Preparation method and application of hollow urchin-like 1D / 3D NiCuCo heterostructure nanomaterial

Abstract

The application discloses a preparation method and application of a hollow urchin-like 1D / 3D NiCuCo heterostructure nanomaterial. The application combines Ni, Cu and Co together under the action of urea through a simple hydrothermal method, and then centrifugation, washing and freeze-drying are carried out to prepare the hollow urchin-like 1D / 3D NiCuCo heterostructure nanomaterial. The prepared hollow urchin-like 1D / 3D NiCuCo heterostructure nanomaterial has more active sites, can promote PMS to generate more free radicals, efficiently degrades pollutants in water, and can degrade pollutants by about 95% in 5 minutes, and has good stability. The application has the characteristics of high economic benefit and simple preparation process, and has good economic benefit and environmental benefit.

Description

Technical Field

[0001] The present invention belongs to the field of material technology, and in particular relates to a preparation method and application of a hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial. Background Art

[0002] Peroxymonosulfate (PMS) oxidation technology (also known as peroxymonosulfate system) is an advanced oxidation technology used to degrade pollutants in water. This technology utilizes persulfate (PMS, often referred to as peroxymonosulfate, Oxone, or sodium or potassium persulfate) as an oxidant. Under appropriate conditions, it generates highly reactive sulfate radicals (SO₄•⁻). These radicals are capable of non-selectively oxidizing and mineralizing organic pollutants in water. Key bottlenecks faced by PMS systems in degrading pollutants in water include controversy over the type of active oxidant, the influence of pH, the complexity of pollutants in actual water bodies, the formation and action of singlet oxygen, catalyst cycle stability, and optimization of PMS concentration.

[0003] Therefore, it is necessary to find a material that can be stably applied to the PMS system. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method for synthesizing hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterials. The present invention utilizes a simple hydrothermal synthesis method to combine three metals, Ni, Cu, and Co, under the action of urea, and then centrifuges, washes, and freeze-dries to form a hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial. The present invention provides a green synthesis method for hollow sea urchin-shaped 1D / 3DNiCuCo heterostructure nanomaterials that is simple to prepare, versatile, and highly applicable. Moreover, the prepared hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial can effectively degrade pollutants in water. The method is simple, low-cost, and has good economic and environmental benefits.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for preparing a hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial comprises the following steps:

[0007] (1) dissolving a divalent nickel salt, a divalent copper salt, a divalent cobalt salt, and urea in ultrapure water to obtain a mixed solution, and uniformly dispersing the solution by ultrasonication;

[0008] (2) The mixed solution obtained in step (1) was transferred to a polytetrafluoroethylene reactor and placed in an oven for hydrothermal reaction;

[0009] (3) The solution obtained in step (2) is centrifuged and freeze-dried to obtain a hollow sea urchin-like 1D / 3D NiCuCo heterostructure nanomaterial.

[0010] Furthermore, in step (1), the divalent nickel salt is nickel chloride hexahydrate, the divalent copper salt is copper chloride dihydrate, and the divalent cobalt salt is cobalt chloride hexahydrate.

[0011] Furthermore, the molar ratio of the divalent nickel salt, divalent copper salt, divalent cobalt salt, and urea in step (1) is 8.5 mmol: 1 mmol: 1.5 mmol: 60 mmol; and the volume of ultrapure water is 50 mL.

[0012] Furthermore, the ultrasonication time in step (1) is 15 minutes.

[0013] Furthermore, the temperature of the hydrothermal reaction in step (2) is 120° C., and the time of the hydrothermal reaction is 24 h.

[0014] Furthermore, the centrifugal speed in step (3) is 8000 rpm, the centrifugation time is 3 min, and the centrifugation is performed twice alternately with ethanol and deionized water.

[0015] Furthermore, the freeze-drying step in step (3) is to place the product in a vacuum freeze dryer for 12 hours.

[0016] A hollow sea urchin-like 1D / 3D NiCuCo heterostructure nanomaterial prepared by the above method and its application in efficient water treatment.

[0017] The beneficial effects of the present invention are:

[0018] (1) This invention uses a simple hydrothermal synthesis method to combine Ni, Cu, and Co metals under the action of urea. The resulting mixture is then centrifuged, washed, and freeze-dried to form a hollow sea urchin-like 1D / 3D NiCuCo heterostructured nanomaterial. This provides a novel synthesis method for hollow sea urchin-like catalysts, offering new insights into the preparation of highly efficient catalysts for degrading pollutants in water.

