A multifunctional evaporator based on Ti-MOF derivatives, its preparation method and application

Abstract

A Ti-MOF derivative multifunctional evaporator and a preparation method and application thereof, the preparation method first prepares the Ti-MOF derivative multifunctional evaporator with photothermal-photocatalysis coordination by growing NH2-MIL-125(Ti) in situ on the functionalized carbon felt and then carbonizing, the original three-dimensional network interlaced structure of the carbon felt is conducive to light collection, the introduction of polydopamine and NH2-MIL-125(Ti) improves the hydrophilicity of the carbon felt, and provides a convenient channel for water transport, in the photocatalysis process, the carbon felt accelerates the electron transfer and improves the photoelectron-hole separation efficiency, the evaporation rate of the CPM air evaporator reaches 2.21 kg / m 2 h under 1 sunlight, and the photothermal-photocatalysis coordinated removal efficiency of a 50mg / L ciprofloxacin solution is twice that of pure photocatalysis, the Ti-MOF derivative multifunctional evaporator has high photocatalytic activity, high photothermal conversion performance and good chemical stability; the preparation process is simple, the cost is low, and the Ti-MOF derivative multifunctional evaporator has extremely high benefits in water treatment and the like.

Description

Technical Field

[0001] This invention belongs to the field of functional materials technology, and relates to water treatment materials, specifically to a Ti-MOF derivative multifunctional evaporator and its preparation method and application. Background Technology

[0002] In recent years, freshwater scarcity has become one of the most pressing threats facing humanity. Solar energy, as a green, environmentally friendly, and abundant energy source, is widely used in photovoltaic power generation, solar desalination, and photovoltaic cells. Solar-driven interfacial evaporation technology is one of the most promising technologies in freshwater production. It rapidly evaporates water molecules through perfect interfacial thermal positioning, avoiding heating of the entire bulk phase, significantly reducing heat loss, and increasing the temperature of the evaporation surface. This expands the range of rainwater, mine water, and neutral water sources for purification by obtaining pure water from more diverse sources. Unconventional water resources often contain various pollutants, such as metal ions, organic matter, and microorganisms. These pollutants can adsorb into the evaporator, covering photoactive sites, blocking water transport channels, and reducing evaporation efficiency.

[0003] Therefore, combining solar evaporation with water purification technology can effectively solve the above problems. Fortunately, photocatalysis, as an environmental purification technology, has the advantages of high efficiency, environmental friendliness, low energy consumption, and no secondary pollution. In addition, heat has a positive effect on photocatalysis; high temperature enhances the carrier transfer and separation of semiconductors, and improves the ability and efficiency of molecular oxygen activation. The combination of solar evaporation and water purification technology has high application potential in purifying unconventional water sources. Li et al. synthesized a 2D / 2D reduced graphene oxide / polypyrrole (c-GPP) aerogel with photocatalytic degradation and photothermal evaporation properties through interface confinement. The broad spectral response of rGO and PPy endowed the aerogel with excellent light collection ability and promoted the generation of photogenerated carriers. This resulted in excellent photothermal performance and photogenerated electron-hole separation efficiency. (Desalination, 2024, 117295) Han et al. prepared a self-floating photothermal photocatalytic membrane, which consists of a photothermal layer, a photocatalytic layer, and a hydrophobic layer. The construction of photothermal-photocatalysts can significantly improve the light intensity loss caused by light passing through the solution in traditional photothermal-photocatalytic systems, and has great application potential in the field of treating organic pollutants in wastewater using sunlight. (CN116237074A) Dong et al. loaded titanium dioxide and carbon nitride into the porous capillary structure of wood using a solvothermal method, and then carbonized it to obtain a lignocellulosic carbon material with photocatalytic and photothermal properties. This material can effectively improve the light response range and photocatalytic activity of the composite material. (CN115805065A) However, the materials used in the above methods are expensive, the preparation process is complex, and the energy consumption is high, which is not conducive to large-scale preparation. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a multifunctional evaporator based on Ti-MOF derivatives, its preparation method, and its applications. This invention produces a multifunctional evaporator based on Ti-MOF derivatives with high photocatalytic activity, high photothermal conversion performance, and good chemical stability. Furthermore, the preparation process is simple and low-cost, and it offers significant benefits in water treatment and other fields.

