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WO2024007199A1 - 钛酸钡纳米颗粒复合共价有机骨架异质结及其制备方法 - Google Patents

钛酸钡纳米颗粒复合共价有机骨架异质结及其制备方法 Download PDF

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WO2024007199A1
WO2024007199A1 PCT/CN2022/104161 CN2022104161W WO2024007199A1 WO 2024007199 A1 WO2024007199 A1 WO 2024007199A1 CN 2022104161 W CN2022104161 W CN 2022104161W WO 2024007199 A1 WO2024007199 A1 WO 2024007199A1
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Prior art keywords
barium titanate
heterojunction
covalent organic
organic framework
nanoparticle composite
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PCT/CN2022/104161
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English (en)
French (fr)
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路建美
李娜君
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苏州大学
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Priority to PCT/CN2022/104161 priority Critical patent/WO2024007199A1/zh
Publication of WO2024007199A1 publication Critical patent/WO2024007199A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

Definitions

  • the invention relates to the technical fields of inorganic-organic nanocomposite materials and piezoelectric-photocatalysis, and specifically relates to the preparation of barium titanate nanoparticles/covalent organic framework heterojunction and its piezoelectric-photocatalytic degradation and removal of organic pollutants in water bodies. .
  • the prior art discloses a barium titanate nanomaterial for catalytically degrading trace organic pollutants in water and its preparation and application.
  • the barium titanate nanomaterial uses titanium hydroxide precursor and barium hydroxide octahydrate as titanic acid respectively.
  • the titanium source and barium source of barium nanomaterials are prepared by hydrothermal or solvothermal methods using sodium hydroxide and ethanol as reaction aids.
  • the prior art discloses an Ag NWs@BaTiO 3 core-sheath composite piezoelectric photocatalytic material and its preparation method and application.
  • the surface sheath is the piezoelectric material barium titanate BaTiO 3 and the core is silver nanowire Ag NWs.
  • the existing technology discloses a barium titanate/potassium niobate composite piezoelectric photocatalyst.
  • BaTiO 3 nanospheres with a particle size of 30-50 nm are evenly distributed on prism-shaped KNbO 3. It has good stability and excellent catalytic activity.
  • the preparation method of barium titanate catalyst is relatively complicated, and the treatment effect needs to be improved.
  • the purpose of the present invention is to provide a method for preparing barium titanate nanoparticles/covalent organic framework heterojunction.
  • the composite material formed can effectively remove bisphenol A in water under the combined action of ultrasonic vibration and light.
  • polyvinylpyrrolidone (PVP) and branched polyethylenimine (BPEI) are first modified on the surface of barium titanate, and then 1,3,5-tris(4-ammonium titanate) is encapsulated through a simple encapsulation method.
  • Phenyl)benzene (TAPB) and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP) are condensed on the surface of barium titanate to form a TAPB-DMTP-COF (TD-COF) shell, which is wrapped in titanium on the surface of barium acid nanoparticles.
  • TD-COF TAPB-DMTP-COF
  • the barium titanate in the present invention can form a core-shell heterojunction structure with TD-COF, and at the same time has good adsorption performance and piezoelectric-photocatalytic performance.
  • Experimental results show that under the combined action of ultrasound and light, the composite material has better performance in removing bisphenol A from water than barium titanate nanoparticles or pure TD-COF.
  • a barium titanate nanoparticle composite covalent organic framework heterojunction and its preparation method includes the following steps: (1) Barium titanate with a particle size of 30 to 100 nanometers The nanoparticles are mixed with an ethanol solution containing polyvinylpyrrolidone (PVP) and branched polyethyleneimine (BPEI) to obtain modified barium titanate nanoparticles; (2) Modified barium titanate nanoparticles, 1, 3,5-Tris(4-aminophenyl)benzene (TAPB) and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP) are mixed to obtain composite covalent barium titanate nanoparticles through an encapsulation reaction Organic framework heterojunction (BTO@TD-COF).
  • PVP polyvinylpyrrolidone
  • BPEI branched polyethyleneimine
  • a method for removing pollutants in water bodies including the following steps: placing barium titanate nanoparticle composite covalent organic framework heterojunction (BTO@TD-COF) into water bodies containing pollutants, ultrasonic and/or illuminating, Complete the removal of pollutants in water bodies.