[0019] (2) The hollow sea urchin-like 1D / 3D NiCuCo nanomaterial prepared in the present invention is a hollow sea urchin-like structure formed by the combination of needles and hollow spheres, and the size of a single particle is about 4 μm.

[0020] (3) The hollow sea urchin-shaped 1D / 3D NiCuCo nanomaterials prepared in the present invention are more porous and have more active sites than the same type of (hollow sea urchin) materials, and can degrade a variety of organic pollutants in seconds.

[0021] (4) The raw materials and equipment required for the preparation method of the present invention are simple and easy to obtain, the process is simple, easy to operate and safe, and the cost is relatively low; compared with products prepared by other traditional methods, it has a high efficiency in pollutant degradation and is an environmentally friendly new material with great promotion and application value and use prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a scanning electron microscope (SEM) image of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention.

[0023] Figure 2 This is a scanning electron microscope (SEM) image of the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1 of the present invention.

[0024] Figure 3 This is a scanning electron microscope (SEM) image of the spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2 of the present invention.

[0025] Figure 4 This is a transmission electron microscope (TEM) image of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention.

[0026] Figure 5 These are the X-ray diffraction (XRD) patterns of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2. It can be seen from the figures that the Co element was successfully incorporated into the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial.

[0027] Figure 6 Schematic diagram of the enrofloxacin degradation rate of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2.

[0028] Figure 7 Schematic diagram of the ciprofloxacin degradation rate of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2.

[0029] Figure 8Schematic diagram of tetracycline degradation rate of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2.

[0030] Figure 9 This is a schematic diagram of the cyclic degradation rate of enrofloxacin in the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention.

[0031] Figure 10 These are the N2 adsorption-desorption curves of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2.

[0032] Figure 11 These are the oxygen vacancy curves of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2.

[0033] Figure 12 Schematic diagram of the degradation rate of enrofloxacin by the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterials prepared in Example 1 of the present invention and nanomaterials synthesized from other transition metals. DETAILED DESCRIPTION

[0034] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings, i.e., embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0035] Example 1

[0036] Preparation of hollow sea urchin-like 1D / 3D NiCuCo heterostructure nanomaterials:

[0037] (1) Weigh 4.25 mmol of nickel chloride hexahydrate, 0.5 mmol of copper chloride dihydrate, 0.75 mmol of cobalt chloride hexahydrate, and 30 mmol of urea and dissolve them in a beaker containing 50 ml of ultrapure water;

[0038] (2) Place the beaker in an ultrasonic machine and sonicate for 15 minutes, then transfer the solution to a 100 ml polytetrafluoroethylene reactor.

[0039] (3) The reactor was placed in an oven at 120°C for 24 h to perform a hydrothermal reaction;

[0040] (4) The hydrothermal solution was centrifuged twice with ethanol and deionized water at 8000 rpm for 3 min, and then placed in a vacuum freeze dryer for 12 h to obtain a hollow sea urchin-like 1D / 3D NiCu heterostructure nanomaterial.

[0041] Figure 1 This is a scanning electron microscope (SEM) image of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention. It can be seen from the image that the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial is a hollow sea urchin-shaped structure formed by the combination of needles and hollow spheres, and the size of a single particle is about 4μm. Figure 4 This is a transmission electron microscope (TEM) image of a hollow sea urchin-like 1D / 3DNiCuCo heterostructure nanomaterial. From the image, it can be seen that the hollow sea urchin-like 1D / 3DNiCuCo heterostructure nanomaterial is a hollow sea urchin-like structure formed by the combination of needles and hollow spheres, and the size of a single particle is about 4μm.

[0042] Comparative Example 1

[0043] Preparation of hollow sea urchin-like 1D / 3D NiCu heterostructure nanomaterials:

[0044] (1) Weigh 5 mmol nickel chloride hexahydrate, 0.5 mmol copper chloride dihydrate, and 30 mM urea and dissolve them in a beaker containing 50 ml ultrapure water;

[0045] (2) Place the beaker in an ultrasonic machine and ultrasonicate for 15 minutes, then transfer the solution to a 100 ml polytetrafluoroethylene reactor;

[0046] (3) Place the reactor in an oven at 120°C for 24 hours to perform a hydrothermal reaction;

[0047] (4) The hydrothermal solution was centrifuged twice with ethanol and deionized water at 8000 rpm for 3 min, and then placed in a vacuum freeze dryer for 12 h to obtain hollow sea urchin-like 1D / 3D NiCuCo heterostructure nanomaterials.