[0005] To achieve the above objectives, the present invention employs the following technical solution:

[0006] A method for preparing a multifunctional evaporator based on Ti-MOF derivatives includes the following steps:

[0007] Step 1: Functionalize the carbon felt by encapsulating it with polydopamine, then wash it with water and vacuum dry it to obtain the functionalized carbon felt;

[0008] Step 2: NH2-MIL-125(Ti) is loaded onto the surface of functionalized carbon felt by hydrothermal method. The synthesized composite material is washed with methanol and vacuum dried to obtain carbon felt functionalized with NH2-MIL-125(Ti).

[0009] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) functionalized obtained in Step 2 at 100-1000℃ in air or argon atmosphere for 1-10 hours, with a heating rate of 1-10℃ / min, to obtain a Ti-MOF derivative multifunctional evaporator.

[0010] Preferably, the method for functionalizing carbon felt by encapsulating polydopamine in step one includes:

[0011] The carbon felt was immersed in Tris-Cl (pH=8.5) solution for 1 hour, then dopamine hydrochloride was added to a concentration of 0.1-20 mg / mL and kept under magnetic stirring for another 10-30 hours. Finally, it was washed with water and vacuum dried to obtain functionalized carbon felt.

[0012] Preferably, the method for loading NH2-MIL-125(Ti) onto the surface of a functionalized carbon felt in step two includes:

[0013] Add 0.1-1g of 2-aminoterephthalic acid and 0.1-1g of tetrabutyl titanate to 1-30mL of DMF, then add 1-30mL of methanol and stir for 30min. Then add the functionalized carbon felt prepared in step one and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and hydrothermally react at 100-300℃ for 10-30h.

[0014] Preferably, the vacuum drying temperature in steps one and two is 70°C.

[0015] The present invention also protects a multifunctional evaporator of Ti-MOF derivative prepared by the method described above and its application in water treatment.

[0016] Compared with the prior art, the present invention has the following technical effects:

[0017] The preparation method of the present invention first treats the product by encapsulating polydopamine, then further grows NH2-MIL-125(Ti) in situ on a functionalized carbon felt, and then performs a carbonization step to prepare a multifunctional evaporator of Ti-MOF derivative with photothermal-photocatalytic synergy.

[0018] The original three-dimensional interwoven network structure of the carbon felt is beneficial for light collection. The introduction of polydopamine and NH2-MIL-125(Ti) improves the hydrophilicity of the carbon felt, providing a convenient channel for water transport. Simultaneously, during photocatalysis, the carbon felt accelerates electron transfer and improves the efficiency of photogenerated electron-hole separation. The Ti-MOF derivative multifunctional evaporator prepared in this invention achieves an evaporation rate of 2.21 kg / m³ under one day of sunlight. 2 Furthermore, the photothermal and photocatalytic synergistic removal efficiency of 50 mg / L ciprofloxacin solution is twice that of pure photocatalysis, demonstrating high photocatalytic activity, high photothermal conversion performance, and good chemical stability.

[0019] The preparation process of this invention is simple and low-cost, and it has extremely high benefits in water treatment and other fields. Attached Figure Description

[0020] Figure 1 These are scanned images of the multifunctional evaporator containing Ti-MOF derivatives prepared according to this invention;

[0021] Figure 2 The UV-Vis-NIR spectrophotometer curves of the Ti-MOF derivative multifunctional evaporator prepared in this invention are shown.

[0022] Figure 3 Water evaporation curve of the Ti-MOF derivative multifunctional evaporator prepared in this invention;

[0023] Figure 4 This is the gas-liquid interface temperature rise curve of the Ti-MOF derivative multifunctional evaporator prepared in this invention;

[0024] Figure 5 This is the UV-Vis absorbance curve of the Ti-MOF derivative multifunctional evaporator prepared in this invention;

[0025] Figure 6 This is the photocatalytic degradation curve of the Ti-MOF derivative multifunctional evaporator prepared in this invention;

[0026] Figure 7This is the photothermal-photocatalytic synergistic degradation curve of the Ti-MOF derivative multifunctional evaporator prepared in this invention. Detailed Implementation

[0027] The specific content of the present invention will be further explained in detail below with reference to the embodiments.