  • BTO@TD-COF barium titanate nanoparticle composite covalent organic framework heterojunction
  • the barium titanate nanoparticles are barium titanate nanospheres (BTO);
  • the mass ratio of barium titanate nanoparticles, PVP, and BPEI is (30 ⁇ 50): (0.8 ⁇ 1.2) ⁇ 1, preferably 40:1:1;
  • the mass and weight ratio of PVP and BPEI relative to the ethanol solution is (0.03 ⁇ 0.07):1, preferably 0.05:1;
  • the mixing time is 18 ⁇ 30 h, preferably 24 h;
  • barium titanate nanoparticles are added to the ethanol solution of PVP and BPEI, magnetically stirred for 24 hours, centrifuged and washed after stirring, and dried to obtain modified barium titanate nanoparticles.
  • the present invention first uses PVP and BPEI to modify the barium titanate nanoparticles, which facilitates the growth of TD-COF on the surface of the barium titanate nanoparticles during the polycondensation process, thereby better wrapping the barium titanate nanoparticles.
  • step (2) the molar ratio of DMTP and TAPB is (0.5 ⁇ 2):1, preferably 1.5:1; 1,3,5-tris(4-aminophenyl)benzene (TAPB),
  • the mass ratio of the modified barium titanate nanoparticles is 10.5:1.95 ⁇ 9.75, preferably 10.5:5 ⁇ 6, such as 10.5:5.86.
  • the encapsulation reaction is carried out in the presence of acetic acid and in an organic solvent.
  • the modified barium titanate, TAPB and DMTP are mixed, and the added concentration is 10 ⁇ 17.5 M, preferably 17.5 M acetic acid, and the reaction is carried out at room temperature for 2 hours. Then add 8 ⁇ 12 M, preferably 10 M acetic acid and continue the reaction for 4 hours at 70 ° C. After Soxhlet extraction and drying, the barium titanate nanoparticle composite covalent organic framework heterojunction is obtained.
  • the organic solvents are 1,4-dioxane and n-butanol.
  • the barium titanate nanoparticle composite covalent organic framework heterojunction is placed into water containing pollutants, stirred in the dark, and then used ultrasonic-assisted illumination to achieve the removal of pollutants in the water.
  • the invention further discloses the application of barium titanate nanoparticles/covalent organic framework heterojunction in degrading pollutants in water, and the preferred pollutant is bisphenol A.
  • the barium titanate nanoparticles/covalent organic framework heterojunction disclosed in the present invention has the advantages of high stability, excellent performance and simple preparation method; 2.
  • the barium titanate nanoparticles disclosed in the present invention/ The existence of the voltage electric field in the covalent organic framework heterojunction can reduce the recombination rate of free carriers and effectively promote the separation of free carriers; 3.
  • This invention combines COF and barium titanate materials for the first time, and the existence of a built-in electric field It can effectively improve the photocatalytic performance of COF materials. At the same time, the excellent performance of COF materials enables composite materials to handle a large number of water pollutants.
  • Figure 1 shows the scanning electron microscopy and transmission electron microscopy images of TAPB-DMTP-COF.
  • the upper left corner is the transmission electron microscopy image.
  • Figure 2 shows the scanning electron microscope image and the transmission electron microscope image of the barium titanate nanoparticle/covalent organic framework heterojunction.
  • the upper left corner is the transmission electron microscope image.
  • Figure 3 shows the degradation curve of bisphenol A in water using different catalysts.
  • Figure 4 is a transmission electron microscope image of the barium titanate nanoparticle/covalent organic framework heterojunction.
  • Figure 5 is a cyclic degradation curve of bisphenol A in water by barium titanate nanoparticles/covalent organic framework heterojunction.
  • Covalent organic framework materials are an emerging class of crystalline porous organic materials. Due to their large specific surface area and good porosity, combined with barium titanate, they show good adsorption and degradation in water pollution treatment. ability, becoming a promising photocatalyst for environmental remediation.
  • the present invention obtains barium titanate nanoparticles/covalent organic framework heterojunction through a simple encapsulation method, and achieves the purpose of degrading water pollutants under the simultaneous action of ultrasound and light.
  • the raw materials of the present invention are existing products, and the specific preparation operations and testing methods are conventional technologies.
  • Example 1 Surface modification of barium titanate.
