Recyclable titanium ferrite carbon micromaterial and preparation method thereof
By preparing titanium ferrite/carbon microtube photocatalytic materials, the problem of treating harmful algae in eutrophic water bodies has been solved, achieving efficient inactivation and recyclability, and is suitable for treating harmful algae in eutrophic water bodies.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WENZHOU UNIV
- Filing Date
- 2023-05-13
- Publication Date
- 2026-07-21
AI Technical Summary
Existing technologies are insufficient to effectively treat harmful algae in eutrophic waters, especially algal blooms caused by Microcystis aeruginosa, and traditional methods may be harmful to the environment.
Using titanium ferrite/carbon microtube photocatalyst, titanium ferrite is loaded onto carbon microtubes through a preparation process to form a composite photocatalyst. Its unique physicochemical properties are utilized to generate free radicals that damage algal cells, and the photocatalyst can be easily recovered through magnetic properties.
It achieves highly efficient inactivation of harmful algae in eutrophic waters, the material is recyclable, reducing costs, and does not cause secondary pollution to the environment.
Smart Images
Figure CN117753416B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a recyclable titanium ferrite carbon microtube photocatalytic algae control material and its preparation method. Background Technology
[0002] Eutrophication is a global problem facing freshwater and marine ecosystems. Natural water bodies such as lakes, rivers, and reservoirs provide basic ecosystem services for life on Earth, including drinking water, irrigation, and recreation. Under traditional extensive urban development models, large amounts of nutrients such as nitrogen and phosphorus are discharged into natural water bodies, causing eutrophication and leading to the rapid proliferation of algae and other plankton. Microcystis aeruginosa is a major algae species causing frequent algal blooms, resulting in a decrease in dissolved oxygen concentration and severely impacting the ecological environment. Furthermore, its metabolic byproducts, microcystin toxins, are harmful to the environment, making its research of significant importance. In addition, because its growth is unaffected by environmental factors, it is highly tolerant of harsh environments, has a small size, and can easily survive and reproduce rapidly under laboratory conditions, making it one of the representative harmful algae. Eutrophication can trigger cyanobacterial blooms. The accumulation of large amounts of cyanobacteria on the water surface leads to serious water quality problems such as scum, the production of toxic metabolites, oxygen deficiency, and unpleasant odors. Therefore, a safe and efficient method for treating algal blooms is urgently needed. Photocatalysis is generally considered a green and feasible method for inactivating algae in water bodies.
[0003] Carbon microtubes possess a tubular structure similar to carbon nanotubes and share the unique physical and chemical properties of both. The tubular structure of carbon microtubes also facilitates improved mass transfer efficiency and induces the generation of free radicals on the surface of carbon materials via photocatalysts. Free radicals are a major cause of algal cell damage; therefore, carbon microtubes and carbon nanotube carriers, by promoting free radical generation, hold great potential for controlling algal blooms. Summary of the Invention
[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a titanium ferrite / carbon microtube photocatalytic algae control material and its preparation method, which has a recyclable photocatalytic algae control effect.
[0005] A method for preparing a titanium ferrite / carbon microtube photocatalytic algae-controlling material, comprising the following steps:
[0006] 1) Dry agricultural waste, calcine it at 500-800℃ in an oxygen-free environment, cool it to room temperature, and grind it into powder to obtain carbonaceous precursor powder;
[0007] 2) Mix the carbon precursor powder with the catalyst evenly, keep the temperature constant at 170-200℃ for 1-2 hours, and then heat to 700-900℃ under nitrogen protection and keep the temperature constant for 2-6 hours to obtain carbon microtube substrate.
[0008] 3) Prepare an organic titanate alcohol solution with a concentration of 5-20%, add 10-30% iron salt, 5-10% carbon microtubes and 40-60% alkaline solution, mix evenly, heat at 60-80℃ for 0.5-3 hours, filter and collect the product, dry at 100-120℃, and then transfer it to a muffle furnace for high-temperature oxygen-free calcination at 700-900℃ for 3-5 hours to obtain titanium ferrite / carbon microtube photocatalytic algae control material;
[0009] Preferably, the agricultural waste is one or more of the following: corn cobs, straw, weeds, and fruit peels.
