CN112588322A - Super-hydrophobic polymer/titanium-based photocatalytic aerogel block and preparation method thereof - Google Patents
Super-hydrophobic polymer/titanium-based photocatalytic aerogel block and preparation method thereof Download PDFInfo
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- CN112588322A CN112588322A CN202011599300.8A CN202011599300A CN112588322A CN 112588322 A CN112588322 A CN 112588322A CN 202011599300 A CN202011599300 A CN 202011599300A CN 112588322 A CN112588322 A CN 112588322A
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- tio
- titanium
- hydrophobic
- aerogel
- super
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Abstract
The invention discloses a super-hydrophobic polymer/titanium-based photocatalytic aerogel block and a preparation method thereofWater (W/O) type gel emulsion, preparing aerogel with continuously adjustable pore structure, shape and density by using the water (W/O) type gel emulsion as a template, and finally passing through hydrophobic nano SiO2And (3) carrying out aftertreatment on the sol to obtain the super-hydrophobic polymer/titanium-based photocatalytic aerogel block. The aerogel block material obtained by the invention has excellent adsorbability and photocatalytic activity, super-hydrophobicity, high toughness and large block morphology, is convenient for realizing device design and recycling of the material, and enables the adsorption/photocatalytic technology to be better applied to the fields of water treatment, oil-water separation and the like.
Description
Technical Field
The invention belongs to the technical field of environmental protection materials, and particularly relates to a super-hydrophobic polymer/titanium-based photocatalytic aerogel block material with functions of adsorbing and degrading pollutants by visible light photocatalysis and a preparation method thereof.
Background
With the rapid development of industry and agriculture, water pollution, particularly petroleum and organic matters, is more and more serious, organic wastewater has complex components and is difficult to biodegrade, the organic wastewater is accumulated and stored in natural environments such as water, soil and the like, the ecological environment and human health are seriously damaged, and the effective treatment of the organic wastewater is a research focus and a difficult point in the current pollution control field.
The traditional method for treating organic pollutants mainly comprises the following steps: physical treatment technology, chemical treatment technology, biological treatment technology. The traditional treatment method has the problems of strict reaction conditions, narrow application range, low degradation efficiency, high energy consumption, easy generation of secondary pollution and the like. Photocatalytic degradation technology is receiving increasing attention due to its advantages of low selectivity to pollutants, mild reaction conditions, and fast reaction rate. TiO 22The photocatalyst is widely applied, but has wide band gap, low sunlight utilization rate and difficult recovery, so the development of the high-efficiency photocatalytic material capable of being repeatedly used has important significance. An ideal material for efficient removal of micropollutants from water would generally have the following advantages: firstly, the adsorbent has higher adsorption capacity and rapid degradation capability on target pollutants; secondly, the material has higher mechanical strength and is not easy to dissolve in water so as to avoid secondary pollution to the environment(ii) a Third, lower cost. Researchers have developed a series of studies, such as doping, depositing noble metals, etc., in widening the spectral response range of photocatalysts to improve the utilization rate of sunlight.
In recent years, the photocatalyst is made into aerogel to better exert the characteristics of the nano material, so as to improve the use efficiency of the photocatalyst, and the photocatalyst is more and more noticed. Such as Melone, by adopting a sol-gel method combined with freeze drying at-80 ℃ to prepare TiO2Aerogels (Melone L, Altomarea L, Alferi I, et al. ceramic aerogels from TEM-PO-oxidized cellulose nanoparticles: Synthesis, chromatography, and photocatalytic properties. journal of Photochemistry and Photobiology A: chemistry.2013,261: 53-60); preparation of CrO by Weersighe et al using supercritical drying technique2Doped SiO2-TiO2Aerogels (Weerasinghe M N P, Kenneth J K. chromium oxide loaded silica aerogels: Novel visible light photocatalytic materials for environmental registration. J PHOTOCOCH PHOTOBIO A.2013,254, 62-70); bin and the like are dried under normal pressure by adopting a formamide drying control agent to prepare TiO2Aerogel (bin, zhangdingri, song 28156. At present, each preparation method either needs a high-end drying process and a complex preparation process, or needs a toxic organic solvent, which is not beneficial to developing practical application or is not environment-friendly.