[0048] Figure 2 This is a scanning electron microscope (SEM) image of the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1 of the present invention. It can be seen from the image that the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial is a hollow sea urchin-shaped structure formed by the combination of needles and hollow spheres, and the size of a single particle is about 4μm.

[0049] Comparative Example 2

[0050] Preparation of spherical NiCo heterostructure nanomaterials:

[0051] (1) Weigh 5 mmol of nickel chloride hexahydrate, 0.5 mmol of cobalt chloride hexahydrate, and 30 mM of urea and dissolve them in a beaker containing 50 ml of ultrapure water;

[0052] (2) Place the beaker in an ultrasonic machine and ultrasonicate for 15 minutes, then transfer the solution to a 100 ml polytetrafluoroethylene reactor;

[0053] (3) Place the reactor in an oven at 120°C for 24 hours to perform a hydrothermal reaction;

[0054] (4) The hydrothermal solution was centrifuged twice with ethanol and deionized water at 8000 rpm for 3 min, and then placed in a vacuum freeze dryer for 12 h to obtain spherical NiCo heterostructure nanomaterials.

[0055] Figure 3 This is a scanning electron microscope (SEM) image of the thorny spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2 of the present invention. It can be seen from the image that the thorny spherical NiCo heterostructure nanomaterial is a thorny spherical structure formed by the combination of needles and solid spheres, and the size of a single particle is about 1.5μm.

[0056] Comparative Example 3

[0057] The difference of Example 1 of this comparative example is only that cobalt chloride hexahydrate is replaced by anhydrous zinc chloride.

[0058] Comparative Example 4

[0059] The difference of Example 1 of this comparative example is only that cobalt chloride hexahydrate is replaced by manganese chloride tetrahydrate.

[0060] Application Example 1 Water Pollutant Degradation Experiment

[0061] The hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial obtained in Example 1 was used to degrade water pollutants, and the specific steps were as follows:

[0062] (1) Weigh 4 mg of hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterials into a 100 ml beaker, and then measure 40 ml of 10 ppm enrofloxacin solution and add it to the beaker;

[0063] (2) Ultrasonicate the mixed solution for 10 seconds in an ultrasonic machine. Place a stirring bar in the beaker and place it on a magnetic stirring table. Use a pipette to add 80 μl of the prepared 1 mol / L PMS aqueous solution and start the timer.

[0064] (3) From the start of the timing, draw the solution from the beaker with a 2 ml syringe every 10 s, 30 s, 60 s, 120 s, and 300 s, then filter it through a filter and measure its absorbance using a UV-visible spectrophotometer;

[0065] (4) The degradation tests of ciprofloxacin and tetracycline are the same as above.

[0066] Application Example 2 Water Pollutant Degradation Experiment

[0067] The hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial obtained in Comparative Example 1 was used to degrade water pollutants, and the specific steps were as follows:

[0068] (1) Weigh 4 mg of hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterials into a 100 ml beaker, and then measure 40 ml of 10 ppm enrofloxacin solution and add it to the beaker;

[0069] (2) Ultrasonicate the mixed solution for 10 seconds in an ultrasonic machine. Place a stirring bar in the beaker and place it on a magnetic stirring table. Use a pipette to add 80 μl of the prepared 1 mol / L PMS aqueous solution and start the timer.

[0070] (3) From the start of the timing, draw the solution from the beaker with a 2 ml syringe every 10 s, 30 s, 60 s, 120 s, and 300 s, then filter it through a filter and measure its absorbance using a UV-visible spectrophotometer;

[0071] (4) The degradation tests of ciprofloxacin and tetracycline are the same as above.

[0072] Application Example 3 Water Pollutant Degradation Experiment

[0073] The spherical NiCo heterostructure nanomaterials obtained in Comparative Example 2 were used to degrade water pollutants, and the specific steps were as follows:

[0074] (1) Weigh 4 mg of spherical NiCo heterostructured nanomaterials into a 100 ml beaker, then add 40 ml of 10 ppm enrofloxacin solution into the beaker;

[0075] (2) Ultrasonicate the mixed solution for 10 seconds in an ultrasonic machine. Place a stirring bar in the beaker and place it on a magnetic stirring table. Use a pipette to add 80 μl of the prepared 1 mol / L PMS aqueous solution and start the timer.

