Photocatalyst for Tetracycline antibiotic adsorbent in water and Manufacturing method thereof

Abstract

The present invention relates to a catalyst for the adsorption and photodegradation of tetracycline antibiotics in water and a method for producing the same, and more specifically, to a TiO2@Fe-N / C catalyst capable of adsorbing tetracycline antibiotics in water and photodegrading them in the visible light region and a method for producing the same. The method for producing a tetracycline antibiotic adsorption and photodecomposition catalyst in water according to the present invention comprises a first step of producing TiO2@ZIF8 by stirring ZIF8 and TiO2, a second step of producing TiO2@N / C by sublimating zinc through annealing of TiO2@ZIF8, and a third step of producing TiO2@Fe-N / C by adding Fe to TiO2@N / C and annealing.

Description

Technology Field

[0001] The present invention relates to a catalyst for the adsorption and photodegradation of tetracycline antibiotics in water and a method for producing the same, and more specifically, to a TiO2@Fe-N / C catalyst capable of adsorbing tetracycline antibiotics in water and photodegrading them in the visible light region and a method for producing the same. Background Technology

[0002] Waste medicines refer to medicines that cannot be used in general households and other places due to expiration, deterioration, spoilage, etc. Such waste medicines are classified as hazardous household waste that can cause harm to health and the surrounding environment, such as inducing disease or physical injury, and must be collected through a separate dedicated collection container and incinerated in accordance with Article 14 of the Waste Management Act.

[0003] However, many people do not recognize the importance of collecting expired medicines and dispose of them through household sewers, and such disposed medicines affect soil and aquatic ecosystems. In fact, when the water quality of rivers was investigated, it was confirmed that numerous pharmaceutical substances were detected, and the adsorption and collection of antibiotics in water are required.

[0004] As part of research on catalysts for removing tetracycline (TC), one of the most widely used antibiotics, by adsorbing and photodegrading it, the inventors developed a catalyst capable of effectively removing antibiotics by using Fe-NC with a porous structure as a material capable of adsorbing antibiotics, thereby achieving more effective adsorption performance, and using Fe-doped TiO2 as a material capable of degrading the adsorbed antibiotics, thereby allowing photodegradation even in the visible light region. Prior art literature

[0005] Korean Registered Patent No. 10-2715551 The problem to be solved

[0006] The objective of the present invention to solve the above-mentioned problems is to provide a TiO2@Fe-N / C catalyst capable of adsorbing tetracycline antibiotics in water and photodegrading in the visible light region, and a method for manufacturing the same. means of solving the problem

[0007] The method for preparing a tetracycline antibiotic adsorption and photodecomposition catalyst in water according to the present invention for solving the above problem comprises: a first step of preparing TiO2@ZIF8 by stirring ZIF8 and TiO2; a second step of preparing TiO2@N / C by sublimating zinc through annealing of TiO2@ZIF8; and a third step of preparing TiO2@Fe-N / C by adding Fe to TiO2@N / C and annealing.

[0008] The above TiO2 is characterized by being added in an amount of 0.5 to 20 wt% of the total catalyst 100 wt%.

[0009] The annealing of the above 2nd and 3rd steps is characterized by being performed at 700 to 900 ℃.

[0010] The tetracycline antibiotic adsorption and photodecomposition catalyst in water according to the present invention is manufactured by the manufacturing method described above. Effects of the invention

[0011] As described above, according to the tetracycline antibiotic adsorption and photodecomposition catalyst in water and the method for manufacturing the same according to the present invention, there is an effect of adsorbing tetracycline antibiotics in water.