Disclosure of Invention
The invention aims to provide a super-hydrophobic polymer/titanium-based photocatalytic aerogel block material with efficient adsorption-photocatalytic degradation functions on organic pollutants in water and a preparation method thereof. The preparation method has simple operation process and mild reaction condition, and does not need toxic organic solvent. Through the hydrophobization treatment of the high-efficiency photocatalyst, the high-efficiency photocatalyst is better dispersed in the oil phase of the gel emulsion, and a polymer/photocatalyst aerogel block material with good composite effect is obtained. The aerogel prepared by the method has the advantages of super hydrophobicity, high flexibility, high adsorbability, high catalytic activity, easy processing and easy recycling.
Aiming at the purposes, the super-hydrophobic polymer/titanium-based photocatalytic aerogel bulk material adopted by the invention is prepared by the following method:
1. preparation of gel emulsion
Mixing the oil phase and distilled water in a mixer at room temperature to obtain gel emulsion; wherein the oil phase comprises the following components in percentage by mass: 1 to 5 percent of gelling agent, 3 to 10 percent of initiator, 3 to 10 percent of cross-linking agent, 5 to 10 percent of hydrophobic titanium-based photocatalyst and 70 to 85 percent of monomer.
2. Preparation of super-hydrophobic polymer/titanium-based photocatalytic aerogel block
Prepolymerizing the gel emulsion prepared in the step 1 at 40-50 ℃ for 1-3 h, heating to 70-85 ℃ for polymerization for 3-5 h, cooling, taking out the block, washing, drying, and then adding hydrophobic nano SiO2And soaking the sol for 10-60 min for super-hydrophobicity treatment, washing and drying to obtain the super-hydrophobic polymer/titanium-based photocatalytic aerogel block.
In the step 1, the volume ratio of the oil phase to the distilled water is 1: 3-4.
The oil phase preferably comprises the following components in percentage by mass: 2 to 3 percent of gelling agent, 5 to 8 percent of initiator, 6 to 8 percent of cross-linking agent, 6 to 8 percent of hydrophobic titanium-based photocatalyst and 75 to 80 percent of monomer.
The hydrophobic titanium-based photocatalyst is TiO subjected to hydrophobic treatment by using a silane coupling agent2、TiO2/C3N4、TiO2Graphene oxide and TiO2/C3N4Graphene oxide and TiO2/Ag@AgCl、TiO2/Bi2WO6Any one of them.
The monomer is any one of methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, ethyl acrylate, butyl acrylate, vinyl acetate, butenyl acetate and styrene, and preferably any one of methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate and styrene.
The silane coupling agent is any one of silane coupling agents KH-550, KH560 and KH 570.
The gelling agent is preferably a mixture of aramid fiber 1414 and tween 60 in a mass ratio of 1: 1.
The initiator is benzoyl peroxide or a mixture of benzoyl peroxide and N, N-dimethylaniline or N, N-diethylaniline; the crosslinking agent is divinylbenzene.
The hydrophobic nano SiO2Nano SiO in sol2The mass concentration of (A) is 2.5-3.0%, and the preparation and characterization of the silica super-hydrophobic sol suitable for fabrics are carried out according to the documents of Liutao, Zhang Tong, Dong Wengying, Zhang Weihong [ J]Guangzhou chemical, 2017, 45 (22): 34-36 "by the methods disclosed in the opening paragraph.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the super-hydrophobic polymer/titanium-based photocatalytic aerogel bulk material is simple, the preparation process is carried out under conventional conditions, the conditions are mild, high-end drying processes such as freeze drying and supercritical drying are not needed, and an organic solvent harmful to human bodies and the environment is not needed. Through the hydrophobization treatment of the titanium-based photocatalyst, the titanium-based photocatalyst is better dispersed in the oil phase of the gel emulsion, and the aerogel block with good organic/inorganic composite condition is obtained. The introduction of the titanium-based photocatalyst ensures that the aerogel block has good photocatalytic activity, and the hydrophobic nano SiO is used2And (3) carrying out aftertreatment on the sol to greatly improve the hydrophobicity of the aerogel block. The aerogel has excellent adsorbability and photocatalytic activity, super-hydrophobicity, high strength and toughness and large block morphology, has a good adsorption-photocatalytic degradation function on organic pollutants, has the advantages of easiness in processing and recycling, and is expected to be used in the fields of urban domestic wastewater, industrial and agricultural wastewater treatment, oil-water separation and the like.
Drawings
FIG. 1 shows a superhydrophobic PS/TiO film prepared in example 12X-ray diffraction patterns of/Ag @ AgCl aerogel and the hydrophobic PS aerogel prepared in comparative example 1.
