CN116002814A - Ultrafiltration membrane with photocatalysis-photo-thermal synergistic performance and preparation method and application thereof - Google Patents
Ultrafiltration membrane with photocatalysis-photo-thermal synergistic performance and preparation method and application thereof Download PDFInfo
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention belongs to the technical field of photocatalysis-photo-thermal-membrane separation synergy, and particularly relates to an ultrafiltration membrane with photocatalysis-photo-thermal synergy performance, and a preparation method and application thereof. The preparation method comprises the following steps: a) Preparation of Pd-TiO by reduction 2 A photocatalyst; b) Preparing a PEDOT polymer by a one-pot method; c) Pd-TiO to be prepared 2 The photocatalyst and PEDOT polymer powder are mixed and dispersed in PVDF casting solution in proportion, and the casting solution is scraped into a film by a phase inversion method. Pd-TiO prepared by the application 2 The PEDOT photocatalysis-photo-thermal PVDF ultrafiltration membrane generates active free radicals under the condition of simulating sunlight, is used for instantly degrading pollutants in water body intercepted by a membrane structure, effectively captures irradiation light, improves quantum efficiency, simultaneously enables the membrane to have a photo-thermal effect, has excellent photocatalysis-photo-thermal-membrane separation synergistic performance, and shows good application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalysis-photo-thermal-membrane separation synergy, and particularly relates to an ultrafiltration membrane with photocatalysis-photo-thermal synergy performance, and a preparation method and application thereof.
Background
Ultrafiltration (UF) is a low pressure membrane filtration technology commonly used for water purification and wastewater treatment. Compared with the traditional separation technology, the ultrafiltration has the main advantages of high water yield, good product water quality and small occupied area. However, organic contamination of ultrafiltration membranes is a major obstacle limiting the widespread use of ultrafiltration. Membrane fouling is mainly caused by deposition of nonpolar solutes, hydrophobic particles, bacteria on or in the membrane pores, resulting in reduced separation efficiency, membrane permeability and membrane lifetime, thus increasing operating costs and even causing malfunctions.
In recent years, photocatalytic technology has been considered as a sustainable environmental remediation technology. The photocatalysis is combined with membrane separation, and active oxygen species, mainly hydroxyl radicals (OH), can be generated in situ through the photocatalysis reaction so as to resist organic pollution of the membrane. Separation membranes prepared using photocatalytic nanoparticles have been attracting attention due to their superior characteristics (e.g., antifouling and photocatalytic properties) compared to conventional membranes. Titanium dioxide (TiO) 2 ) Is one of the most widely used photocatalysts, and has good chemical and thermal stability and excellent photoactivity because of low cost. Various TiO-based materials have been studied to date 2 Is a photocatalytic film of (a). However, the original TiO 2 The base photocatalytic film still faces serious problems because it can only respond to uv light and the nanostructured TiO 2 The photogenerated carriers of the semiconductor are readily recombined. To overcome these problems, researchers have proposed that in TiO 2 In recent years, the photocatalytic activity of the method for forming the heterojunction by loading the noble metal on the surface can be improved by loading the noble metal, and the photo-generated free electron resonance oscillation can be accelerated to be quickly converted into heat.
PEDOT (3, 4-ethylenedioxythiophene) has been widely studied for its unique optical, photo-thermal and conductive properties. Optical properties are often used for degradation of environmental pollutants, optical and thermal properties are often used for tumor treatment, and electrical conductivity properties are used for the preparation of solar thin film batteries. At present, the method for preparing a semiconductor photocatalytic heterojunction by compounding PEDOT with other materials is reported in literature to be used for photocatalytic degradation of dye wastewater. Or prepared into a photocatalysis film for separating pollutants by the film. And preparing a conductive film on substrates such as PVDF film, ceramic film, spinning cloth and the like by using monomer EDOT (3, 4-ethylenedioxythiophene) of PEDOT through a vapor deposition method, wherein the conductive film is used for separating pollutants by a photoelectrocatalysis film or a solar conductive cell film. However, the photo-thermal properties of PEDOT for membrane separation of contaminants have not been reported, and it is reported in the literature that PEDOT alone cannot exhibit photo-thermal properties in separation membranes because the thermal conductivity of PEDOT membranes is generally low (+.1W m-1K-1) the heat of photo-thermal generation can be confined within the membrane.
