Core-shell type composite micro-nanoparticles and preparation method thereof

A micro-nano particle, core-shell technology, used in chemical instruments and methods, special compound water treatment, organic compound/hydride/coordination complex catalysts, etc., can solve the problems of high temperature operation, harsh conditions, and complexity. Achieve the effects of mild reaction conditions, low cost and simple process

Active Publication Date: 2018-12-21

FUJIAN NORMAL UNIV

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AI-Extracted Technical Summary

Problems solved by technology

In the prior art, TiO is usually treated by the "grafting to" method and the "grafting from surface" method. 2 To achieve modification, although the "grafting from the surface" metho...

Method used

Known from above-mentioned description, utilize conjugated polymer as raw material, polyfluorene micro-nano particle is obtained TiO through steps such as sulfonation Composite micro-nano particle coated, because the spherical surface characteristic of polyfluorene micro-nano particle and high Quantum efficiency, TiO2-coated polyfluorene composite micro-nanoparticle components have a synergistic effect, and this synergistic effect enhances the photocatalytic activity of TiO2. The invention adopts a solid-phase oxidation coupling method to prepare polyfluorene micro-nano particles, and the method has a simple process, does not need a solvent, and is environmentally friendly. The core-shell type composite micro-nano particle has low preparation cost, mild reaction conditions, energy saving and environmental protection. When carrying out the solid-phase oxidation coupling reaction, grind until no irritating smell is produced, and the mass fraction of the concentrated sulfuric acid used in the sulfonation reaction is at least 70%.

The core-shell type composite micro-nano particle that embodiment two to embodiment six is made adopts the above-mentioned same method to carry out...

Abstract

The invention discloses core-shell type composite micro-nanoparticles and a preparation method thereof. Each core-shell type composite micro-nanoparticle comprises an inner core layer and a shell layer, wherein the shell layer is a titanium dioxide layer; the inner core layer is a polyfluorene layer. The preparation method of the core-shell type composite micro-nanoparticles comprises the following steps: taking a fluorene monomer as a raw material; preparing through a solid-phase oxidative coupling method to prepare polyfluorene micro-nanoparticles; carrying out sulfonation reaction on the polyfluorene micro-nanoparticles and concentrated sulfuric acid to obtain sulfonated micro-nanoparticles; carrying out adsorption and hydrolysis reaction on the sulfonated micro-nanoparticles and tetra-n-butyl titanate in sequence to obtain the core-shell type composite micro-nanoparticles. The core-shell type composite micro-nanoparticles have the advantages of good photocatalysis effect, stable chemical performance and the like; the preparation method has the advantages of simple technology, energy saving and environment protection, low manufacturing cost and the like.

Application Domain

Water/sewage treatment by irradiationWater treatment compounds +2

Technology Topic

Solid phasesPhotocatalysis +10

Image

Examples

Experimental program(8)
Effect test(1)

Example Embodiment

[0022] A method for preparing core-shell composite micro-nano particles, using fluorene monomer as a raw material to prepare polyfluorene micro-nano particles by a solid-phase oxidative coupling method; sulfonating the polyfluorene micro-nano particles with concentrated sulfuric acid , To obtain sulfonated micro-nano particles; the sulfonated micro-nano particles and tetra-n-butyl titanate are sequentially adsorbed and hydrolyzed to obtain the core-shell composite micro-nano particles.

[0023] Reaction principle: Polyfluorene micro-nano particles can undergo sulfonation reaction in concentrated sulfuric acid, grafted with sulfonic acid groups, polyfluorene micro-nano particles with sulfonic acid groups can adsorb tetra-n-butyl titanate, tetra-n-titanate Butyl ester can be hydrolyzed to get TiO 2 , TiO 2 Coated on the surface of polyfluorene micro-nano particles to form core-shell micro-nano particles.

[0024] It can be seen from the above description that conjugated polymers are used as raw materials to obtain TiO from polyfluorene micro-nano particles through sulfonation and other steps. 2 Coated composite micro-nano particles, due to the spherical surface characteristics and high quantum efficiency of polyfluorene micro-nano particles, TiO 2 The coated polyfluorene composite micro-nanoparticles have a synergistic effect between the components, and this synergistic effect enhances the TiO 2 The photocatalytic activity. The invention adopts a solid-phase oxidative coupling method to prepare polyfluorene micro-nano particles. The method has simple process, no solvent, and is environmentally friendly. The core-shell type composite micro-nano particles have low preparation cost, mild reaction conditions, energy saving and environmental protection. During the solid-phase oxidative coupling reaction, grinding until no pungent odor is produced, and the mass fraction of concentrated sulfuric acid used in the sulfonation reaction is at least 70%.

[0025] Further, the catalytic oxidant of the solid-phase oxidative coupling method is anhydrous ferric chloride.

[0026] It can be seen from the above description that the amount of anhydrous ferric chloride is at least three times the amount of fluorene monomer.

[0027] Further, the polyfluorene micro-nano particles are first dispersed in absolute ethanol, and then concentrated sulfuric acid is added to perform a sulfonation reaction. The temperature of the sulfonation reaction is 38-42° C. and the time is 1-8 h.

