CN112588322B - 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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- CN112588322B CN112588322B CN202011599300.8A CN202011599300A CN112588322B CN 112588322 B CN112588322 B CN 112588322B CN 202011599300 A CN202011599300 A CN 202011599300A CN 112588322 B CN112588322 B CN 112588322B
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- aerogel
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Abstract
The invention discloses a super-hydrophobic polymer/titanium-based photocatalytic aerogel block and a preparation method thereof 2 And (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 2 2 The photocatalyst is widely applied, but has wide band gap, low sunlight utilization rate and difficult recovery, so that 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 the material is not easy to dissolve in water so as to avoid secondary pollution to the environment; 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 TiO 2 Aerogels (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 technique 2 Doped SiO 2 -TiO 2 Aerogel (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 adopt formamide drying control agent for drying under normal pressure to prepare TiO 2 Aerogel (bin, zhangdingri, song \28156, et al. Atmospheric pressure drying process for preparing iron-doped carbon dioxide aerogel. Artificial lens academic report 2012,41 (4), 905-910). 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 gelatinizing 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 SiO 2 Soaking the sol for 10-60 min for super-hydrophobic 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 agent 2 、TiO 2 /C 3 N 4 、TiO 2 Graphene oxide and TiO 2 /C 3 N 4 Graphene oxide and TiO 2 /Ag@AgCl、TiO 2 /Bi 2 WO 6 Any 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, 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.
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 SiO 2 Nano SiO in sol 2 The 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 the use of high-end drying processes is not neededOrganic solvent harmful to human body and environment. The titanium-based photocatalyst is better dispersed in the oil phase of the gel emulsion through the hydrophobization treatment of the titanium-based photocatalyst, 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 used 2 And (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 1 2 X-ray diffraction patterns of/Ag @ AgCl aerogel and the hydrophobic PS aerogel prepared in comparative example 1.
FIG. 2 is the super hydrophobic PS/TiO prepared in example 1 2 Scanning electron microscope photo of/Ag @ AgCl aerogel.
FIG. 3 is the superhydrophobic PS/TiO prepared in example 1 2 EDS diagram of/Ag @ AgCl aerogel.
FIG. 4 shows the superhydrophobic PS/TiO prepared in example 1 2 Contact angle test chart of/Ag @ AgCl aerogel.
FIG. 5 shows the superhydrophobic PS/TiO prepared in example 1 2 The mechanical property diagram of the/Ag @ AgCl fresh aerogel.
FIG. 6 shows a superhydrophobic PS/TiO film prepared in example 1 2 the/Ag @ AgCl dry aerogel mechanical property diagram.
FIG. 7 shows a superhydrophobic PS/TiO film prepared in example 1 2 The adsorption amount of/Ag @ AgCl to an organic solvent.
FIG. 8 shows a superhydrophobic PS/TiO coating prepared in example 1 2 Ag @ AgCl aerogel, super-hydrophobic PS/TiO prepared in example 2 2 Ultraviolet absorption spectra of the aerogel and the superhydrophobic PS aerogel prepared in comparative example 1.
FIG. 9 shows a superhydrophobic PS/TiO film prepared in example 1 2 Ag @ AgCl aerogel, examples2 prepared super-hydrophobic PS/TiO 2 Adsorption-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 1 2 And 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 examples 2 The 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 sol obtained above, and the resulting sol was concentrated appropriately while removing ammonia by rotary evaporation to give a final sol volume of 500mL. 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 percent 2 And (3) sol.
Example 1
1. Preparation of gel emulsions
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 TiO 2 And 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 TiO 2 The preparation method of/Ag @ AgCl comprises the following steps:
(1) 14mL (51.31 mmol) of isopropyl titanate was added to 162g of 20% by volume aqueous ethanol solution,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 TiO 2 。
(2) 5g of TiO 2 Dispersing in 150mL deionized water, uniformly dispersing in deionized water, and adding 50mL 0.1mol/L AgNO 3 Stirring 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 TiO 2 /AgCl; reuse wavelength>Irradiating with 400nm visible light for 30min to obtain TiO 2 /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 weighed 2 adding/Ag @ AgCl 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 TiO 2 /Ag@AgCl。
2. Preparation of super-hydrophobic PS/TiO 2 Ag @ AgCl aerogel block material
Introducing nitrogen into the gel emulsion prepared in the step 1, prepolymerizing for 3 hours at 45 ℃, heating to 80 ℃, performing polymerization for 3 hours, naturally cooling, taking out a block, washing with water, drying, and then adding hydrophobic nano SiO 2 with the mass concentration of 2.6% 2 Soaking in the sol for 30min for super-hydrophobic treatment, washing with water, and drying to obtain super-hydrophobic PS/TiO 2 The Ag @ AgCl aerogel block material.