Disclosure of Invention
In one aspect, the invention provides a preparation method of an ultrafiltration membrane with photocatalysis-photo-thermal synergistic performance, which comprises the steps of mixing Pd-TiO 2 The photocatalyst and the PEDOT polymer are mixed and dispersed in polyvinylidene fluoride (PVDF) film after ultrasonic treatment to prepare Pd-TiO 2 The preparation method has the advantages of simple process and low cost.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an ultrafiltration membrane with photocatalysis-photo-thermal synergistic performance,
by combining Pd-TiO 2 The photocatalyst and the PEDOT polymer are mixed and dispersed in polyvinylidene fluoride (PVDF) film after ultrasonic treatment to prepare Pd-TiO 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membranes.
In some technical schemes, the method comprises the following steps:
a) Preparation of Pd-TiO by reduction 2 A photocatalyst;
b) Preparing a PEDOT polymer by a one-pot method;
c) Pd-TiO to be prepared 2 The photocatalyst and PEDOT polymer powder are mixed and dispersed in PVDF casting solution in proportion, and the casting solution is scraped into a film by a phase inversion method.
In some technical schemes, the step a specifically comprises the following steps:
proper amount of TiO 2 Ultrasonically dispersing the nano particles into distilled water, and adding polyvinylpyrrolidone (PVP), L-Ascorbic Acid (AA) and KBr and 0.5-1.0mmol/L K into the dispersion liquid according to the proportion 2 PdCl 4 The solution undergoes a reduction reaction, and Pd-TiO is obtained after washing and drying 2 A photocatalyst.
In some technical schemes, the step b specifically comprises the following steps:
dissolving sodium 2-ethylhexyl succinate sulfonate (AOT) in n-hexane, and sequentially adding 1-10 mol/L FeCl 3 .6H 2 And (3) carrying out polymerization reaction on the O solution and the 3, 4-Ethylenedioxythiophene (EDOT) solution, washing and drying to obtain the PEDOT polymer.
In some technical schemes, the step c specifically comprises the following steps:
the prepared Pd-TiO 2 Mixing photocatalyst and PEDOT polymer powder in proportion, ultrasonic dispersing in organic solvent, adding quantitative polyvinylpyrrolidone (PVP) pore-forming agent and film material PVDF powder, heating, vacuum standing, defoaming to obtain uniform casting solution, pouring the casting solution onto glass plate, scraping to obtain film by using automatic film coater, immersing the film and glass plate in deionized water to solidify and fall off, and storing in deionized water to obtain stable Pd-TiO 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membranes.
In some technical schemes, pd-TiO in the casting solution 2 The mixed addition amount of the catalyst and PEDOT is 1.0 to 3.0 weight percent, and Pd-TiO 2 The mixing ratio of the PEDOT and the PEDOT is between 0.5 and 1.8:0.2 to 1.5.
In some technical schemes, the molecular weight of PVP in the casting film liquid is 5000-13800, and the addition amount is 3.0wt%; and/or the number of the groups of groups,
the adding amount of PVDF in the casting solution is 10-15 wt%; and/or the number of the groups of groups,
the water bath temperature for curing the film was 25℃and the doctor blade height of the automatic film coater was 0.25mm.
On the other hand, the invention provides an ultrafiltration membrane with photocatalysis-photo-thermal synergistic performance, which is prepared by adopting the preparation method and has excellent photocatalysis-photo-thermal synergistic performance; has the photocatalytic activity under the full wave band; and has hydrophilicity.
In other aspects, the invention provides application of an ultrafiltration membrane with photocatalysis-photo-thermal synergistic performance in photocatalysis-photo-thermal-membrane separation synergistic removal of water pollutants.