[0028] Example 1

[0029] This embodiment provides a method for preparing a multifunctional evaporator based on Ti-MOF derivatives. The preparation method specifically includes the following steps:

[0030] Step 1: Immerse the carbon felt in Tris-Cl (pH=8.5) solution for 1 hour, then add dopamine hydrochloride to a concentration of 0.5 mg / mL and keep it under magnetic stirring for another 10 hours. After washing with water, vacuum dry at 70°C to obtain functionalized carbon felt.

[0031] Step 2: Add 1g of 2-aminoterephthalic acid and 0.1g of tetrabutyl titanate to 30mL of N,N-dimethylacetamide (DMF), then add 1mL of methanol and stir for 30min. Then add the functionalized carbon felt and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and react hydrothermally at 100℃ for 30h. Wash the synthesized composite material with methanol and finally vacuum dry at 70℃ to obtain carbon felt loaded with NH2-MIL-125(Ti).

[0032] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) at 1000℃ for 1 hour in air atmosphere, with a heat treatment rate of 10℃ / min, to obtain a Ti-MOF derivative multifunctional evaporator.

[0033] like Figure 1 As shown, the Ti-MOF derivative is in particulate form and is uniformly loaded on the surface of the functionalized carbon felt.

[0034] Example 2

[0035] This embodiment provides a method for preparing a multifunctional evaporator based on Ti-MOF derivatives. The preparation method specifically includes the following steps:

[0036] Step 1: Immerse the carbon felt in Tris-Cl (pH=8.5) solution for 1 hour, then add dopamine hydrochloride to a concentration of 5 mg / mL and keep it under magnetic stirring for another 10 hours. After washing with water, vacuum dry at 70°C to obtain functionalized carbon felt.

[0037] Step 2: Add 0.5g of 2-aminoterephthalic acid and 0.5g of tetrabutyl titanate to 18mL of DMF, then add 5mL of methanol and stir for 30min. Then add the functionalized carbon felt and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and react hydrothermally at 200℃ for 30h. Wash the synthesized composite material with methanol and finally vacuum dry at 70℃ to obtain carbon felt loaded with NH2-MIL-125(Ti).

[0038] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) at 1000℃ for 1 hour in air atmosphere, with a heat treatment rate of 5℃ / min, to obtain a Ti-MOF derivative multifunctional evaporator.

[0039] like Figure 2 As shown, due to the inheritance of the three-dimensional nanopores and full-spectrum light absorption of carbon felt, the light absorption of the Ti-MOF derivative multifunctional evaporator is as high as 98%.

[0040] Example 3

[0041] This embodiment provides a method for preparing a multifunctional evaporator based on Ti-MOF derivatives. The preparation method specifically includes the following steps:

[0042] Step 1: Immerse the treated carbon felt in Tris-Cl (pH=8.5) solution for 1 hour, then add dopamine hydrochloride to a concentration of 5 mg / mL and keep it under magnetic stirring for another 20 hours. After washing with water, vacuum dry at 70°C to obtain functionalized carbon felt.

[0043] Step 2: Add 0.1g of 2-aminoterephthalic acid and 0.6g of tetrabutyl titanate to 30mL of DMF, then add 5mL of methanol and stir for 30min. Then add the functionalized carbon felt and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and react hydrothermally at 200℃ for 30h. Wash the synthesized composite material with methanol and finally vacuum dry at 70℃ to obtain carbon felt loaded with NH2-MIL-125(Ti).

[0044] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) at 1000℃ for 1 hour in air atmosphere, with a heat treatment rate of 10℃ / min, to obtain a Ti-MOF derivative multifunctional evaporator.

[0045] like Figure 3As shown, the water evaporation capacity of the Ti-MOF derivative multifunctional evaporator is as high as 2.21 kg / m2 h. The introduction of polydopamine and NH2-MIL-125(Ti) enhances the hydrophilicity of the evaporator, providing an effective pathway for water transport.