  • the specific steps are as follows: 10 mL of ethanol containing 200 mg of barium titanate nanospheres (D90 particle size 50 nm, purchased from Aladdin (Shanghai) Reagent Co., Ltd.) was added dropwise to 5 mg of barium titanate nanospheres. PVP and 5 mg BPEI in 10 mL of ethanol, and then the resulting mixture was stirred regularly at room temperature for 24 h. Finally, the product was washed with ethanol three times and dried at 60 ° C to obtain modified barium titanate (XBTO).
  • XBTO modified barium titanate
  • Example 2 Preparation of TAPB-DMTP-COF, the specific steps are as follows: 1,3,5-tris(4-aminophenyl)benzene (10.5 mg, 0.03 mmol), 2,5-dimethoxybenzene-1 , a mixture of 4-dicarboxaldehyde (8.7 mg, 0.045 mmol), 1,4-dioxane (2 mL) and n-butanol (2 mL) was conventionally sonicated for 60 minutes, and then 0.1 mL acetic acid was added and reacted at room temperature 2 h, then add 0.4 mL of 10 M acetic acid, and then react at 70°C for 4 h; after the reaction is completed, it is cooled to room temperature, the mixture is filtered and extracted with 250 mL of tetrahydrofuran Soxhlet for 24 h, and then dried at 60 ° C.
  • Figure 1 is a scanning electron microscope image of the above simple TAPB-DMTP-COF. It can be seen from the figure that simple TAPB-DMTP-COF has a regular nanosphere morphology.
  • Figure 2 is a scanning electron microscope image of the above-mentioned barium titanate nanoparticle composite covalent organic framework heterojunction. From the picture, it can be seen that the barium titanate nanoparticle composite covalent organic framework heterojunction still maintains a regular nanosphere morphology. , and it can be clearly seen that TAPB-DMTP-COF completely wraps barium titanate.
  • Example 4 Preparation of barium titanate nanoparticle composite covalent organic framework heterojunctions with different mass ratios. The specific steps are as follows: 1,3,5-tris(4-aminophenyl)benzene (10.5 mg, 0.03 mmol) , 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (8.7 mg, 0.045 mmol), 1,4-dioxane (2 mL), n-butanol (2 mL), and modification of 1.95 mg After the barium titanate mixture was sonicated for 60 minutes, 0.1 mL of acetic acid was added and reacted at room temperature for 2 h.
  • Example 5 Preparation of barium titanate nanoparticle composite covalent organic framework heterojunctions with different mass ratios. The specific steps are as follows: 1,3,5-tris(4-aminophenyl)benzene (10.5 mg, 0.03 mmol) , 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (8.7 mg, 0.045 mmol), 1,4-dioxane (2 mL), n-butanol (2 mL), and modification of 9.75 mg After the barium titanate mixture was sonicated for 60 minutes, 0.1 mL of acetic acid was added and reacted at room temperature for 2 h.
  • Example 6 Piezoelectric-photocatalytic degradation experiment of bisphenol A by different catalysts: Place 5 mg of catalyst in a small beaker of 50 mL bisphenol A aqueous solution with a concentration of 20 mg/L, and adsorb it in the dark for 2 hours. During this period, Take a sample of 1 mL after 60 minutes, filter it through a filter head (0.22 ⁇ m), and then inject it into a high-performance liquid phase sample bottle.
  • the catalysts are existing barium titanate nanospheres, TAPB-DMTP-COF, and BTO/TD-COF (BTO-3@TD-COF).
  • the degradation results of bisphenol A are shown in Figure 3.
  • the BTO/TD-COF of the present invention Complete degradation of bisphenol A was achieved 30 minutes after adsorption equilibrium.
  • Example 7 Using other catalysts, bisphenol A is degraded according to the method of Example 6. After 30 minutes of adsorption equilibrium, the residual rate of bisphenol A is as shown in Table 1; using BTO-3@TD-COF as the catalyst, in Example Based on method six, omitting ultrasound or light, 30 minutes after adsorption equilibrium, the residual rate of bisphenol A is as shown in Table 1.
  • XBTO+TD-COF refers to the regular grinding and mixing of modified barium titanate and TAPB-DMTP-COF for 30 minutes.
  • Example 8 Replace the barium titanate nanospheres in Example 1 with barium titanate cubes (D90 particle size 10 nm, purchased from Aladdin (Shanghai) Reagent Co., Ltd.), and leave the rest unchanged to obtain modified barium titanate. ; Then according to the method of Example 3, a barium titanate nanoparticle composite covalent organic framework heterojunction is obtained, and Figure 4 is a transmission electron microscope image thereof; Bisphenol A is degraded according to the method of Example 6, and after 30 minutes of adsorption equilibrium , Bisphenol A residual rate is 40%.