[0028] It can be seen from the above description that the first dispersion of polyfluorene micro-nano particles is beneficial to improve the sulfonation effect.

[0029] Further, first disperse the sulfonated micro-nano particles in absolute ethanol, and then add tetra-n-butyl titanate to adsorb the tetra-n-butyl titanate on the sulfonated micro-nano particles, and the adsorption temperature is 25~30℃, time is 2~8h.

[0030] It can be seen from the above description that the dispersion of sulfonated micro-nano particles is beneficial to uniform adsorption of tetra-n-butyl titanate.

[0031] Further, the sulfonated micro-nano particles with tetra-n-butyl titanate adsorbed are first washed with ethanol, and then subjected to a hydrolysis reaction in an ethanol/water mixed solution, the temperature of the hydrolysis reaction is 25-30°C, and the time For 3~5h.

[0032] It can be seen from the above description that the purpose of washing is to remove unadsorbed tetra-n-butyl titanate, and the volume ratio of ethanol to water in the ethanol/water mixed solution is 1:1.

[0033] Further, the sulfonated micro-nano particles are washed and centrifuged sequentially, and then reacted with tetra-n-butyl titanate.

[0034] It can be seen from the above description that the purpose of washing is to remove concentrated sulfuric acid.

[0035] Further, the polyfluorene micro-nano particles or sulfonated micro-nano particles are dispersed in absolute ethanol by an ultrasonic dispersion method, and the ultrasonic dispersion time is at least 10 min.

[0036] It can be seen from the above description that the dispersion effect of ultrasonic dispersion is good.

[0037] Further, it also includes washing, centrifuging and drying the core-shell composite micro-nano particles in sequence.

[0038] It can be seen from the above description that post-treatment of core-shell composite micro-nano particles can improve their quality and purity, and improve the photocatalytic effect.

Example Embodiment

[0039] Example one

[0040] Please refer to figure 1 , The first embodiment of the present invention is:

[0041] A core-shell type composite micro-nano particle, comprising a core layer 1 and a shell layer 2. The shell layer 2 is a titanium dioxide layer, the core layer 1 is a polyfluorene layer, and the core-shell type composite micro-nano particles The particle size is 5-10μm.

Example Embodiment

[0042] Example two

[0043] Please refer to figure 2 The second embodiment of the present invention is a method for preparing core-shell composite micro-nano particles, which includes the following steps:

[0044] Step 1: Put 0.83g (5mmol) of fluorene and 3.24g (20mmol) of anhydrous ferric chloride in a glass mortar, grind with a mallet for half an hour at room temperature, and then wash the mixture with 5% hydrochloric acid ethanol solution , Suction filtration and drying to obtain the crude product, and then extract with absolute ethanol to obtain polyfluorene micro-nano particles.

[0045] Step 2: Perform a sulfonation reaction between the polyfluorene micro-nano particles and concentrated sulfuric acid to obtain sulfonated micro-nano particles. Specifically: the polyfluorene micronanoparticles are first dispersed in absolute ethanol by ultrasonic dispersion, and then concentrated sulfuric acid is added to carry out the sulfonation reaction. The ultrasonic dispersion time is at least 10 minutes, and the sulfonation reaction temperature is 40 minutes. ℃, time is 3h, can be heated by oil bath, the mass fraction of concentrated sulfuric acid used in sulfonation reaction is at least 70%. The sulfonated micro-nano particles are washed and centrifuged in sequence to remove unreacted concentrated sulfuric acid, and absolute ethanol is used as a solvent during washing.

[0046] Step 3: Adsorb and hydrolyze the sulfonated micro-nano particles and tetra-n-butyl titanate sequentially to obtain the core-shell composite micro-nano particles. Specifically: first disperse the sulfonated micro-nano particles in 100 mL of absolute ethanol by means of ultrasonic dispersion, the ultrasonic dispersion time is at least 10 minutes, and then add 100 mL of tetra-n-butyl titanate, under the action of magnetic stirring The tetra-n-butyl titanate is adsorbed on the sulfonated micro-nano particles at a temperature of 25° C. and a time of 8 h. The sulfonated micro-nanoparticles adsorbed with tetra-n-butyl titanate are washed and centrifuged with ethanol to remove excess tetra-n-butyl titanate, and then undergo a hydrolysis reaction in an ethanol/water mixed solution. The temperature is 25℃, the time is 4h, and the volume ratio of ethanol to water in the ethanol/water mixed solution is 1:1.

[0047] Step 4: Washing, centrifuging and drying the core-shell composite micro-nano particles in sequence, and the washing solvent is absolute ethanol.

PUM

Property	Measurement	Unit
Particle size	5.0 ~ 10.0	µm

Description & Claims & Application Information

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Core-shell type composite micro-nanoparticles and preparation method thereof

AI-Extracted Technical Summary

Problems solved by technology

Method used

Abstract

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Example Embodiment

Example Embodiment

Example Embodiment

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Description & Claims & Application Information

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