The reaction equation for this example is as follows:
comparative example 1
At room temperature, 6g of styrene, 0.1g of aramid 1414, 0.1g of Tween 60, 0.5g of benzoyl peroxide and 0.6g of divinylbenzene are completely mixed on a mixerAfter mixing uniformly, 28g of distilled water is added dropwise, shaking is carried out, and the gel emulsion is obtained by mixing on a mixing machine. 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% 2 And 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 an X-ray diffractometer (XRD) type D2 Phaser, and the results of XRD analysis are shown in fig. 1. As can be seen, the PS aerogel XRD is basically diffuse, indicating that it is amorphous, but the PS/TiO is 2 TiO appears at 25.3 degrees, 27.4 degrees and 34.4 degrees on/Ag @ AgCl aerogel 2 The characteristic diffraction peaks of anatase, brookite and rutile of (a) respectively appear at 27.4 °, 33.4 °, 54.6 ° and 57.2 ° of AgCl, and at 38.30 ° and 43.22 ° of Ag. TiO indicating hydrophobization treatment 2 the/Ag @ AgCl and PS are successfully compounded. SiO is not present in the sample 2 Characteristic peaks due to SiO therein 2 Is 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, with pore diameters and pore throats on the micro-nanometer scale, 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 sample 2 AgCl and Ag diffraction peak analysis.
The contact angle of the material in example 1 is measured by using a DSA-100 type surface contact angle measuring instrument to characterize the hydrophobicity of the aerogel material, and the result is shown in figure 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 used 2 Hydrophobic TiO of alternate example 1 2 The rest of the procedure was the same as in example 1 to give superhydrophobic PS/TiO 2 An aerogel block. Wherein the hydrophobic TiO 2 The preparation method comprises the following steps:
(1) Adding 14mL (51.31 mmol) 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 TiO 2 。
(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 weighed 2 Adding 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 TiO 2 。
Example 3
In this example, an equal mass of hydrophobic TiO was used 2 /C 3 N 4 Hydrophobic TiO of alternative example 1 2 The rest of the procedure was the same as in example 1 to give superhydrophobic PS/TiO 2 /C 3 N 4 An aerogel block. Wherein the hydrophobic TiO 2 /C 3 N 4 The preparation method comprises the following steps:
(1) Adding 14mL (51.31 mmol) 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 TiO 2 And (4) gelling.
(2) 1g of TiO 2 Mixing the gel with 1g melamine, calcining at 600 ℃ for 4h, and naturally cooling to obtain TiO 2 /C 3 N 4 。
(3) 3mL of silane coupling agent KH-570 and 30mL of silane coupling agent KH-570 were addedMixing ionized water with 270mL of absolute ethyl alcohol, and adjusting the pH value to about 4; 3.0g of TiO are weighed 2 /C 3 N 4 Adding 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 TiO 2 /C 3 N 4 。
Example 4
In this example, an equal mass of hydrophobic TiO was used 2 Replacement of hydrophobic TiO in example 1 by/GRO 2 The rest of the procedure was the same as in example 1 to give superhydrophobic PS/TiO 2 GRO aerogel block. Wherein the hydrophobic TiO 2 The preparation method of/GRO comprises the following steps:
(1) Adding 14mL (51.31 mmol) 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 TiO 2 。
(2) 5g of TiO 2 Dispersing in 150mL of deionized water, adding 50mL of 10mg/mL graphene oxide (GRO) dispersion water solution, stirring at room temperature for 20min, and aging for 24h. Centrifugally washing the aged product until the upper layer is colorless clear liquid, filtering and drying to obtain TiO 2 /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 weighed 2 GRO 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 TiO 2 /GRO。
Example 5
In this example, an equal mass of hydrophobic TiO was used 2 /C 3 N 4 Replacement of hydrophobic TiO in example 1 by/GRO 2 Ag @ AgCl, other steps same as example 1, to obtain super-hydrophobic PS/TiO 2 /C 3 N 4 GRO aerogel block. Wherein the hydrophobic TiO 2 /C 3 N 4 The preparation method of/GRO comprises the following steps:
(1) 14mL (51.31 mmol) of titanic acidAdding isopropyl ester into 162g ethanol water solution with volume fraction of 20%, adding 36mL 6mol/L hydrochloric acid, heating and stirring at 60 deg.C for 6h, aging for 12h, filtering, washing for several times, and drying to obtain TiO 2 And (4) gelling.
(2) 1g of TiO 2 Mixing the gel with 1g melamine, calcining at 600 ℃ for 4h, and naturally cooling to obtain TiO 2 /C 3 N 4 。
(3) 5g of TiO 2 /C 3 N 4 Dispersing in 150mL of deionized water, adding 50mL of 10mg/mL graphene oxide (GRO) dispersion water solution, stirring at room temperature for 20min, and aging for 24h. Centrifugally washing the aged product until the upper layer is colorless clear liquid, filtering and drying to obtain TiO 2 /C 3 N 4 /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 weighed 2 /C 3 N 4 GRO 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 TiO 2 /C 3 N 4 /GRO。
Example 6
In this example, an equal mass of hydrophobic TiO was used 2 /Bi 2 WO 6 Hydrophobic TiO of alternative example 1 2 The rest of the procedure was the same as in example 1 to give superhydrophobic PS/TiO 2 /Bi 2 WO 6 An aerogel block. Wherein the hydrophobic TiO 2 /Bi 2 WO 6 The preparation method comprises the following steps:
(1) Adding 14mL (51.31 mmol) 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 TiO 2 。
(2) 0.2mmol of Bi (NO) 3 ) 3 ·5H 2 O is added into 20mL of ethylene glycol and stirred for 30min until completely dissolved, and is marked as solution A. Simultaneously, 0.8mmol TiO 2 And 0.4mmol of Na 2 WO 4 ·2H 2 O 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 TiO 2 /Bi 2 WO 6 。
(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 weighed 2 /Bi 2 WO 6 Adding 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 TiO 2 /Bi 2 WO 6 。
Example 7
In this example, styrene in example 1 was replaced with an equal mass of methyl methacrylate, and the procedure was otherwise the same as in example 1 to obtain superhydrophobic polymethyl methacrylate/TiO 2 The Ag @ AgCl aerogel block material.