  • barium titanate cubes D90 particle size 10 nm, purchased from Aladdin (Shanghai) Reagent Co., Ltd.
  • Example 9 Cyclic degradation experiment of BTO-3@TD-COF on bisphenol A in water.
  • Example 6 the composite material recovered after ultrasonic illumination for 30 minutes was washed with deionized water and 95% ethanol in sequence, dried in a vacuum oven, and then re-added to the newly taken 50 mL of bisulfite with a concentration of 20 mg/L.
  • Phenol A solution was stirred for 2 h under dark conditions to achieve adsorption equilibrium. After equilibrium, transfer the solution to an ultrasonic cleaner, turn on the xenon light source (visible light) while turning on the ultrasound, take 1 mL every 5 minutes, filter it with a 0.22 ⁇ m filter head, and put it into a high-performance liquid phase sample bottle.
  • xenon light source visible light
  • the invention discloses a barium titanate nanoparticle/covalent organic framework heterojunction composite material that can effectively adsorb and degrade water-soluble organic pollutants under simultaneous stimulation by ultrasound and light.
  • 1,3,5-Tris(4-aminophenyl)benzene (TAPB) and 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMTP) were condensed and encapsulated in titanate through a simple encapsulation method.
  • a covalent organic framework shell (TD-COF) is formed on the surface of barium nanoparticles (BTO), and a barium titanate nanoparticle/covalent organic framework core-shell heterojunction (BTO@TD-COF) is constructed; in piezoelectricity and illumination , the catalytic performance is significantly improved.
  • BTO barium nanoparticles
  • BTO@TD-COF barium titanate nanoparticle/covalent organic framework core-shell heterojunction

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Abstract