[0012] In addition, according to the tetracycline antibiotic adsorption and photodecomposition catalyst in water and the method for manufacturing the same according to the present invention, the bandgap energy of the catalyst is lowered by introducing Fe, thereby enabling photodecomposition in the visible light region. Brief explanation of the drawing

[0013] FIG. 1 is a schematic diagram of the preparation of a tetracycline antibiotic adsorption and photodecomposition catalyst in water according to the present invention. Figure 2 shows the XRD results at each manufacturing step of the catalyst TiO2@Fe-N / C according to the present invention. Figure 3 shows SEM images of each manufacturing step of the catalyst TiO2@Fe-N / C according to the present invention. Figure 4 shows the wavelength range and band gap change of the catalyst TiO2@Fe-N / C according to the present invention. FIG. 5 is a graph showing the tetracycline (TC) decomposition ability of the catalyst TiO2@Fe-N / C according to the present invention. Figure 6 is a graph showing the performance retention characteristics of the catalyst TiO2@Fe-N / C according to the present invention upon reuse. Specific details for implementing the invention

[0014] The specific features and advantages of the present invention will be described in detail below with reference to the accompanying drawings. Prior to this, if it is determined that a detailed description of the functions and configurations related to the present invention may unnecessarily obscure the essence of the invention, such detailed description will be omitted.

[0015] The present invention relates to a catalyst for the adsorption and photodegradation of tetracycline antibiotics in water and a method for producing the same, and more specifically, to a TiO2@Fe-N / C catalyst capable of adsorbing tetracycline antibiotics in water and photodegrading them in the visible light region and a method for producing the same.

[0016] The method for producing a tetracycline antibiotic adsorption and photodecomposition catalyst in water according to the present invention comprises a first step of producing TiO2@ZIF8 by stirring ZIF8 and TiO2, a second step of producing TiO2@N / C by sublimating zinc through annealing of TiO2@ZIF8, and a third step of producing TiO2@Fe-N / C by adding Fe to TiO2@N / C and annealing.

[0017] Step 1 involves preparing TiO2@ZIF8 by stirring ZIF8 and TiO2, where ZIF-8 particles are a zinc precursor (zinc nitrate hexahydrate (Zn(NO3)) 2·ZIF-8 particles are synthesized by mixing and stirring 6H2O)) and 2-methylimidazole (Hmim, 98%, Aldrich), and after stirring is complete, washing and centrifuging are performed several times.

[0018] Subsequently, TiO2 is loaded into ZIF-8, wherein the TiO2 may be added in an amount of 0.5 to 20 wt% of the total catalyst 100 wt%.

[0019] If the above TiO2 is less than 0.5 wt% of the total 100 wt% of the catalyst, it is difficult to achieve an antibiotic degradation effect by the photocatalyst, and if it exceeds 20 wt%, it is difficult to lower the band gap region of the photocatalyst, which limits the photodegradation of antibiotics in the visible light region, so it is desirable not to exceed the above range of addition amount.

[0020] In the second step, TiO2@N / C is produced by sublimating zinc through the annealing of TiO2@ZIF8, wherein the annealing is performed at 700 to 900 ℃, and preferably at 750 to 850 ℃.

[0021] Step 3 involves preparing TiO2@Fe-N / C by adding Fe to TiO2@N / C and annealing, using TiO2@N / C and an iron precursor (FeCl 3· After stirring 6H2O), annealing is performed at 700 to 900 ℃. Preferably, the annealing process can be performed at 750 to 850 ℃.

[0022] Hereinafter, the tetracycline antibiotic adsorption and photodecomposition catalyst in water according to the present invention will be described.

[0023] The tetracycline antibiotic adsorption and photodegradation catalyst in water according to the present invention is manufactured by the manufacturing method described above and has the effect of adsorbing tetracycline antibiotics in water while simultaneously being capable of photodegradation in the visible light region. As the detailed process and structure have been described above, a detailed description thereof will be omitted.

[0024] The present invention will be described in detail below with reference to a preferred embodiment. However, the following embodiment is intended to specifically illustrate the present invention and is not limited thereto.

[0025] 1. TiO 2 Preparation of Fe-N / C catalyst

[0026] 1-1. TiO 2 @ZIF8's manufacturing

[0027] zinc nitrate hexahydrate (Zn(NO3) 2· ZIF8 was synthesized by mixing and stirring 6H2O and 2-methylimidazole (Hmim, 98%, Aldrich), and after stirring was completed, ZIF-8 particles were obtained by washing several times and centrifuging. To confirm the photodegradation characteristics according to the concentration and amount of TiO2 added, 1, 10, and 20 wt% of TiO2 were loaded onto ZIF-8.