FIG. 2 shows the superhydrophobic PS/TiO prepared in example 12Scanning electron microscope photo of/Ag @ AgCl aerogel.
FIG. 3 is the superhydrophobic PS/TiO prepared in example 12EDS diagram of/Ag @ AgCl aerogel.
FIG. 4 shows the superhydrophobic PS/TiO prepared in example 12Contact angle test chart of/Ag @ AgCl aerogel.
FIG. 5 shows the superhydrophobic PS/TiO prepared in example 12a/Ag @ AgCl fresh aerogel mechanical property diagram.
FIG. 6 shows a superhydrophobic PS/TiO film prepared in example 12a/Ag @ AgCl dry aerogel mechanical property diagram.
FIG. 7 shows a superhydrophobic PS/TiO film prepared in example 12Graph of the amount of adsorbed/Ag @ AgCl in organic solvent.
FIG. 8 is the superhydrophobic PS/TiO prepared in example 12Ag @ AgCl aerogel, super-hydrophobic PS/TiO prepared in example 22Uv absorption spectra of aerogels and superhydrophobic PS aerogels prepared in comparative example 1.
FIG. 9 shows a superhydrophobic PS/TiO film prepared in example 12Ag @ AgCl aerogel, super-hydrophobic PS/TiO prepared in example 22Adsorption-photocatalytic degradation kinetics curves of the aerogel and the superhydrophobic PS aerogel prepared in comparative example 1 for the dye.
FIG. 10 shows a superhydrophobic PS/TiO film prepared in example 12And testing the stability of the/Ag @ AgCl aerogel.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, but the scope of the invention is not limited to these examples.
Hydrophobic nano SiO 2.6% mass concentration used in the following examples2The preparation method of the sol comprises the following steps: adding 30mL of ammonia water into 300mL of absolute ethyl alcohol, uniformly mixing, pouring into a 1000mL round-bottom flask, and magnetically stirring at room temperature, wherein the solution is marked as solution A; another 16mL of ethyl orthosilicate was added to 300mL of absolute ethanol, and the mixture was stirred uniformly and recorded as solution B. And quickly pouring the solution B into a flask in which the solution A is positioned under the condition of quick stirring, and stirring and reacting for 12 hours at room temperature to obtain light blue nano-silica sol. 200mL of absolute ethanol was added to the obtained sol, and the mixture was appropriately concentrated while removing ammonia by rotary evaporation,the total volume of the final sol was 500 mL. Taking 100mL of sol, adjusting the pH value of the sol to be 8.5 by using glacial acetic acid or ammonia water, transferring 1.5mL of dodecyl trimethoxy silane into the sol by using a pipette, adding the mixture into a single-neck flask after uniformly stirring, placing the flask into an oil bath at the temperature of 80 ℃, stirring and refluxing for reaction for 3 hours to obtain the hydrophobic nano SiO with the mass concentration of 2.6 percent2And (3) sol.
Example 1
1. Preparation of gel emulsion
At room temperature, 6g of styrene (PS), 0.1g of aramid 1414, 0.1g of Tween 60, 0.5g of benzoyl peroxide, 0.6g of divinylbenzene, 0.6g of hydrophobic TiO2And completely and uniformly mixing the Ag @ AgCl on a mixer, dropwise adding 28g of distilled water, shaking, and mixing on the mixer to obtain the gel emulsion.
The above hydrophobic TiO2The preparation method of/Ag @ AgCl comprises the following steps:
(1) adding 14mL (51.31mmol) of isopropyl titanate into 162g of 20% ethanol aqueous solution by volume fraction, adding 36mL of 6mol/L hydrochloric acid, heating and stirring at 60 ℃ for 6h, aging for 12h, filtering, washing for several times, drying, grinding into fine powder, calcining at 650 ℃ for 4h, and naturally cooling to obtain TiO2。
(2) 5g of TiO2Dispersing in 150mL deionized water, uniformly dispersing in deionized water, and adding 50mL of 0.1mol/L AgNO3Stirring the aqueous solution at room temperature for 20-30 min, adding 50mL of 0.1mol/L hydrochloric acid, stirring for 20-30 min, aging for 12h, filtering, washing with deionized water, and drying to obtain TiO2/AgCl; reuse wavelength>Irradiating with 400nm visible light for 30min to obtain TiO2/Ag@AgCl。
(3) Mixing 3mL of silane coupling agent KH-570, 30mL of deionized water and 270mL of absolute ethyl alcohol, and adjusting the pH value to about 4; 3.0g of TiO are weighed2adding/Ag @ AgCl into the mixed solution, stirring at a constant speed for 3h at 60 ℃, cleaning with the mixed solution of deionized water and absolute ethyl alcohol, and drying to obtain hydrophobic TiO2/Ag@AgCl。
2. Preparation of super-hydrophobic PS/TiO2Ag @ AgCl aerogel block material
Introducing nitrogen into the gel emulsion prepared in the step 1Prepolymerization is carried out for 3h at 45 ℃, then the temperature is raised to 80 ℃ for polymerization for 3h, natural cooling is carried out, the block is taken out, washed by water and dried, and then hydrophobic nano SiO with mass concentration of 2.6 percent is carried out2Soaking in the sol for 30min for super-hydrophobic treatment, washing with water, and drying to obtain super-hydrophobic PS/TiO2Ag @ AgCl aerogel block.