本发明公开了一种钛酸钡纳米颗粒复合共价有机骨架异质结的制备方法与应用；将钛酸钡纳米颗粒与含有聚乙烯吡咯烷酮与支化聚乙烯亚胺的溶液混合，得到修饰后的钛酸钡纳米颗粒；将修饰后的钛酸钡纳米颗粒、1,3,5-三（4-氨苯基)苯和2,5-二甲氧基苯-1,4-二甲醛混合，通过封装反应得到钛酸钡纳米颗粒复合共价有机骨架异质结本发明选择钛酸钡与共价有机骨架（COFs）组成压电-光复合材料，结合二者的优势，其催化性能可以得到明显的提升。

Description

钛酸钡纳米颗粒复合共价有机骨架异质结及其制备方法 技术领域
本发明涉及无机-有机纳米复合材料及压电-光催化技术领域，具体涉及钛酸钡纳米颗粒/共价有机骨架异质结的制备及其对水体有机污染物的压电-光催化降解去除。
 背景技术
随着现代化进程的不断推进，人们的生活水平得到了很大提高，但也因此带来一连串的环境污染与能源短缺问题。为解决这些问题，需要探索并开发新能源驱动的低能耗且普适性强的环境修复技术。光催化材料，能够将太阳能转化为化学能，有望用于解决当前日益严重的环境问题。然而，光生电子与空穴的快速结合导致光催化效率低下，限制了光催化技术的实际应用。虽然已经探索了各种各样的策略来提高光催化效率，如金属或非金属掺杂、形貌调控、带隙工程和异质结结构，但在光催化过程中仍有巨大的有效电荷转移潜力。现有技术公开了一种用于催化降解水中微量有机污染物的钛酸钡纳米材料及其制备和应用，该钛酸钡纳米材料以氢氧化钛前驱物、八水合氢氧化钡分别作为钛酸钡纳米材料的钛源、钡源，以氢氧化钠、乙醇作为反应助剂，通过水热或溶剂热法制备。现有技术公开了一种Ag NWs@BaTiO 3芯鞘复合压电光催化材料及其制备方法和应用，表面鞘为压电材料钛酸钡BaTiO 3，芯为银纳米线Ag NWs。现有技术公开了钛酸钡/铌酸钾复合压电光催化剂，粒径为30‑50nm的BaTiO 3纳米球均布在棱柱状的KNbO 3上，稳定性较好，具有优良的催化活性。纵观现有技术，关于钛酸钡的催化剂制备方法较复杂，且处理效果还需改善。
技术问题
本发明的目的是提供一种钛酸钡纳米颗粒/共价有机骨架异质结的制备方法，所形成的复合材料在超声振动以及光照的共同作用下可以有效去除水体中的双酚A。作为具体的实施例，首先将聚乙烯吡咯烷酮（PVP）与支化聚乙烯亚胺（BPEI）修饰在钛酸钡的表面，然后通过简单的封装方法将1,3,5-三（4-氨苯基)苯（TAPB）和2,5-二甲氧基苯-1,4-二甲醛（DMTP）在钛酸钡表面缩聚形成TAPB-DMTP-COF（TD-COF）壳层，包裹在钛酸钡纳米颗粒表面上。本发明中的钛酸钡能与TD-COF形成核壳异质结结构，同时具有良好的吸附性能以及压电-光催化性能。实验结果表明在超声和光照共同作用下复合材料去除水体中双酚A的性能比钛酸钡纳米颗粒或者纯TD-COF优异。
 技术解决方案
为达到上述目的，本发明具体技术方案如下：一种钛酸钡纳米颗粒复合共价有机骨架异质结，其制备方法包括以下步骤：（1）将粒径为30～100纳米的钛酸钡纳米颗粒与含有聚乙烯吡咯烷酮（PVP）与支化聚乙烯亚胺（BPEI）的乙醇溶液混合，得到修饰后的钛酸钡纳米颗粒；（2）将修饰后的钛酸钡纳米颗粒、1,3,5-三（4-氨苯基)苯（TAPB）和2,5-二甲氧基苯-1,4-二甲醛（DMTP）混合，通过封装反应得到钛酸钡纳米颗粒复合共价有机骨架异质结（BTO@TD-COF）。
一种去除水体中污染物的方法，包括以下步骤：将钛酸钡纳米颗粒复合共价有机骨架异质结（BTO@TD-COF）置入含有污染物的水体中，超声和/或光照，完成水体中污染物的去除。
上述技术方案中，步骤（1）中，钛酸钡纳米颗粒为钛酸钡纳米球（BTO）；钛酸钡纳米颗粒、PVP、BPEI的质量比为（30~50）∶（0.8 ~1.2）∶1，优选40∶1∶1；PVP、BPEI的质量和相对于乙醇溶液的重量比为（0.03~0.07）∶1，优选0.05∶1；混合的时间为18~30 h，优选24 h；优选的，将钛酸钡纳米颗粒加入PVP和BPEI乙醇溶液中，磁力搅拌24 h，搅拌结束后离心洗涤，干燥后得到修饰后的钛酸钡纳米颗粒。本发明首先采用PVP以及BPEI修饰钛酸钡纳米颗粒，利于TD-COF在缩聚过程中能在钛酸钡纳米颗粒表面上生长，从而更好的将钛酸钡纳米颗粒包裹起来。