[0010] Preferably, the catalyst is one or more of nickel nitrate, ferric nitrate, cobalt nitrate, and potassium nitrate, and the amount used is 0.05 to 0.1 times the weight of agricultural waste.
[0011] Preferably, the organic titanate is one of tetrabutyl titanate, isopropyl titanate, n-propyl titanate, methyl titanate, and tetraethyl titanate, with a concentration of 5 to 20%.
[0012] Preferably, the alcohol solvent is one or more of methanol, ethanol, propanol, and ethylene glycol.
[0013] Preferably, the iron salt is one or more of ferric chloride, ferric sulfate, and ferric nitrate, with a concentration of 10 to 30%.
[0014] Preferably, the alkaline solution is one or more of sodium hydroxide, potassium hydroxide, and magnesium hydroxide, with a concentration of 40% to 60%.
[0015] The beneficial effects of this invention are as follows: The recyclable titanium ferrite / carbon microtube photocatalytic algae control material and its preparation method proposed in this invention fully utilize agricultural waste as raw materials, and through composite modification of titanium ferrite, obtain a magnetically recyclable photocatalytic algae control material to remove harmful algae in eutrophic water bodies and control cyanobacterial blooms. Due to the structure of the carbon microtubes, the obtained photocatalytic material possesses many unique physicochemical properties, showing potential applications in the field of eutrophic water treatment. The titanium ferrite / carbon microtube photocatalytic algae control material and its preparation method proposed in this invention have a simple process flow, novel material structure, and are easy to recycle, possessing strong application value.
[0016] Figure Labels
[0017] Figure 1 Scanning electron microscope image of titanium ferrite / carbon microtube photocatalytic material.
[0018] Figure 2 The photocatalytic algae control effect of titanium ferrite / carbon microtubes, and the changes in (a) chla, (b) Fv / Fm and (c) pH during the inactivation process.
[0019] Figure 3 This is a schematic diagram of the magnetic recycling of materials according to the present invention. Detailed Implementation
[0020] This invention provides a titanium ferrite / carbon microtube photocatalytic algae control material and its preparation method, which exhibits recyclable photocatalytic algae control. The microstructure of the material is shown in the attached figure. Figure 1 As shown.
[0021] Titanium ferrite (TiFe2O4) is a novel photocatalyst with a band gap of 2.37 eV, thus exhibiting superior photocatalytic performance.
[0022] This invention innovatively utilizes titanium ferrite composites with carbon microtube materials to prepare a recyclable photocatalytic algae-controlling material, the algae-controlling effect of which is shown in the attached figure. Figure 2 As shown.
[0023] This invention proposes a recyclable titanium ferrite carbon microtube photocatalytic algae control material and its preparation method. The specific implementation includes the following steps:
[0024] The first step in the preparation is the preparation of the carbonaceous precursor.
[0025] Agricultural waste has a complex composition and contains abundant organic matter, which increases its hydrophobicity and makes it difficult to come into contact with eutrophic water bodies. Therefore, it is necessary to remove impurities from it.
[0026] Impurities present in agricultural waste are removed by anaerobic calcination, thus obtaining carbonaceous precursors.
[0027] The second step in the preparation is the fabrication of carbon microtubes.
[0028] Carbon microtube substrate is obtained by uniformly mixing carbon precursor powder with catalyst, pressing it into shape, and maintaining the temperature at 170-200℃ in an oven for 1-2 hours. Then, under nitrogen protection, it is heated to 700-900℃ and maintained at that temperature for 2-6 hours.
[0029] The third step in the preparation is to prepare composite titanium ferrite.
