystal structure of the synthesized self-assembled hollow InOOH nanospheres, as shown in FIG. Figure 2As shown, the prepared InOOH single crystal has a diameter of 500-800nm, and is monodispersed, uniform in size, and hollow. Each InOOH structure is actually composed of a large number of small nanospheres with an average size of about 20-30 nanometers. These nanospheres are in close contact with each other, stacked, and arranged neatly;
[0037] Furthermore, for the product in this example, the morphologies of the prepared samples were studied via field emissionscanning electron microscopy (Tescan MIRA LMS, Czech) and transmission electron microscopy (JEOL, JEM-F200, Japan) to determine the crystal structure of the synthesized self-assembled hollow InOOH nanospheres, as shown in FIG. Figure 3 As shown, Figure 3 (a) The contrast between the dark edge and the light center confirms its hollow structure, and the pore structure is clearly visible; Figure 3 As shown by the arrow in (b), it may come from the gaps between the stacked nanospheres. The high-resolution image confirms that the lattices of different nanohollow spheres adopt the same orientation ( Figure 3 (c)), indicating potential homoepitaxial aggregation;
[0038] At the same time, the crystal structure of the synthesized self-assembled hollow InOOH nanospheres was determined by high-power scanning electron microscopy (SEM). Figure 4 As shown, the particles on the surface have an average size of about 20-30 nanometers; the average size of the InOOH composed of the whole is about 500-800 nanometers, with a rough surface and a hollow interior.
[0039] 2) Comparative Example:
[0040] In order to study the relationship between the high degree of self-assembled superstructure and performance, two types of InOOH nanocrystals with different morphologies from the products in the examples were used for comparison:
[0041] (a) The synthesis of star-shaped InOOH is as follows:
[0042] S1, 0.88 ml of InCl 3 Aqueous solution (0.51M volume molar concentration), 5 ml of water and 0.367 g of NaAc·3H 2 O was placed in a beaker and stirred to form a clear solution with a pH of about 6, and 24.0 ml of ethylene glycol was added during stirring;
[0043] S2. After waiting for 10 minutes, the mixed solution was transferred to a hydrothermal autoclave with a capacity of 50 mL, and the hydrothermal autoclave was heated at 180° C. for 12 hours.
[0044] (b) The preparation of linear InOOH is as follows:
[0045] S1, 0.1g InCl 3 ·4H 2 O was dispersed in a mixture of 6 ml oleylamine and 10 ml ethanol;
[0046] S2. Place the above mixed solution in a 25 ml hydrothermal kettle and heat at 150°C for 10 hours.
[0047] Based on the three InOOH samples obtained in the examples and comparative examples: self-assembled hollow InOOH, star-shaped, and linear, they were used as photocatalysts to photocatalytically degrade tetracycline:
[0048] First, 80 mg of the catalyst was dispersed in 100 mL of a 20 mg·L-1 sodium sulfate (tetracycline) solution and stirred in the dark for 1 h to reach equilibrium;
[0049] Then, a 300W xenon lamp with a 420nm filter was used as the light source, and 2mL of the suspension was taken out every 20 minutes. Except for the use of 20mg·L-1 tetracycline solution, photocatalytic removal of tetracycline pollutants was used under all other conditions, and tetracycline was measured at 357nm (for stability and recyclability experiments, the used catalyst was washed with 0.5mol·L-1 HNO 3 , ethanol and water for three times, and then dried in a freeze dryer for later use);
[0050] Then, the absorption spectra of the samples were measured using a UV-visible spectrophotometer (UV-2550, Shimadzu, Japan) and the degradation calibration was performed by using the absorbance method at a wavelength of 357 nm and deionized water solution as the standard sample.
[0051] Finally, the photocatalytic degradation performance of the products of the embodiments and comparative examples was calculated, and the specific conditions of the degradation performance of the three catalysts were as follows: Figure 5 As shown, the self-assembled hollow InOOH single crystal has the best photocatalytic degradation performance, the degradation effect becomes more significant with the increase of reaction time, and the degradation efficiency is the highest.
[0052] In the process of photocatalytic degradation by photocatalyst, the reference data are as follows:
[0053] Time Ct / Co(empty ball) Ct / Co(Linear) Ct / Co(star) 0 1 1 1 20 0.8 0.57 0.77 40 0.7 0.51 0.66 60 0.6 0.43 0.55
[0054] Finally, it should be noted that: Obviously, the above embodiments are only examples for clearly explaining the present invention, and are not intended to limit the implementation methods. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the scope of protection of the present invention.
Claims
1. A method for preparing a hollow self-assembled hollow InOOH nanosphere structure, characterized in that: include: Step 1: Mix 10 ml of ethylene glycol and 5 ml of pure water to obtain solution A; Step 2: Add 0.3 mmol of indium nitrate tetrahydrate to mixed solution A, then add 0.15 ml of acetic acid and stir for 10 min to obtain solution B after complete dissolution; Step 3: Transfer solution B to a hydrothermal autoclave with an internal volume of 20 ml; Step 4: Place the hydrothermal autoclave in an electric oven for heating, and then cool naturally to room temperature; Step 5: The product is washed with deionized water and ethanol, centrifuged, and then dried in a freeze dryer to obtain a hollow self-assembled hollow InOOH nanosphere structure.
2. The method for preparing a hollow self-assembled hollow InOOH nanosphere structure according to claim 1, characterized in that: The concentration of ethylene glycol used in step 1 is 99%, and the fusion of ethylene glycol and pure water is carried out by ultrasonic stirring with deionized water.
3. The method for preparing a hollow self-assembled hollow InOOH nanosphere structure according to claim 1, characterized in that: In the step 2, the concentration of indium nitrate is 99.99%, and indium nitrate, acetic acid and mixed solution A are mixed by ultrasonic and magnetic stirring.
4. The method for preparing a hollow self-assembled hollow InOOH nanosphere structure according to claim 1, characterized in that: In the step 3, the hydrothermal autoclave is heated in an electric oven at a temperature of 180° C. and the heating is continued for 12 hours.
5. The method for preparing a hollow self-assembled hollow InOOH nanosphere structure according to claim 1, characterized in that: The products produced in steps 1 to 5 are measured using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and high-power scanning electron microscopy to observe the internal and external structural characteristics of the products.
6. The method for preparing a hollow self-assembled hollow InOOH nanosphere structure according to claim 1, characterized in that: The products produced in step 1 to step 5 are compared with a comparative example, which includes star-shaped InOOH nanospheres and linear InOOH nanospheres.
7. The method for preparing a hollow self-assembled hollow InOOH nanosphere structure according to claim 6, characterized in that: The synthesis of the comparative example of star-shaped InOOH nanospheres includes: S1, putting 0.88 ml of InCl3 aqueous solution, 5 ml of water and 0.367 g of NaAc·3H2O into a beaker, stirring to form a clear solution with a pH of about 6, and adding 24.0 ml of ethylene glycol during the stirring process; S2, after waiting for 10 minutes, transferring the mixed solution to a hydrothermal kettle with a capacity of 50 mL, and heating the hydrothermal kettle at 180°C for 12 hours.
8. The method for preparing a hollow self-assembled hollow InOOH nanosphere structure according to claim 6, characterized in that: The synthesis of the comparative example of linear InOOH nanospheres includes: S1, dispersing 0.1 g of InCl3·4H2O into a mixture of 6 ml of oleylamine and 10 ml of ethanol; S2, placing the mixture in a 25 ml hydrothermal kettle and heating it at 150° C. for 10 hours.