The reaction equation for this example is as follows:
comparative example 1
At room temperature, completely and uniformly mixing 6g of styrene, 0.1g of aramid 1414, 0.1g of tween 60, 0.5g of benzoyl peroxide and 0.6g of divinylbenzene in a mixer, dropwise adding 28g of distilled water, shaking and mixing in the mixer to obtain the gel emulsion. Introducing nitrogen into the prepared gel emulsion, pre-polymerizing for 3h at 45 ℃, then heating to 80 ℃ for polymerization for 3h, naturally cooling, taking out the block, washing with water, drying, and then adding hydrophobic nano SiO with mass concentration of 2.6%2And soaking the sol for 30min for super-hydrophobicity treatment, washing and drying to obtain the hydrophobic PS aerogel block.
The phase structures of the samples obtained in example 1 and comparative example 1 were characterized by means of an X-ray diffractometer (XRD) type D2 Phaser, the XRD analysis results being shown in FIG. 1. As can be seen, the PSaerogel XRD is essentially diffuse, indicating that it is amorphous, but PS/TiO2TiO appears at 25.3 degrees, 27.4 degrees and 34.4 degrees on the/Ag @ AgCl aerogel2The characteristic diffraction peaks of anatase, brookite and rutile respectively show the characteristic peaks of AgCl at 27.4 degrees, 33.4 degrees, 54.6 degrees and 57.2 degrees, and simultaneously show the characteristic peaks of Ag at 38.30 degrees and 43.22 degrees. TiO indicating hydrophobization treatment2the/Ag @ AgCl and the PS are successfully compounded. SiO is not present in the sample2Characteristic peaks due to SiO therein2Is a sol.
The morphology and the components of the sample obtained in example 1 were characterized by a JSM-6380 scanning electron microscope, and the results are shown in FIG. 2. From fig. 2 (magnified 1000 times), it can be seen that the aerogel material has a loose porous structure, has micro-nanometer pore size and pore throat, and most of the pores are open pores. And micro-nano holes are distributed on the wall of the large hole of the aerogel material from a small figure which is magnified by 20000 times. The energy spectrum analysis of the sample is shown in FIG. 3, and it can be seen from FIG. 3 that the sample contains C, O, N, Ti, Si, Cl, Ag and other elements, and TiO is in the XRD pattern of the sample2AgCl and Ag diffraction peak analysis.
The contact angle of the material of example 1 is measured by a DSA-100 type surface contact angle measuring instrument to characterize the hydrophobicity of the aerogel material, and the result is shown in FIG. 4. The contact angle was 124.2 °, indicating that the surface of the aerogel bulk was superhydrophobic.
The mechanical property curves of the fresh wet gas gel and the dried aerogel obtained in example 1 were tested by using a CTM2503 electronic universal tester, as shown in FIG. 5 and FIG. 6. FIG. 5 shows that fresh wet gas gel compression strength can reach 6.07MPa and compression ratio reaches 70.75%. FIG. 6 shows that the dry aerogel compression strength can reach 2.30MPa and the compression rate reaches 12.21%. Both show high flexibility of the material.