[0030] Titanium ferrite is loaded onto a carbon substrate through high-temperature calcination. The present invention utilizes an organic titanate alcohol solution mixed with iron salts, followed by hydrothermal reaction and high-temperature calcination to synthesize a novel photocatalyst, titanium ferrite. Compared to existing technologies, this invention does not use doped composite nanoparticles. Testing revealed that the material of this invention has a band gap of 2.37 eV, exhibiting excellent light response range and thus superior photocatalytic performance. Furthermore, the composite-modified material possesses magnetic properties and is easily recyclable; testing showed a magnetic recovery rate of over 95%, enabling effective recycling and cost savings. The magnetic characteristics also broaden the application of this material; for example, in flowing water, its magnetic properties ensure stable retention at a designated location to exert its characteristics.
[0031] The following are various preparation examples to further illustrate the details of the preparation method of the present invention.
[0032] Example 1
[0033] 1) Dry the corn cobs, calcine them at 500℃ in an oxygen-free environment, cool them to room temperature, and grind them into powder to obtain carbonaceous precursor powder;
[0034] 2) Mix the carbon precursor powder with 0.05 times its weight of nickel nitrate evenly, keep the temperature at 170°C for 2 hours, and then heat to 800°C under nitrogen protection and keep the temperature at 800°C for 5 hours to obtain carbon microtube substrate.
[0035] 3) Prepare a 5% tetrabutyl titanate ethanol solution, add 10% ferric chloride, 5% carbon microtubes and 40% sodium hydroxide, mix well, heat at 80°C for 1 hour, filter and collect the product, dry at 100°C, and then transfer it to a muffle furnace for high-temperature oxygen-free calcination at 900°C for 3 hours to obtain titanium ferrite / carbon microtube photocatalytic algae control material.
[0036] Example 2
[0037] 1) Dry the straw, calcine it at 600℃ in an oxygen-free environment, cool it to room temperature, and grind it into powder to obtain carbonaceous precursor powder;
[0038] 2) Mix the carbon precursor powder with 0.05 times its weight of cobalt nitrate evenly, keep the temperature constant at 200℃ for 1.5 hours, and then heat to 900℃ under nitrogen protection and keep the temperature constant for 3 hours to obtain carbon microtube substrate.
[0039] 3) Prepare a 10% titanium isopropyl glycol solution, add 20% ferric nitrate, 10% carbon microtubes and 50% alkaline solution, mix well, heat at 70°C for 3 hours, filter and collect the product, dry at 120°C, and then transfer it to a muffle furnace for high-temperature oxygen-free calcination at 850°C for 4 hours to obtain titanium ferrite / carbon microtube photocatalytic algae control material;
[0040] Example 3
[0041] 1) Dry the fruit peel, calcine it at 800℃ in an oxygen-free environment, cool it to room temperature, and grind it into powder to obtain carbonaceous precursor powder;
[0042] 2) Mix the carbon precursor powder with 0.02 times its weight of nickel nitrate evenly, keep the temperature at 180°C for 4 hours, and then heat to 700°C under nitrogen protection and keep the temperature at 700°C for 5 hours to obtain the carbon substrate.
[0043] 3) Prepare a 15% titanate-propanol-methanol solution, add 15% ferric sulfate, 8% carbon microtubes and 60% alkaline solution, mix well and heat at 60°C for 2 hours, filter and collect the product to dry at 100°C, then transfer it to a muffle furnace and calcine at 800°C in an oxygen-free environment for 5 hours to obtain titanium ferrite / carbon microtube photocatalytic algae control material;
[0044] Example 4
[0045] 1) Dry the weeds, calcine them at 500℃ in an oxygen-free environment, cool them to room temperature, and grind them into powder to obtain carbonaceous precursor powder;
[0046] 2) Mix the carbon precursor powder with 0.03 times its weight of nickel nitrate evenly, keep the temperature at 185°C for 2 hours, and then heat to 850°C under nitrogen protection and keep the temperature at 3 hours to obtain the carbon substrate.