[0076] (3) From the start of the timing, draw the solution from the beaker with a 2 ml syringe every 10 s, 30 s, 60 s, 120 s, and 300 s, then filter it through a filter and measure its absorbance using a UV-visible spectrophotometer;

[0077] (4) The degradation tests of ciprofloxacin and tetracycline are the same as above.

[0078] Figure 6 This is a schematic diagram of the enrofloxacin degradation rate of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spiny ball-shaped NiCo heterostructure nanomaterial prepared in Comparative Example 2. It can be seen that the degradation rate of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial is greater than that of the other prepared materials, and the degradation degree can reach 95% in 5 minutes. Figure 7 This is a schematic diagram of the ciprofloxacin degradation rate of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3DNiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spiny spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2. It can be seen that the degradation rate of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial is greater than that of the other prepared materials, and the degradation degree can reach 95% in 5 minutes. Figure 8 This is a schematic diagram of the tetracycline degradation rate of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spiny ball-shaped NiCo heterostructure nanomaterial prepared in Comparative Example 2. It can be seen that the degradation rate of the hollow sea urchin-shaped 1D / 3DNiCuCo heterostructure nanomaterial is greater than that of the other prepared materials, and the degradation degree can reach 95% in 5 minutes. Figure 9 This is a schematic diagram of the cyclic degradation rate of enrofloxacin by the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention. It can be seen that the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial can still achieve a degradation rate of more than 80% in 20 minutes after cyclic degradation of enrofloxacin four times, indicating that it has good degradation stability. Figure 10 These are the N2 adsorption-desorption curves of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the thorn-shaped NiCo heterostructure nanomaterial prepared in Comparative Example 2. It can be seen from the figure that the specific surface area of ​​the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial is much larger than that of the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial and the thorn-shaped NiCo heterostructure nanomaterial, which exposes more active sites. Figure 11These are the oxygen vacancy curves of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention, the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial prepared in Comparative Example 1, and the spherical NiCo heterostructure nanomaterial prepared in Comparative Example 2. It can be seen from the figure that the oxygen vacancies of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial are much increased compared with those of the hollow sea urchin-shaped 1D / 3D NiCu heterostructure nanomaterial and the spherical NiCo heterostructure nanomaterial, and the oxygen vacancy defects also provide more active sites. Figure 12 This is a schematic diagram of the degradation rate of enrofloxacin by the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared in Example 1 of the present invention and nanomaterials synthesized by other transition metals. It can be seen that the nanomaterial doped with metal Co has a better degradation effect than the nanomaterial doped with Zn and Mn.

[0079] It will be easily understood by those skilled in the art that the above description is merely a preferred example of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a hollow sea urchin-like 1D / 3D NiCuCo heterostructure nanomaterial, characterized by: The following steps are involved: (1) dissolving a divalent nickel salt, a divalent copper salt, a divalent cobalt salt, and urea in ultrapure water to obtain a mixed solution, and uniformly dispersing the solution by ultrasonication; (2) The mixed solution obtained in step (1) was transferred to a polytetrafluoroethylene reactor and placed in an oven for hydrothermal reaction; (3) The solution obtained in step (2) is centrifuged and freeze-dried to obtain a hollow sea urchin-like 1D / 3D NiCuCo heterostructure nanomaterial; The molar ratio of the divalent nickel salt, divalent copper salt, divalent cobalt salt, and urea in step (1) is 8.5 mmol: 1 mmol: 1.5 mmol: 60 mmol; the volume of ultrapure water is 50 mL; The temperature of the hydrothermal reaction in step (2) is 120° C., and the time of the hydrothermal reaction is 24 h.

2. The method for preparing the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial according to claim 1, characterized in that: In step (1), the divalent nickel salt is nickel chloride hexahydrate, the divalent copper salt is copper chloride dihydrate, and the divalent cobalt salt is cobalt chloride hexahydrate.

3. The method for preparing the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial according to claim 1, characterized in that: The ultrasonication time in step (1) is 15 minutes.

4. The method for preparing the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial according to claim 1, characterized in that: The centrifugal speed in step (3) is 8000 rpm, the centrifugation time is 3 min, and the centrifugation is performed twice alternately with ethanol and deionized water.

5. The method for preparing the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial according to claim 1, characterized in that: The freeze-drying step in step (3) is to place the product in a vacuum freeze dryer for 12 hours. 6 . A hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial prepared by the preparation method according to any one of claims 1 to 5 .

7. Use of the hollow sea urchin-shaped 1D / 3D NiCuCo heterostructure nanomaterial as claimed in claim 6 in efficient water treatment.

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