Example 2
In this example, an equal mass of hydrophobic TiO was used2Hydrophobic TiO of alternative example 12Ag @ AgCl, the other steps being the same as in example 1, to obtain super-hydrophobic PS/TiO2An aerogel block. Wherein the hydrophobic TiO2The preparation method comprises the following steps:
(1) adding 14mL (51.31mmol) of isopropyl titanate into 162g of 20% ethanol aqueous solution by volume fraction, adding 36mL of 6mol/L hydrochloric acid, heating and stirring at 60 ℃ for 6h, aging for 12h, filtering, washing for several times, drying, grinding into fine powder, calcining at 650 ℃ for 4h, and naturally cooling to obtain TiO2。
(2) Mixing 3mL of silane coupling agent KH-570, 30mL of deionized water and 270mL of absolute ethyl alcohol, and adjusting the pH value to about 4; 3.0g of TiO are weighed2Adding into the mixed solution, stirring at 60 deg.C for 3 hr, cleaning with mixed solution of deionized water and anhydrous ethanol, and dryingTo obtain hydrophobic TiO2。
Example 3
In this example, an equal mass of hydrophobic TiO was used2/C3N4Hydrophobic TiO of alternative example 12Ag @ AgCl, the other steps being the same as in example 1, to obtain super-hydrophobic PS/TiO2/C3N4An aerogel block. Wherein the hydrophobic TiO2/C3N4The preparation method comprises the following steps:
(1) adding 14mL (51.31mmol) of isopropyl titanate into 162g of 20% ethanol aqueous solution by volume fraction, adding 36mL of 6mol/L hydrochloric acid, heating and stirring at 60 ℃ for 6h, aging for 12h, filtering, washing for several times, and drying to obtain TiO2And (4) gelling.
(2) 1g of TiO2Mixing the gel with 1g melamine, calcining at 600 ℃ for 4h, and naturally cooling to obtain TiO2/C3N4。
(3) Mixing 3mL of silane coupling agent KH-570, 30mL of deionized water and 270mL of absolute ethyl alcohol, and adjusting the pH value to about 4; 3.0g of TiO are weighed2/C3N4Adding into the mixed solution, stirring at 60 deg.C for 3 hr, cleaning with mixed solution of deionized water and anhydrous ethanol, and drying to obtain hydrophobic TiO2/C3N4。
Example 4
In this example, an equal mass of hydrophobic TiO was used2Replacement of hydrophobic TiO in example 1 by/GRO2Ag @ AgCl, the other steps being the same as in example 1, to obtain super-hydrophobic PS/TiO2GRO aerogel block. Wherein the hydrophobic TiO2The preparation method of/GRO comprises the following steps:
(1) adding 14mL (51.31mmol) of isopropyl titanate into 162g of 20% ethanol aqueous solution by volume fraction, adding 36mL of 6mol/L hydrochloric acid, heating and stirring at 60 ℃ for 6h, aging for 12h, filtering, washing for several times, drying, grinding into fine powder, calcining at 650 ℃ for 5h, and naturally cooling to obtain TiO2。
(2) 5g of TiO2Dispersing in 150mL deionized water, and adding 50mL 10mg/mL graphene oxide (GRO) componentDispersing the water solution, stirring at room temperature for 20min, and aging for 24 h. Centrifugally washing the aged product until the upper layer is colorless clear liquid, filtering and drying to obtain TiO2/GRO。
(3) Mixing 3mL of silane coupling agent KH-570, 30mL of deionized water and 270mL of absolute ethyl alcohol, and adjusting the pH value to about 4; 3.0g of TiO are weighed2GRO is added into the mixed solution, stirred for 3 hours at a constant speed at 60 ℃, cleaned by the mixed solution of deionized water and absolute ethyl alcohol and dried to obtain hydrophobic TiO2/GRO。
Example 5
In this example, an equal mass of hydrophobic TiO was used2/C3N4Replacement of hydrophobic TiO in example 1 by/GRO2Ag @ AgCl, the other steps being the same as in example 1, to obtain super-hydrophobic PS/TiO2/C3N4GRO aerogel block. Wherein the hydrophobic TiO2/C3N4The preparation method of/GRO comprises the following steps:
(1) adding 14mL (51.31mmol) of isopropyl titanate into 162g of 20% ethanol aqueous solution by volume fraction, adding 36mL of 6mol/L hydrochloric acid, heating and stirring at 60 ℃ for 6h, aging for 12h, filtering, washing for several times, and drying to obtain TiO2And (4) gelling.
