CN103934017A - Preparation method of microemulsion with efficient photocatalytic activity - Google Patents

Abstract

The invention discloses a preparation method of a microemulsion with efficient photocatalytic activity. The microemulsion is prepared from an MCF and Ti(SO4)2 serving as raw materials through a hydrothermal method, a vacuum activation method and an aid regulation and control method. Compared with the conventional F-doping method, the preparation method of the microemulsion with efficient photocatalytic activity has the advantages that equipment used in the vacuum activation method is simple, the production cost is reduced greatly, and industrial popularization is facilitated; by adopting the vacuum activation method, F doping of TiO2 can be realized, and hydrophobic modification of MCF can be realized; F atoms preferably substitute oxygen vacancies in vacuum activation, so that the photocatalysis of a catalyst is enhanced; under the assistance of a surfactant, a group surfactant and a continuous phase, the catalyst can be uniformly dispersed into a solution to form the microemulsion, so that industrial application is facilitated.

Description

A kind of preparation method with the microemulsion of high efficiency photocatalysis activity

Technical field

The present invention relates to nano-photocatalyst material field, relate in particular to a kind of preparation method with the microemulsion of high efficiency photocatalysis activity.

Background technology

As everyone knows, solar energy is a kind of clean free of contamination green energy resource, how efficiently to utilize solar energy, is key subjects in current environment field.TiO ₂as a kind of photochemical catalyst, can effectively utilize sun light quantity, realize efficient degradation to environmental pollutants, there are the potentiality of sustainable development.But TiO ₂not the band-gap energy that maximum application limitation is it and the spectrum of sunshine not mating extremely, TiO ₂the ultraviolet light that can only absorbing wavelength be less than 387nm.In order to realize the utilization to the full spectrum of solar energy, metal and nonmetal doping cause people's extensive concern.

Due to TiO ₂there are a large amount of hydrophily oh groups in surface, the ability of catalyst surface absorption organic pollution is weakened, and photo-quantum efficiency also reduces greatly.So, about how replacing catalyst surface hydroxyl, reduce the concern that its hydrophilic research is subject to more and more researchers.Can take lyophobic dust as substrate, by TiO ₂be deposited in hydrophobicity substrate, thereby reach TiO ₂carry out the improved object of hydrophobicity.At present, with comparatively extensive to the research of Hydrophobic Mesoporous molecular sieve, wherein fluoride has good chemical stability, causes adopting the zeolite molecular sieve of fluoride modification to have higher heat endurance and super-hydrophobicity.

Summary of the invention

Technical problem to be solved by this invention is that a kind of preparation method that can improve solar energy utilization ratio and can cross the convenient microemulsion with high efficiency photocatalysis activity in coating is provided.

In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of preparation method with the microemulsion of high efficiency photocatalysis activity, comprises the following steps:

1), preparation MCF molecular sieve: using P123 as surfactant, take TEOS as silicon source, stir 20h at 37 ℃, gained slurry is hydro-thermal 24h at 100 ℃, obtains MCF molecular sieve;

2), preparation MCF load TiO ₂catalyst: with titanium sulfate (Ti (SO ₄) ₂) be titanium source, MCF is carrier, by hydro-thermal reaction, obtains loaded catalyst MCF/TiO ₂;

3), preparation F doping MCF/TiO ₂catalyst: using NH4F as F source, evenly mix NH4F and MCF/TiO by spheroidal graphite method ₂catalyst, under 300 ℃ of vacuum activatings, obtains F doping MCF/TiO afterwards ₂catalyst;

4), preparation F doping MCF/TiO ₂microemulsion: by a certain amount of MCF/TiO ₂catalyst under agitation slowly add by Qu Latong-100, n-hexyl alcohol and the solution that forms of cyclohexane in, be made into microemulsion.

Further, TiO in described step 2 ₂high dispersive is in MCF duct.

Compared with prior art, usefulness of the present invention is: the preparation method of this microemulsion with high efficiency photocatalysis activity is with respect to the method for traditional doped F, and vacuum activating method equipment is simple, greatly reduces production cost, is conducive to industrialization promotion; Vacuum activating method not only can realize TiO ₂f doping, can also realize the hydrophobically modified to MCF simultaneously; F atom can preferentially replace oxygen defect in vacuum activating, thereby strengthens the photocatalysis of catalyst; At surfactant, group surfactant, and under the assistance of continuous phase, catalyst can be dispersed in solution, form microemulsion, so that industrial applications.

accompanying drawing explanation:

Below in conjunction with accompanying drawing, the present invention is further described.

Fig. 1 is the F doping MCF/TiO of embodiment 1 preparation ₂tEM schematic diagram;

Fig. 2 is the MCF/TiO of embodiment 1 preparation ₂with F doping MCF/TiO ₂xRD spectra;

Fig. 3 is the UV-DRS spectrogram of the catalyst of embodiment 1 preparation;

Fig. 4 is the F doping MCF/TiO of embodiment 1 preparation ₂, vacuum activating MCF/TiO ₂and MCF/TiO ₂photocatalytic activity figure at the lower degraded of Xe lamp (AM 1.5) MO.

the specific embodiment:

Below in conjunction with the drawings and specific embodiments, describe the present invention.