上述技术方案中，步骤（2）中，DMTP和TAPB的摩尔比为（0.5~2）∶1，优选1.5∶1；1,3,5-三（4-氨苯基)苯（TAPB）、修饰后的钛酸钡纳米颗粒的质量比为10.5∶1.95~9.75，优选10.5∶5~6，比如10.5∶5.86。
上述技术方案中，封装反应在乙酸存在下、有机溶剂中进行，优选的，将修饰后的钛酸钡、TAPB和DMTP混合，加入浓度为10~17.5 M，优选17.5 M乙酸常温反应2 h，然后加入8~12 M，优选10 M乙酸在70 oC下继续反应4 h，索氏提取后干燥得到钛酸钡纳米颗粒复合共价有机骨架异质结。有机溶剂为1,4 -二氧六环和正丁醇。
上述技术方案中，将钛酸钡纳米颗粒复合共价有机骨架异质结置入含有污染物的水中，避光搅拌后用超声辅助光照，实现水中污染物的去除。
本发明进一步公开了钛酸钡纳米颗粒/共价有机骨架异质结在降解处理水中污染物中的应用，优选污染物为双酚A。
 有益效果
本发明的优点：1. 本发明公开的钛酸钡纳米颗粒/共价有机骨架异质结具有稳定性高、性能出色与制备方法简单等优点；2. 本发明公开的钛酸钡纳米颗粒/共价有机骨架异质结中压电场的存在可以降低自由载流子的复合率，有效促进自由载流子的分离；3. 本发明首次将COF和钛酸钡材料结合，内置电场的存在能有效提升了COF材料的光催化性能，同时COF材料的优异性能使得复合材料能够处理大量的水体污染物。
 附图说明
图1为TAPB-DMTP-COF的扫描电镜图与透射电镜图，其中左上角为透射电镜图。
图2为钛酸钡纳米颗粒/共价有机骨架异质结的扫描电镜图与透射电镜图，其中左上角为透射电镜图。
图3为不同催化剂对水中双酚A的降解曲线图。
图4为钛酸钡纳米颗粒/共价有机骨架异质结的透射电镜图。
图5为钛酸钡纳米颗粒/共价有机骨架异质结对水中双酚A的循环降解曲线图。
 本发明的实施方式
压电材料在受到外界应力时，会在其相对表面产生正负电荷，由此建立的内置电场能够抑制光生电子与空穴复合。本发明将压电与光催化有效结合，达到十分优异的污染物降解能力。共价有机骨架材料（COFs），是一类新兴的晶体多孔有机材料，由于其具有大的比表面积、良好的孔隙度，结合钛酸钡，在水污染处理方面同时展现出良好的吸附以及降解能力，成为一种应用于环境修复方向很有前途的光催化剂。本发明通过简单的封装方法得到钛酸钡纳米颗粒/共价有机骨架异质结，在超声和光照的同时作用下，实现降解水体污染物的目的。本发明的原料为现有产品，具体制备操作以及测试方法为常规技术。
实施例一 钛酸钡的表面修饰，具体步骤如下：将含有  200 mg 钛酸钡纳米球（D90粒径50 nm，购自阿拉丁（上海）试剂有限公司）的10 mL乙醇滴加入含有5 mg PVP和5 mg BPEI的10 mL乙醇中，再将得到的混合液在常温下常规搅拌24 h，最后用乙醇洗涤产物三次，在60 oC下干燥，得到修饰后的钛酸钡（XBTO）。
实施例二TAPB-DMTP-COF的制备，具体步骤如下：将1,3,5-三（4-氨苯基)苯 （10.5 mg, 0.03 mmol）、2,5-二甲氧基苯-1,4-二甲醛（8.7 mg, 0.045 mmol）、1,4 -二氧六环（2 mL）和正丁醇（2 mL）的混合物常规超声60分钟，然后加入0.1mL乙酸，在室温下反应2 h，随后添加0.4 mL 10 M 的乙酸，然后在70°C下反应4 h；反应结束后冷却到室温，将混合物过滤后用250 mL四氢呋喃索氏提取24 h，然后在60 oC下干燥，得到TAPB-DMTP-COF（TD-COF）。附图1为上述单纯TAPB-DMTP-COF的扫描电镜图。从图中可以看到单纯的TAPB-DMTP-COF具有规整的纳米球形貌。
实施例三 钛酸钡纳米颗粒复合共价有机骨架异质结的制备，具体步骤如下：将1,3,5-三（4-氨苯基)苯（10.5 mg, 0.03 mmol）、2,5-二甲氧基苯-1,4-二甲醛（8.7 mg, 0.045 mmol）、1,4 -二氧六环（2 mL）、正丁醇（2 mL）和5.86 mg的修饰后钛酸钡的混合物常规超声60分钟，然后加入0.1mL乙酸，在室温下反应2 h，随后添加0.4 mL 10 M 的乙酸，然后在70°C下反应4 h；反应结束后冷却到室温，将混合物过滤后用250 mL四氢呋喃索氏提取24 h，然后在60 oC下干燥，得到最终产物钛酸钡纳米颗粒复合共价有机骨架异质结（BTO-3@TD-COF）。附图2为上述钛酸钡纳米颗粒复合共价有机骨架异质结的扫描电镜图，从图中可以看到钛酸钡纳米颗粒复合共价有机骨架异质结仍然保持规整的纳米球形貌，且明显能看出TAPB-DMTP-COF将钛酸钡完全包裹。