(2) 1g of TiO2Mixing the gel with 1g melamine, calcining at 600 ℃ for 4h, and naturally cooling to obtain TiO2/C3N4。
(3) 5g of TiO2/C3N4Dispersing in 150mL deionized water, adding 50mL of 10mg/mL graphene oxide (GRO) dispersed aqueous solution, stirring at room temperature for 20min, and aging for 24 h. Centrifugally washing the aged product until the upper layer is colorless clear liquid, filtering and drying to obtain TiO2/C3N4/GRO。
(3) Mixing 3mL of silane coupling agent KH-570, 30mL of deionized water and 270mL of absolute ethyl alcohol, and adjusting the pH value to about 4; 3.0g of TiO are weighed2/C3N4GRO is added into the mixed solution, stirred for 3 hours at a constant speed at 60 ℃, cleaned by the mixed solution of deionized water and absolute ethyl alcohol and dried to obtain hydrophobic TiO2/C3N4/GRO。
Example 6
In this example, an equal mass of hydrophobic TiO was used2/Bi2WO6Hydrophobic TiO of alternative example 12Ag @ AgCl, the other steps being the same as in example 1, to obtain super-hydrophobic PS/TiO2/Bi2WO6An aerogel block. Wherein the hydrophobic TiO2/Bi2WO6The preparation method comprises the following steps:
(1) adding 14mL (51.31mmol) of isopropyl titanate into 162g of 20% ethanol aqueous solution by volume fraction, adding 36mL of 6mol/L hydrochloric acid, heating and stirring at 60 ℃ for 6h, aging for 12h, filtering, washing for several times, drying, grinding into fine powder, calcining at 650 ℃ for 5h, and naturally cooling to obtain TiO2。
(2) 0.2mmol of Bi (NO)3)3·5H2O was added to 20mL of ethylene glycol and stirred for 30min until completely dissolved, and was recorded as solution A. Simultaneously, 0.8mmol TiO2And 0.4mmol of Na2WO4·2H2O was added to 20mL of ethylene glycol and stirred for 30min, and the resulting white suspension was designated as solution B. And mixing the solution A and the solution B, stirring until the solution A and the solution B are well dispersed, transferring the mixture to a 200mL stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out solvothermal reaction for 16h at 80 ℃. Washing with anhydrous ethanol and deionized water for 3 times, and drying to obtain TiO2/Bi2WO6。
(3) Mixing 3mL of silane coupling agent KH-570, 30mL of deionized water and 270mL of absolute ethyl alcohol, and adjusting the pH value to about 4; 3.0g of TiO are weighed2/Bi2WO6Adding into the mixed solution, stirring at 60 deg.C for 3 hr, cleaning with mixed solution of deionized water and anhydrous ethanol, and drying to obtain hydrophobic TiO2/Bi2WO6。
Example 7
In this example, styrene in example 1 was replaced with an equal mass of methyl methacrylate, and the other steps were the same as in example 1 to obtain super-hydrophobic polymethyl methacrylate/TiO2Ag @ AgCl aerogel block.
Example 8
This implementationIn example, the styrene of example 1 was replaced with an equal mass of t-butyl methacrylate and the procedure of example 1 was otherwise the same to obtain superhydrophobic poly (t-butyl methacrylate)/TiO2Ag @ AgCl aerogel block.
Respectively taking 0.1g of aerogel block prepared in example 1, respectively placing the aerogel block into 50mL of cyclohexane, normal hexane, toluene, benzene, dichloromethane, tetrahydrofuran, gasoline and diesel oil at room temperature until the adsorption is balanced, taking out the block, weighing the block, and calculating the maximum adsorption amount q of each organic solvent by using a formula 1-1v。
In the formula qvThe adsorption capacity of the aerogel to the organic solvent is g/g; w1、W2Dry and wet gel mass, g, respectively. The results of the test of the maximum adsorption amount of the aerogel blocks to the organic solvent are shown in fig. 7. As can be seen from FIG. 7, the aerogel block has good adsorptivity for benzene, toluene, dichloromethane, tetrahydrofuran, n-hexane and cyclohexane respectively reaching 32.2g/g, 28.3g/g, 36.9g/g, 27.6g/g, 18.9g/g and 17.1 g/g. The material has better adsorbability on gasoline and kerosene, and the adsorbability is respectively 16.1g/g and 11.2g/g, which shows that the material can be used as an oil-water separation material.