[0046] Example 4

[0047] This embodiment provides a method for preparing a multifunctional evaporator based on Ti-MOF derivatives. The preparation method specifically includes the following steps:

[0048] Step 1: Immerse the treated carbon felt in Tris-Cl (pH=8.5) solution for 1 hour, then add dopamine hydrochloride to a concentration of 10 mg / mL and keep it under magnetic stirring for another 24 hours. After washing with water, vacuum dry at 70°C to obtain functionalized carbon felt.

[0049] Step 2: Add 0.1g of 2-aminoterephthalic acid and 0.6g of tetrabutyl titanate to 10mL of DMF, then add 5mL of methanol and stir for 30min. Then add the functionalized carbon felt and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and react hydrothermally at 200℃ for 24h. Wash the synthesized composite material with methanol and finally vacuum dry at 70℃ to obtain carbon felt loaded with NH2-MIL-125(Ti).

[0050] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) at 400℃ for 10 hours in an argon atmosphere at a heat treatment rate of 5℃ / min to obtain a Ti-MOF derivative multifunctional evaporator.

[0051] like Figure 4 As shown, the temperature rise of the gas-liquid interface of the Ti-MOF derivative multifunctional evaporator is as follows: the evaporator surface temperature rises to 40℃ within 15 minutes and stabilizes at 41℃ within 60 minutes.

[0052] Example 5

[0053] This embodiment provides a method for preparing a multifunctional evaporator based on Ti-MOF derivatives. The preparation method specifically includes the following steps:

[0054] Step 1: Immerse the treated carbon felt in Tris-Cl (pH=8.5) solution for 1 hour, then add dopamine hydrochloride to a concentration of 20 mg / mL and keep it under magnetic stirring for another 30 hours. After washing with water, vacuum dry at 70°C to obtain functionalized carbon felt.

[0055] Step 2: Add 0.5g of 2-aminoterephthalic acid and 1g of tetrabutyl titanate to 10mL of DMF, then add 3mL of methanol and stir for 30min. Then add the functionalized carbon felt and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and react hydrothermally at 150℃ for 10h. Wash the synthesized composite material with methanol and finally vacuum dry at 70℃ to obtain carbon felt loaded with NH2-MIL-125(Ti).

[0056] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) at 400℃ for 5 hours in an argon atmosphere, with a heat treatment rate of 5℃ / min, to obtain a Ti-MOF derivative multifunctional evaporator.

[0057] like Figure 5 As shown, the Ti-MOF derivative multifunctional evaporator has a distinct light absorption edge at 400 nm.

[0058] Example 6

[0059] This embodiment provides a method for preparing a multifunctional evaporator based on Ti-MOF derivatives. The preparation method specifically includes the following steps:

[0060] Step 1: Immerse the treated carbon felt in Tris-Cl (pH=8.5) solution for 1 hour, then add dopamine hydrochloride to a concentration of 20 mg / mL and keep it under magnetic stirring for another 10 hours. After washing with water, vacuum dry at 70°C to obtain functionalized carbon felt.

[0061] Step 2: Add 0.5g of 2-aminoterephthalic acid and 1g of tetrabutyl titanate to 30mL of DMF, then add 3mL of methanol and stir for 30min. Then add the functionalized carbon felt and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and react hydrothermally at 150℃ for 30h. Wash the synthesized composite material with methanol and finally vacuum dry at 70℃ to obtain carbon felt loaded with NH2-MIL-125(Ti).

[0062] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) at 1000℃ for 5 hours in an argon atmosphere at a heat treatment rate of 5℃ / min to obtain a Ti-MOF derivative multifunctional evaporator.

[0063] like Figure 6 As shown, since the Ti-MOF derivatives are small nanoparticles with a large specific surface area, the dark adsorption efficiency in a 50 mg / L ciprofloxacin solution is 60%, and the photocatalytic efficiency is 79.6%.

[0064] Example 7

[0065] This embodiment provides a method for preparing a multifunctional evaporator based on Ti-MOF derivatives. The preparation method specifically includes the following steps:

[0066] Step 1: Immerse the treated carbon felt in Tris-Cl (pH=8.5) solution for 1 hour, then add dopamine hydrochloride to a concentration of 5 mg / mL and keep it under magnetic stirring for another 10 hours. After washing with water, vacuum dry at 70°C to obtain functionalized carbon felt.