实施例四 不同质量比的钛酸钡纳米颗粒复合共价有机骨架异质结的制备，具体步骤如下：将1,3,5-三（4-氨苯基)苯（10.5 mg, 0.03 mmol）、2,5-二甲氧基苯-1,4-二甲醛（8.7 mg, 0.045 mmol）、1,4 -二氧六环（2 mL）、正丁醇（2 mL）和1.95 mg的修饰后钛酸钡的混合物常规超声60分钟，然后加入0.1mL乙酸，在室温下反应2 h，随后添加0.4 mL 10 M 的乙酸，然后在70°C下反应4 h；反应结束后冷却到室温，将混合物过滤后用250 mL四氢呋喃索氏提取24 h，然后在60 oC下干燥，得到最终产物钛酸钡纳米颗粒复合共价有机骨架异质结（BTO-1@TD-COF）。
实施例五 不同质量比的钛酸钡纳米颗粒复合共价有机骨架异质结的制备，具体步骤如下：将1,3,5-三（4-氨苯基)苯（10.5 mg, 0.03 mmol）、2,5-二甲氧基苯-1,4-二甲醛（8.7 mg, 0.045 mmol）、1,4 -二氧六环（2 mL）、正丁醇（2 mL）和9.75 mg的修饰后钛酸钡的混合物常规超声60分钟，然后加入0.1mL乙酸，在室温下反应2 h，随后添加0.4 mL 10 M 的乙酸，然后在70°C下反应4 h；反应结束后冷却到室温，将混合物过滤后用250 mL四氢呋喃索氏提取24 h，然后在60 oC下干燥，得到最终产物钛酸钡纳米颗粒复合共价有机骨架异质结（BTO-5@TD-COF）。
对比例一：将1,3,5-三（4-氨苯基)苯（10.5 mg, 0.03 mmol）、2,5-二甲氧基苯-1,4-二甲醛（8.7 mg, 0.045 mmol）、1,4 -二氧六环（2 mL）、正丁醇（2 mL）和5.86 mg的钛酸钡纳米球（D90粒径50 nm，购自阿拉丁（上海）试剂有限公司）的混合物常规超声60分钟，然后加入0.1mL乙酸，在室温下反应2 h，随后添加0.4 mL 10 M 的乙酸，然后在70°C下反应4 h；反应结束后冷却到室温，将混合物过滤后用250 mL四氢呋喃索氏提取24 h，然后在60 oC下干燥，得到最终产物（WBTO@TD-COF）。
实施例六：不同催化剂对双酚A的压电-光催化降解实验：取5 mg 催化剂置于50 mL浓度为20 mg/L的双酚A水溶液小烧杯中，避光吸附2小时，期间每60 min取样1 mL，经滤头（0.22 μm）过滤后注入高效液相样品瓶中。吸附平衡之后，将样品转移至玻璃试管中，将试管置于超声清洁器中，打开超声（180 W，45 Hz）的同时打开氙灯光源（可见光，300 W），每5 min取样1 mL，经滤头（0.22 μm）过滤除去催化剂后注入高效液相样品瓶中，使用高效液相色谱仪在去离子水：甲醇= 30：70 的流动相中测试样品在290 nm 紫外波长下的吸收曲线，记录在6 min 左右的双酚A 出峰面积，并把初始双酚A 的浓度记为100 %，得到双酚A 的压电催化降解曲线。
催化剂分别为现有钛酸钡纳米球、TAPB-DMTP-COF、BTO/TD-COF（BTO-3@TD-COF），对双酚A的降解结果见图3，本发明BTO/TD-COF在吸附平衡之后30分钟时实现双酚A的完全降解。
实施例七：采用其他催化剂，按照实施例六的方法进行双酚A降解，吸附平衡之后30分钟时，双酚A残留率如表1；采用BTO-3@TD-COF为催化剂，在实施例六的方法基础上，省略超声或者光照，吸附平衡之后30分钟时，双酚A残留率如表1。
。
XBTO+TD-COF是指修饰后的钛酸钡与TAPB-DMTP-COF常规研磨混合30分钟。
实施例八：将实施例一的钛酸钡纳米球更换为钛酸钡立方体（D90粒径10 nm，购自阿拉丁（上海）试剂有限公司），其余不变，得到修饰后的钛酸钡；再根据实施例三的方法，得到钛酸钡纳米颗粒复合共价有机骨架异质结，图4为其透射电镜图；按照实施例六的方法进行双酚A降解，吸附平衡之后30分钟时，双酚A残留率40%。