The superhydrophobic PS/TiO of example 1 was subjected to ultraviolet absorption spectroscopy (UV-vis) model SPECORD.502Ag @ AgCl aerogel, super hydrophobic PS/TiO of example 22The optical absorption characteristics of the aerogel and the superhydrophobic PS aerogel of comparative example 1 were characterized, and the results are shown in fig. 8. As can be seen from figure 8, the PS aerogel only has weak light absorption in the 225-275 nm ultraviolet light region, and compared with the super-hydrophobic PS aerogel, the super-hydrophobic PS/TiO aerogel2Aerogel and super-hydrophobic PS/TiO2the/Ag @ AgCl aerogel obviously enhances light absorption in an ultraviolet region, and the light absorption has obvious red shift. Especially super-hydrophobic PS/TiO2the/Ag @ AgCl aerogel has a strong absorption peak in a wavelength range of 300-400 nm, and the edge of the light absorption peak is close to 600nm, which indicates that plasma Ag @ AgCl and TiO2The synergistic effect of the compounds enhances PS/TiO2The visible light responsiveness of the/Ag @ AgCl aerogel expands the visible light responsiveness range, so that the activity of photocatalytic degradation of pollutants is enhanced.
To demonstrate the photocatalytic effect of the aerogel blocks of the present invention, the inventors used the superhydrophobic PS/TiO prepared in example 1, respectively2Ag @ AgCl aerogel block, super-hydrophobic PS/TiO prepared in example 22The aerogel block and the super-hydrophobic PS aerogel block prepared in the comparative example 1 are subjected to photocatalytic degradation of methyl orange, and the specific method comprises the following steps: respectively taking 0.1g of block material, respectively placing the block material into 100mL of methyl orange aqueous solution with the initial concentration of 50mg/L at room temperature, stirring for 120min in the dark, sampling for 4mL after adsorption balance is achieved, and simultaneously supplementing 4mL of distilled water again. Then, a 200W high-pressure mercury lamp is started to simulate a visible light source, and the distilled water is simultaneously replenished after sampling once at regular intervals. And measuring the concentration of methyl orange in the taken solution by using an ultraviolet spectrophotometer, and calculating the degradation rate by using a formula 1-2 so as to evaluate the photocatalytic degradation effect of the aerogel.
In the formula c0、ctThe initial methyl orange solution concentration, the methyl orange solution concentration at the time t and the g/mL are respectively. The results of the experiment are shown in FIG. 9.
As can be seen from FIG. 9, the superhydrophobic PS/TiO2Ag @ AgCl aerogel and super-hydrophobic PS/TiO2Aerogel adsorptivity is significantly higher than that of super-hydrophobic PS aerogel, because the former two can provide more adsorption sites and have a more desirable slight network structure. FIG. 9 also shows superhydrophobic PS/TiO2Ag @ AgCl aerogel and super-hydrophobic PS/TiO2The aerogel has good visible light catalytic activity, the degradation rates of methyl orange are respectively 90.3% and 81.4% after the aerogel is irradiated for 180min, and the super-hydrophobic PS aerogel hardly degrades the methyl orange under visible light, because the super-hydrophobic PS aerogel does not have the capacity of absorbing visible light. And super-hydrophobic PS/TiO2The excellent visible light catalytic activity of the/Ag @ AgCl aerogel is firstly caused by the super-hydrophobic PS/TiO2The Ag @ AgCl aerogel has more adsorption sites, and good adsorption is the premise of excellent photocatalytic degradability. Second, surface plasmon Ag @ AgCl and TiO2The coupling effect is generated, the separation of photon-generated carriers is promoted, and the visible light catalytic activity of the catalyst is improved. Third, super-hydrophobic PS/TiO2The loose structure of the/Ag @ AgCl aerogel is beneficial to multiple reflections of light in the inner cavity of the aerogel and absorption of the light.
The cycle experiment of the sample of example 1 was carried out 7 times under the same conditions as the above adsorption/photocatalytic performance test, and the results are shown in fig. 10. As can be seen from FIG. 10, after the 2 nd repeated experiment, the superhydrophobic PS/TiO2Compared with the first time, the removal rate of the/Ag @ AgCl aerogel for methyl orange is only reduced by 2.87%, after a 3 rd repeated experiment, the removal rate is reduced by 10.63%, the removal rate of 5 th repeated photocatalysis is 63.45% of that of 1 st photocatalysis, and the removal rate of 7 th repeated photocatalysis can still be 24.47% of that of 1 st photocatalysis, so that the good stability of the aerogel is shown. The reduced removal rate of methyl orange by the aerogel is probably caused by the blockage of pore channels by a small amount of non-desorbed methyl orange and degraded intermediate products thereof in the recycling process.