Example 8
In this example, styrene in example 1 was replaced with equal mass of t-butyl methacrylate, and the other steps were the same as in example 1 to obtain superhydrophobic poly (t-butyl methacrylate)/TiO 2 The Ag @ AgCl aerogel block material.
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 1-1 v 。
In the formula q v The adsorption capacity of the aerogel to the organic solvent is g/g; w 1 、W 2 Dry, wet gel mass, g, respectively. The test result of the maximum adsorption amount of the aerogel block to the organic solvent is shown in the figureShown 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.50 2 Ag @ AgCl aerogel, super hydrophobic PS/TiO of example 2 2 The 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 FIG. 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 aerogel 2 Aerogel and super-hydrophobic PS/TiO 2 the/Ag @ AgCl aerogel obviously enhances the light absorption in an ultraviolet region, and the light absorption has obvious red shift. Especially super-hydrophobic PS/TiO 2 The Ag @ AgCl aerogel has a strong absorption peak in the 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 TiO 2 The synergistic effect of the compounds enhances PS/TiO 2 The visible light responsiveness of the/Ag @ AgCl aerogel expands the visible light responsiveness range, and therefore 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, respectively 2 /Ag @ AgCl aerogel block material and super-hydrophobic PS/TiO prepared in example 2 2 The 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 once every certain time for sampling. 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 c 0 、c t The 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/TiO 2 Ag @ AgCl aerogel and super-hydrophobic PS/TiO 2 Aerogel adsorptivity is significantly higher than superhydrophobic PS aerogels because the former two provide more adsorption sites and have a more desirable slightly networked structure. FIG. 9 also shows superhydrophobic PS/TiO 2 Ag @ AgCl aerogel and super-hydrophobic PS/TiO 2 The 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/TiO 2 The excellent visible light catalytic activity of the/Ag @ AgCl aerogel is firstly caused by the super-hydrophobic PS/TiO 2 the/Ag @ AgCl aerogel has more adsorption sites, and good adsorption is the premise of excellent photocatalytic degradability. Second, surface plasma Ag @ AgCl and TiO 2 The 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/TiO 2 The 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/TiO 2 Compared with the first time, the removal rate of the/Ag @ AgCl aerogel for methyl orange is only reduced by 2.87%, after 3 times of repeated experiments, the removal rate is reduced by 10.63%, the removal rate of 5 times of repeated photocatalysis is 63.45% of that of 1 st photocatalysis, the removal rate of 7 times of repeated photocatalysis can still be 24.47% of that of 1 st photocatalysis, and the good stability of the aerogel is shown. The aerogel pair AThe reduced orange removal rate may be due to small amounts of unresorbed methyl orange and its degraded intermediates plugging pore channels during recycling.
Claims (8)
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: 1-5% of gelatinizing agent, 3-10% of initiator, 3-10% of cross-linking agent, 5-10% of hydrophobic titanium-based photocatalyst and 70-85% of monomer; the volume ratio of the oil phase to the distilled water is 1: 3-4;
the hydrophobic titanium-based photocatalyst is TiO subjected to hydrophobic treatment by using a silane coupling agent 2 、TiO 2 /C 3 N 4 、TiO 2 Graphene oxide and TiO 2 /C 3 N 4 Graphene oxide and TiO 2 /Ag@AgCl、TiO 2 /Bi 2 WO 6 Any one of them; 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 SiO 2 Soaking the sol for 10-60 min for super-hydrophobic 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 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.
3. The method for preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1 or 2, characterized in that: the monomer is any one of methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate and styrene.
4. The method for preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1 or 2, characterized in that: the silane coupling agent is any one of silane coupling agents KH-550, KH560 and KH 570.
5. The method for preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1 or 2, characterized in that: the gelling agent is a mixture of aramid fiber 1414 and tween 60 in a mass ratio of 1.
6. The method for preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1 or 2, 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.
7. The method of preparing the superhydrophobic polymer/titanium-based photocatalytic aerogel block according to claim 1, wherein: the hydrophobic nano SiO 2 Nano SiO in sol 2 The mass concentration of (A) is 2.5-3.0%.
8. The superhydrophobic polymer/titanium-based photocatalytic aerogel monolith prepared by the method of claim 1.
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