[0067] Step 2: Add 0.5g of 2-aminoterephthalic acid and 1g of tetrabutyl titanate to 30mL of DMF, then add 5mL of methanol and stir for 30min. Then add the functionalized carbon felt and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and react hydrothermally at 150℃ for 30h. Wash the synthesized composite material with methanol and finally vacuum dry at 70℃ to obtain carbon felt loaded with NH2-MIL-125(Ti).

[0068] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) at 1000℃ for 5 hours in air atmosphere, with a heat treatment rate of 10℃ / min, to obtain a Ti-MOF derivative multifunctional evaporator.

[0069] like Figure 7 As shown, the photothermal-photocatalytic synergistic degradation of 50 mg / L ciprofloxacin solution is twice that of pure photocatalysis, indicating that the photothermal-photocatalytic synergistic method has higher photocatalytic activity.

[0070] Example 8

[0071] This embodiment provides a method for preparing a multifunctional evaporator based on Ti-MOF derivatives. The preparation method specifically includes the following steps:

[0072] Step 1: Immerse the treated carbon felt in Tris-Cl (pH=8.5) solution for 1 hour, then add dopamine hydrochloride to a concentration of 0.1 mg / mL and keep it under magnetic stirring for another 30 hours. After washing with water, vacuum dry at 70°C to obtain functionalized carbon felt.

[0073] Step 2: Add 1g of 2-aminoterephthalic acid and 0.1g of tetrabutyl titanate to 1mL of DMF, then add 1mL of methanol and stir for 30min. Then add the functionalized carbon felt and stir for 15min. After magnetic stirring, transfer the mixture to a 100mL reactor and react hydrothermally at 300℃ for 10h. Wash the synthesized composite material with methanol and finally vacuum dry at 70℃ to obtain carbon felt loaded with NH2-MIL-125(Ti).

[0074] Step 3: Calcine the carbon felt loaded with NH2-MIL-125(Ti) at 100℃ for 10 hours in air atmosphere, with a heat treatment rate of 1℃ / min, to obtain a Ti-MOF derivative multifunctional evaporator.

[0075] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a Ti-MOF derivative multifunctional evaporator, characterized by, The method comprises the following steps: Step one, functionalizing carbon felt by wrapping polydopamine, washing with water, and vacuum drying to obtain functionalized carbon felt; Step two, loading NH2-MIL-125(Ti) on the surface of the functionalized carbon felt by a hydrothermal method, and washing the synthesized composite material with methanol, and vacuum drying to obtain the functionalized carbon felt loaded with NH2-MIL-125(Ti); Step three, calcining the functionalized carbon felt loaded with NH2-MIL-125(Ti) obtained in step two at 100-1000 ℃ under an argon atmosphere for 1-10 h, with a temperature rising rate of 1-10 ℃ / min, to obtain a Ti-MOF derivative multifunctional evaporator; The method for functionalizing carbon felt by wrapping polydopamine in step one comprises: immersing the carbon felt in a Tris-Cl solution for 1 h, then adding hydrochloric acid dopamine to a concentration of 0.1-20 mg / mL and keeping under magnetic stirring for 10-30 h, and finally washing with water and vacuum drying to obtain the functionalized carbon felt; The method for loading NH2-MIL-125(Ti) on the surface of the functionalized carbon felt in step two comprises: adding 0.1-1 g 2-amino terephthalic acid and 0.1-1 g tetrabutyl titanate in 1-30 mL DMF, then adding 1-30 mL methanol and stirring for 30 min, then adding the functionalized carbon felt prepared in step one and stirring for 15 min, and after magnetic stirring, transferring the mixture to a reaction kettle with a volume of 100 mL, and hydrothermal reaction at 100-300 ℃ for 10-30 h.

2. The method for preparing a Ti-MOF derivative multifunctional evaporator according to claim 1, characterized in that, The vacuum drying temperature in steps one and two is 70 ℃.

3. A Ti-MOF derivative multifunctional evaporator prepared by the method of any one of claims 1-2.

4. Use of the Ti-MOF derivative multifunctional evaporator of claim 3 in water treatment.

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