[0047] 3) Prepare a 15% tetraethyl titanate propanol solution, add 20% ferric chloride, 5% carbon microtubes and 45% alkaline solution, mix well, heat at 75°C for 1.5 hours, filter and collect the product, dry at 115°C, and then transfer it to a muffle furnace for high-temperature oxygen-free calcination at 700°C for 5 hours to obtain titanium ferrite / carbon microtube photocatalytic algae control material;
[0048] Example 5
[0049] 1) Dry the corn cobs, calcine them at 800℃ in an oxygen-free environment, cool them to room temperature, and grind them into powder to obtain carbonaceous precursor powder;
[0050] 2) Mix the carbon precursor powder with 0.02 times its weight of nickel nitrate evenly, keep the temperature at 190°C for 2 hours, and then heat to 850°C under nitrogen protection and keep the temperature at 4 hours to obtain the carbon substrate.
[0051] 3) Prepare a 10% tetrabutyl titanate glycol solution, add 25% ferric nitrate, 10% carbon microtubes and 50% alkaline solution, mix well, heat at 80°C for 1 hour, filter and collect the product, dry at 120°C, and then transfer it to a muffle furnace for high-temperature oxygen-free calcination at 800°C for 4 hours to obtain titanium ferrite / carbon microtube photocatalytic algae control material.
[0052] As shown in the above preparation examples and the accompanying drawings, this invention utilizes an organic titanate alcohol solution mixed with iron salts, followed by hydrothermal reaction and high-temperature calcination to synthesize a novel photocatalyst, titanium ferrite. Compared to existing technologies, this invention uses non-doped composite nanoparticles with a band gap of 2.37 eV, exhibiting superior photocatalytic performance. Furthermore, it is magnetically recyclable with a magnetic recovery rate exceeding 95%. This material fully utilizes agricultural waste as raw material, and the composite-modified titanium ferrite effectively removes harmful algae from eutrophic waters and controls cyanobacterial blooms. Based on the carbon microtube structure, the resulting photocatalytic material possesses many unique physicochemical properties, showing potential applications in eutrophic water treatment. Therefore, this invention features a simple process, novel material structure, convenient recycling, and strong application value.
Claims
1. The application of a recyclable titanium ferrite carbon microtube photocatalytic algae control material in photocatalytic algae control, characterized in that: The preparation steps of the titanium ferrite carbon microtube photocatalytic algae control material are as follows: 1) Dry agricultural waste, calcine it at 500-800℃ in an oxygen-free environment, cool it to room temperature, and grind it into powder to obtain carbon precursor powder; 2) Mix the carbon precursor powder with one or more of nickel nitrate, ferric nitrate, and cobalt nitrate as catalysts, keep it at a constant temperature of 170-200℃ for 1-2 hours, and heat it to 700-900℃ under nitrogen protection, keep it at a constant temperature for 2-6 hours to obtain carbon microtube substrate; 3) Prepare an organic titanate alcohol solution with a concentration of 5-20%, add 10-30% iron salt, add 5-10% carbon microtubes and 40-60% alkaline solution, mix evenly, heat at 60-80℃ for 0.5-3 hours, filter and collect the product, dry it at 100-120℃, and then transfer it to a muffle furnace at 700-900℃. Calcination at ℃ in an oxygen-free environment for 3-5 hours yielded a magnetic TiFe2O4 / carbon microtube photocatalytic algae control material.
2. The application according to claim 1, characterized in that: The agricultural waste mentioned is one or more of the following: corn cobs, straw, weeds, and fruit peels.
3. The application according to claim 1, characterized in that: The catalyst is used at a rate of 0.5% to 2% of the weight of agricultural waste.
4. The application according to claim 1, characterized in that: The organic titanate is one of tetrabutyl titanate, isopropyl titanate, n-propyl titanate, methyl titanate, and tetraethyl titanate.
5. The application according to claim 1, characterized in that: The alcohol solvent is one or more of methanol, ethanol, propanol, and ethylene glycol.
6. The application according to claim 1, characterized in that: The iron salt is one or more of ferric chloride, ferric sulfate, and ferric nitrate.
7. The application according to claim 1, characterized in that: The alkali in the alkaline solution is one or more of sodium hydroxide and potassium hydroxide.