Claims (9)
1. A preparation method of a super-hydrophobic polymer/titanium-based photocatalytic aerogel bulk material is characterized by comprising the following steps:
(1) preparation of gel emulsion
Mixing the oil phase and distilled water in a mixer at room temperature to obtain gel emulsion; wherein the oil phase comprises the following components in percentage by mass: 1 to 5 percent of gelling agent, 3 to 10 percent of initiator, 3 to 10 percent of cross-linking agent, 5 to 10 percent of hydrophobic titanium-based photocatalyst and 70 to 85 percent of monomer;
the hydrophobic titanium-based photocatalyst is TiO subjected to hydrophobic treatment by using a silane coupling agent2、TiO2/C3N4、TiO2Graphene oxide and TiO2/C3N4Graphene oxide and TiO2/Ag@AgCl、TiO2/Bi2WO6Any one of them(ii) a The monomer is any one of methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, ethyl acrylate, butyl acrylate, vinyl acetate, butyl acetate and styrene;
(2) preparation of super-hydrophobic polymer/titanium-based photocatalytic aerogel block
Prepolymerizing the gel emulsion prepared in the step (1) at 40-50 ℃ for 1-3 h, heating to 70-85 ℃ for polymerization for 3-5 h, cooling, taking out the block, washing, drying, and then adding hydrophobic nano SiO2And soaking the sol for 10-60 min for super-hydrophobicity treatment, washing and drying to obtain the super-hydrophobic polymer/titanium-based photocatalytic aerogel block.
2. The method of preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel bulk material of claim 1, wherein: in the step (1), the volume ratio of the oil phase to the distilled water is 1: 3-4.
3. The method of preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel bulk material of claim 1, wherein: in the step (1), the oil phase comprises the following components in percentage by mass: 2 to 3 percent of gelling agent, 5 to 8 percent of initiator, 6 to 8 percent of cross-linking agent, 6 to 8 percent of hydrophobic titanium-based photocatalyst and 75 to 80 percent of monomer.
4. The method for preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1 or 3, characterized in that: the monomer is any one of methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate and styrene.
5. The method for preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1 or 4, characterized in that: the silane coupling agent is any one of silane coupling agents KH-550, KH560 and KH 570.
6. The method for preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1 or 3, characterized in that: the gelling agent is a mixture of aramid fiber 1414 and tween 60 in a mass ratio of 1: 1.
7. The method for preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1 or 3, characterized in that: the initiator is benzoyl peroxide or a mixture of benzoyl peroxide and N, N-dimethylaniline or N, N-diethylaniline; the crosslinking agent is divinylbenzene.
8. The method of preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel bulk material of claim 1, wherein: the hydrophobic nano SiO2Nano SiO in sol2The mass concentration of (A) is 2.5-3.0%.
9. The superhydrophobic polymer/titanium-based photocatalytic aerogel monolith prepared by the method of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644209A (en) * | 2020-08-05 | 2020-09-11 | 上海山恒生态科技股份有限公司 | Preparation method of photocatalyst for treating organic sewage |
| CN111648138A (en) * | 2020-06-11 | 2020-09-11 | 咸阳师范学院 | Super-hydrophobic porous chitosan/Ag @ AgCl-TiO2Composite material and environment-friendly mask |
| CN111729625A (en) * | 2020-06-15 | 2020-10-02 | 宁波锋成先进能源材料研究院 | Nano composite micro-rubber ball and preparation method and application thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111648138A (en) * | 2020-06-11 | 2020-09-11 | 咸阳师范学院 | Super-hydrophobic porous chitosan/Ag @ AgCl-TiO2Composite material and environment-friendly mask |
| CN111729625A (en) * | 2020-06-15 | 2020-10-02 | 宁波锋成先进能源材料研究院 | Nano composite micro-rubber ball and preparation method and application thereof |
| CN111644209A (en) * | 2020-08-05 | 2020-09-11 | 上海山恒生态科技股份有限公司 | Preparation method of photocatalyst for treating organic sewage |
Non-Patent Citations (1)
| Title |
|---|
| 王钦清: "细乳液聚合制备二氧化钛/聚苯乙烯复合微球及其形貌分析", 《应用化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115364904A (en) * | 2022-07-07 | 2022-11-22 | 福建省蓝光节能科技有限公司 | Photocatalyst for volatile organic pollutants and use method thereof |
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