The technical scheme adopted by the invention has at least the following beneficial effects:
1. the application provides a system for controlling the membrane pollution problem by adopting a photocatalysis-photo-thermal technology with brand new design, namely Pd-TiO 2 The PEDOT is compositely loaded in the separation membrane, so that the structure of the membrane is not damaged, the pore canal structure of the separation membrane is enriched, and the interception performance of the ultrafiltration membrane to pollutants is promoted; due to Pd-TiO 2 And the hydrophilicity of PEDOT, the PVDF membrane which is hydrophobic per se can be modified into a hydrophilic membrane, so that the water flux is improved;
2. Pd-TiO of the present application 2 And PEDOT are compositely supported in a separation membrane, and Pd-supported TiO 2 The composite material can effectively collect visible light and generate a plasma induced electric field around the visible light due to the Surface Plasmon Resonance (SPR) effect, and the electric field can promote the formation rate of electrons and holes so as to promote the generation of photocatalytic functional active substances; PEDOT can timely transfer electrons to Pd-TiO when irradiated by light due to good conductivity and thermal effect 2 The thermal effect can exacerbate the electron transport speed to induce more efficient localized heating and accelerate the kinetics and efficiency of photoexcitation, thereby enhancing photocatalytic capacity;
3. Pd-TiO proposed in the present application 2 The PEDOT photocatalysis-photothermal PVDF ultrafiltration membrane has photocatalysis activity under the full wave band, and expands the application scene;
4. Pd-TiO prepared by the application 2 PEDOT photocatalysis-photo-thermal PVDF ultrafiltration membrane generates active free radicals under the condition of simulating sunlight, is used for instantly degrading pollutants in water body intercepted by a membrane structure, effectively captures irradiation light, improves quantum efficiency, simultaneously enables a film to have a photo-thermal effect, has excellent photocatalysis-photo-thermal-membrane separation synergistic performance, and shows good performanceApplication prospect.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, reference will be made to the drawings and the signs used in the embodiments, and it is obvious that the drawings described below are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction (XRD) pattern of the samples prepared in example 1 and comparative examples 1 to 2;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of samples prepared in example 1 and comparative example 3;
FIG. 3 is an infrared spectrum of samples prepared in examples 1 to 3 and comparative examples 3 to 5;
FIG. 4 is a graph showing Raman spectrum analysis of samples prepared in examples 1 to 2 and comparative examples 4 to 5;
FIG. 5 is a photograph showing contact angles of samples prepared in example 1 and comparative examples 3 to 5;
FIG. 6 is an ultraviolet-visible absorption spectrum of samples prepared in examples 1 to 3 and comparative examples 3 to 5;
FIG. 7 is a graph showing the temperature of samples prepared in examples 1 to 3 and comparative examples 3 to 4 with time under 808nm infrared laser;
FIG. 8 is an infrared thermal image of samples prepared in examples 1-3 and comparative examples 3-5 at various times;
FIG. 9 is a graph showing the comparative interception performance of humic acid by the samples prepared in examples 1 to 3 and comparative example 3;
FIG. 10 is a graph showing anti-contamination property test of samples prepared in examples 1 to 3 and comparative examples 3 to 5.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
The following examples are set forth to illustrate, but are not intended to limit, further details of how the present invention may be practiced.
Pd-TiO prepared by the invention 2 The PEDOT/PVDF photocatalytic-photothermal ultrafiltration membrane was structurally characterized by the following means. Carrying out structural analysis by using a Rigaku D/Max-RB type X-ray diffractometer (XRD), carrying out ultraviolet visible diffuse reflection test by using a type UV-2450 spectrophotometer, carrying out Raman spectrum test by using a SuperLabRam II, and analyzing the morphology and structure of a sample by using a HITACHI S-4800 type Scanning Electron Microscope (SEM); water Contact Angle (CA) measurements were performed using a JC2000D1 optical contact angle meter.
Pd-TiO as described in the examples of the present invention 2 The evaluation process of the retention performance of the PEDOT/PVDF photocatalytic-photothermal ultrafiltration membrane is as follows: the effective filtration area of the membrane sample is fixed to be 28.26cm by adopting a self-built circulating cross-flow filtration device 2 . The membrane sample was fixed in a membrane filtration unit, pre-pressed for 30min with ultra pure water at a pressure of 1bar to achieve a stable water flux, setting the filtration pressure to 0.5bar. Meanwhile, the ultrapure water in the feed tank was replaced with a humic acid solution (solution A) having a concentration of 10mg/L, and the solution filtered out in the filtrate tank (solution B) was collected. Measuring the absorbance of the solutions A and B at 254nm by a liquid phase ultraviolet spectrophotometer, converting the absorbance into concentration, and calculating the retention rate (R) of the solutions A and B; the calculation formula is as follows:
wherein, C: concentration of filtered solution in filtrate tank, C 0 : humic acid solution concentration in the feed tank.