Embodiment 1:

1), preparation MCF molecular sieve:

8.0gP123 is joined to (1.6mol/L) in 300mL watery hydrochloric acid, at 37 ℃, be stirred to dissolving, then add 1,3 of the NH4F of 93.4mg and 4.0g, 5-trimethylbenzene, mechanical agitation 1h; Slowly drip the TEOS of 18.28ml again, stir 20h at 37 ℃, gained slurry is hydro-thermal 24h at 100 ℃, washing precipitation, and at 60 ℃ of vacuum drying 12h, then calcine 6h at 550 ℃, obtain MCF molecular sieve.

2), preparation MCF load TiO ₂catalyst:

Titanium sulfate (Ti (SO ₄) ₂) solid 3g is to autoclave inner bag, adds redistilled water 63ml, uses magnetic stirrer 30min, treats that titanium sulfate dissolves completely, mixes; Get the MCF of 2g, add autoclave inner bag, mix with titanium sulfate aqueous solution, magnetic agitation 30min, after solution mixes, then puts into autoclave by inner bag, puts to hydro-thermal 7h in 120 ℃ of baking ovens; Take out afterwards cooling; After cooling, use respectively ethanol and redistilled water washes clean, 60 ℃ of vacuum drying 12h, obtain loaded catalyst MCF/TiO ₂.

3), the MCF/TiO of preparation F doping ₂:

As shown in Figure 1, according to mass ratio, be MCF/TiO ₂: NH4F=2:1, sample is carried out to ball milling, ball milling speed 300rpm, Ball-milling Time 1h, carries out lower 300 ℃ of vacuum to sample afterwards and calcines 3h.

4), be made into microemulsion:

Get the MCF/TiO of 0.2g F doping ₂catalyst slowly add under stirring in the solution that the cyclohexane by Qu Latong-100,6mL n-hexyl alcohol and the 16mL of 10mL forms, be made into microemulsion.

Photocatalytic activity evaluation method provided by the invention is as follows:

As shown in Figures 2 to 4, by declining and separate the visible light catalysis activity that methyl orange (MO, 10mg/L) is evaluated prepared catalyst at visible ray.Photocatalytic degradation experiment is carried out on homemade device, takes 0.0700g catalyst sample and puts into crystal reaction tube, adds the MO solution of 70mL, stirs 2h, so that MO molecule reaches adsorption-desorption balance on the surface of catalyst at dark condition lower magnetic force; With illumination under the Xe lamp of configuration AM1.5 simulated solar irradiation optical filter, continue to stir in the process of illumination again, the distance at light source and quartz ampoule center is 1 cm.

In above-mentioned sunshine and ultraviolet catalytic active testing process, at interval of the regular hour, take out a certain amount of reaction solution, centrifugation, then use filtering head filtration catalizer, clear liquid is injected in cuvette, with Cary100 ultraviolet-visible spectrophotometer, measures the absorbance under maximum absorption wavelength (A) of degradation product solution; Compound Lambert-Beer's law between the absorbance A of degradation product molecule and concentration, so available formula (1) calculates its degradation rate:

Degradation rate=C/C0 * 100%= * 100%.

The preparation method of this microemulsion with high efficiency photocatalysis activity is with respect to the method for traditional doped F, and vacuum activating method equipment is simple, greatly reduces production cost, is conducive to industrialization promotion; Vacuum activating method not only can realize TiO ₂f doping, can also realize the hydrophobically modified to MCF simultaneously; F atom can preferentially replace oxygen defect in vacuum activating, thereby strengthens the photocatalysis of catalyst; At surfactant, group surfactant, and under the assistance of continuous phase, catalyst can be dispersed in solution, form microemulsion, so that industrial applications.

It is emphasized that: be only preferred embodiment of the present invention above, not the present invention is done to any pro forma restriction, any simple modification, equivalent variations and modification that every foundation technical spirit of the present invention is done above embodiment, all still belong in the scope of technical solution of the present invention.

Claims (2)

1. a preparation method with the microemulsion of high efficiency photocatalysis activity, is characterized in that, comprises the following steps:

1), preparation MCF molecular sieve: using P123 as surfactant, take TEOS as silicon source, stir 20h at 37 ℃, gained slurry is hydro-thermal 24h at 100 ℃, obtains MCF molecular sieve;

2), preparation MCF load TiO ₂catalyst: with titanium sulfate (Ti (SO ₄) ₂) be titanium source, MCF is carrier, by hydro-thermal reaction, obtains loaded catalyst MCF/TiO ₂;

3), preparation F doping MCF/TiO ₂catalyst: using NH4F as F source, evenly mix NH4F and MCF/TiO by spheroidal graphite method ₂catalyst, under 300 ℃ of vacuum activatings, obtains F doping MCF/TiO afterwards ₂catalyst;

4), preparation F doping MCF/TiO ₂microemulsion: by a certain amount of MCF/TiO ₂catalyst under agitation slowly add by Qu Latong-100, n-hexyl alcohol and the solution that forms of cyclohexane in, be made into microemulsion.

2. the preparation method with the microemulsion of high efficiency photocatalysis activity according to claim 1, is characterized in that, TiO in described step 2 ₂high dispersive is in MCF duct.