[0028] 1-2.TiO 2 Manufacturing of @N / C

[0029] TiO2@N / C was prepared by annealing TiO2@ZIF8 at 800℃ to sublimate zinc.

[0030] 1-3. TiO 2 @Manufacturing of Fe-N / C

[0031] TiO2@N / C and FeCl 3· TiO2@Fe-N / C was prepared by mixing and stirring 6H2O and then annealing at 800 ℃.

[0032] Figure 1 shows a schematic diagram of the fabrication of TiO2@Fe-N / C.

[0033] 2. Analysis Results

[0034] 2-1. XRD

[0035] X-ray diffraction (XRD) was measured to confirm the presence or absence of synthesis at each stage. Figure 2 shows the XRD results during the preparation stage of TiO2@Fe-N / C.

[0036] Through XRD patterns, it was confirmed that the target material was well formed and synthesized at each stage, and that peak intensity and strength increased as the concentration of TiO2 increased.

[0037] 2-2. SEM

[0038] Figure 3 shows a Scanning Electron Microscope (SEM) image during the preparation of TiO2@Fe-N / C. TiO2 is amorphous, and TiO2@ZIF8, NC, and Fe N / C exhibited a hexagonal structure and were confirmed to have a porous structure.

[0039] 2-3. UV-vis Spectroscopic Analysis

[0040] Fig. 4 is This is a UV-vis graph showing the wavelength range and bandgap changes of TiO2@Fe-N / C. It demonstrated that the introduction of Fe-N / C resulted in absorbance in the visible light range and confirmed that the bandgap energy could be lowered. The bandgap energy was found to be lowest at a TiO2 concentration of 1 wt%.

[0041] 2-4. Antibiotic Degradation Ability

[0042] Figure 5 shows the tetracycline (TC) decomposition ability of the catalyst. As a result of checking the change in the concentration of tetracycline (TC) in water over one hour, it was confirmed that the concentration of tetracycline (TC) decreased over time. In particular, the catalyst containing 1 wt% TiO2 showed a TC decomposition ability of over 70%.

[0043] 2-5. Potential for Catalyst Reuse

[0044] To confirm the reusability of the catalyst, the TC decomposition experiment of the catalyst was repeated 5 times to check the change in performance (as shown in Fig. 6). As a result, it was confirmed that the catalyst performance was maintained even when repeated 5 times.

[0045] As described above, although the present invention has been explained with reference to the attached drawings and with reference to preferred embodiments, those skilled in the art may modify or vary the present invention in various ways without departing from the technical spirit and scope described in the claims of the present invention. Accordingly, the scope of the present invention should be interpreted by the claims described to include such many variations.

[0046] This project (result) is the result of the Local Government-University Cooperation-based Regional Innovation Project, conducted in 2024 with funding from the Ministry of Education and support from the National Research Foundation of Korea (2022RIS-006).

Claims

Claim 1 A method for producing a tetracycline antibiotic adsorption and photodegradation catalyst in water, characterized by comprising: a first step of producing TiO2@ZIF8 by stirring ZIF8 and TiO2; a second step of producing TiO2@N / C by sublimating zinc through annealing of TiO2@ZIF8; and a third step of producing TiO2@Fe-N / C by adding Fe to TiO2@N / C and annealing. Claim 2 A method for preparing a tetracycline antibiotic adsorption and photodecomposition catalyst in water, characterized in that, in claim 1, the TiO2 is added in an amount of 0.5 to 20 wt% of the total catalyst 100 wt%. Claim 3 A method for preparing a tetracycline antibiotic adsorption and photodegradation catalyst in water, characterized in that, in claim 1, the annealing of steps 2 and 3 is performed at 700 to 900 ℃. Claim 4 A tetracycline antibiotic adsorption and photodecomposition catalyst in water produced by the catalyst manufacturing method of any one of claims 1 to 3.

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