实施例九：BTO-3@TD-COF对水中双酚A的循环降解实验。实施例六中经超声光照30 min 后回收的复合材料依次用去离子水和 95%乙醇洗涤，置于真空烘箱中烘干，再重新加入到新取的50 mL浓度为20 mg/L的双酚A溶液中，在黑暗条件下搅拌2 h以达到吸附平衡。平衡后，将溶液转移至超声清洗器中，打开超声的同时打开氙灯光源（可见光），每5 min取1 mL，用0.22 μm的滤头过滤后放入高效液相样品瓶中，使用高效液相色谱仪在去离子水：甲醇=3：7（体积比）的流动相中测试样品在290 nm紫外波长下的吸收曲线，记录6 min左右的双酚A出峰面积，把初始双酚A的浓度记为100%，得到双酚A的压电降解曲线。依照上述步骤重复 5 次，分别测试并记录数据，其结果如附图5所示。从图中可以看出，在5次重复过程中，本发明的压电催化剂始终保持优良的压电催化性能，水溶液中双酚A的最终去除率均大于90%。因此，该催化剂可以重复使用，具有良好的稳定性。
本发明公开了一种能在超声和光照同时激发下有效吸附并降解水溶性有机污染物的钛酸钡纳米颗粒/共价有机骨架异质结复合材料。通过简单的封装方法将1,3,5-三（4-氨苯基)苯（TAPB）和2,5-二甲氧基苯-1,4-二甲醛（DMTP）缩聚并包裹在钛酸钡纳米颗粒（BTO）表面形成共价有机骨架壳层（TD-COF），构建了钛酸钡纳米颗粒/共价有机骨架核壳异质结（BTO@TD-COF）；在压电与光照下，催化性能提升明显。

Claims (10)

  1. 一种钛酸钡纳米颗粒复合共价有机骨架异质结的制备方法，其特征在于，包括以下步骤：
    （1）将钛酸钡纳米颗粒与含有聚乙烯吡咯烷酮与支化聚乙烯亚胺的溶液混合，得到修饰后的钛酸钡纳米颗粒；
    （2）将修饰后的钛酸钡纳米颗粒、1,3,5-三（4-氨苯基)苯和2,5-二甲氧基苯-1,4-二甲醛混合，通过封装反应得到钛酸钡纳米颗粒复合共价有机骨架异质结。
  2. 根据权利要求1所述钛酸钡纳米颗粒复合共价有机骨架异质结的制备方法，其特征在于，钛酸钡纳米颗粒为钛酸钡纳米球；钛酸钡纳米颗粒、聚乙烯吡咯烷酮、支化聚乙烯亚胺的质量比为（30~50）∶（0.8~1.2）∶1。
  3. 根据权利要求1所述钛酸钡纳米颗粒复合共价有机骨架异质结的制备方法，其特征在于，步骤（1）中，混合的时间为18~30 h。
  4. 根据权利要求1所述钛酸钡纳米颗粒复合共价有机骨架异质结的制备方法，其特征在于，2,5-二甲氧基苯-1,4-二甲醛、1,3,5-三（4-氨苯基)苯的摩尔比为（0.5~2）∶1；1,3,5-三（4-氨苯基)苯、修饰后的钛酸钡纳米颗粒的质量比为10.5∶1.95~9.75。
  5. 根据权利要求1所述钛酸钡纳米颗粒复合共价有机骨架异质结的制备方法，其特征在于，封装反应在乙酸存在下、有机溶剂中进行。
  6. 根据权利要求1所述钛酸钡纳米颗粒复合共价有机骨架异质结的制备方法，其特征在于，将修饰后的钛酸钡纳米颗粒、1,3,5-三（4-氨苯基)苯和2,5-二甲氧基苯-1,4-二甲醛混合，加入乙酸常温反应，然后再加入乙酸在60℃~80℃下继续反应，得到钛酸钡纳米颗粒复合共价有机骨架异质结。
  7. 根据权利要求1所述钛酸钡纳米颗粒复合共价有机骨架异质结的制备方法制备的钛酸钡纳米颗粒复合共价有机骨架异质结。
  8. 一种去除水体中污染物的方法，其特征在于，包括以下步骤：将权利要求7所述钛酸钡纳米颗粒复合共价有机骨架异质结置入含有污染物的水体中，超声和/或光照，完成水体中污染物的去除。
  9. 根据权利要求8所述去除水体中污染物的方法，其特征在于，将钛酸钡纳米颗粒复合共价有机骨架异质结置入含有污染物的水中，避光搅拌后用超声结合光照，实现水中污染物的去除。
  10. 权利要求7所述钛酸钡纳米颗粒复合共价有机骨架异质结在降解水中污染物中的应用。
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CN119060281A (zh) * 2024-08-26 2024-12-03 大理大学 一种亚胺连接的共价有机框架的制备以及在光催化降解中的应用

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