The weight (volume) of water filtered by the membrane sample is recorded every 3 minutes in real time by adopting an electronic balance, the water flux of the sample membrane is calculated, and the calculation formula is as follows:
wherein J is the water flux (L/m 2 H.bar), V: volume of permeate side solution (L), A: effective area of membrane sample filtered (m 2 ) T is the filtration time (h), P is the transmembrane pressure difference (bar).
The following examples all prepared Pd-TiO as follows 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membrane:
a) 1000mg of TiO was added at room temperature 2 Dispersing the nanoparticle in 30mL distilled water, ultrasonic treating for 20 min, stirring at 80deg.C, adding 525mg PVP, 600mg AA and 1200mg KBr, and K with different contents 2 PdCl 4 . After heating in air for 3 hours, the sample is washed by deionized water for more than 3 times, organic matters are removed by centrifugation, and the sample is dried in vacuum at 80 ℃ for 12 hours.
b) 3.8g of sodium 2-ethylhexyl succinate sulfonate (AOT) are dissolved in 15ml of n-hexane, and 10mol/L FeCl are added successively 3 .6H 2 O solution, 3, 4-Ethylenedioxythiophene (EDOT) solution with a certain content, standing at room temperature, stirring for 12 hours, washing the sample with ethanol and water for more than 3 times respectively, and vacuum drying at 80 ℃ for 12 hours.
c) The prepared Pd-TiO 2 Mixing with PEDOT in proportion, ultrasonic treating for 30min, dispersing in organic solvent DMF, adding PVP and film material PVDF, stirring at 60 deg.c for 12 hr, and final defoaming in vacuum oven at 60 deg.c for 4 hr. Pouring the casting solution on a glass plate, scraping the casting solution into a film by using an automatic film coating machine, wherein the height of a scraper is 0.25mm; immersing the film and the glass plate into deionized water to solidify and drop the film, and storing in deionized water to obtain Pd-TiO 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membranes.
In the above examples, in step a, the molecular weight of PVP is between 5000 and 13800, preferably 8000; k (K) 2 PdCl 4 The concentration of the solution is in the range of 0.5 to 1.0mmol/L, preferably 1.0mmol/L.
In the above example, in step b, feCl 3 .6H 2 The concentration of the O solution is in the range of 1 to 10mol/L, preferably 10mol/L。
In the above examples, PVP in the casting solution had a molecular weight of 8000 and an addition amount of 3wt%; the adding amount of PVDF in the casting solution is 10-15 wt%, preferably 15wt%; pd-TiO in casting film liquid 2 The mixing addition amount of the PEDOT and the additive is 1.0-3.0 wt%, preferably 2wt%; in the step c, pd-TiO in the casting solution 2 The mixing ratio of the PEDOT and the PEDOT is between 0.5 and 1.8: between 0.2 and 1.5, preferably 0.5:1.5,1:1,1.5:0.5,1.8:0.2; more preferably 1.5:0.5; the water bath temperature for curing the film was 25℃and the doctor blade height of the automatic film coater was 0.25mm.
The invention is further illustrated below in conjunction with specific examples and comparative examples.
Example 1
Pd-TiO 2 The preparation process of the PEDOT photocatalysis-photothermal PVDF ultrafiltration membrane is as follows.
a) 1000mg of TiO was added at room temperature 2 Dispersing the nanoparticle in 30mL distilled water, ultrasonic treating for 20 min, stirring at 80deg.C, adding 525mg PVP, 600mg AA and 1200mg KBr, and K with different contents 2 PdCl 4 After heating in air for 3 hours, the sample is washed by deionized water for more than 3 times, organic matters are removed by centrifugation, and the sample is dried in vacuum at 80 ℃ for 12 hours.
b) 3.8g of sodium 2-ethylhexyl succinate sulfonate (AOT) are dissolved in 15ml of n-hexane, and 10mol/L FeCl are added successively 3 .6H 2 O solution, 3, 4-Ethylenedioxythiophene (EDOT) solution with a certain content, standing at room temperature, stirring for 12 hours, washing the sample with ethanol and water for more than 3 times respectively, and vacuum drying at 80 ℃ for 12 hours.
c) The prepared Pd-TiO 2 Mixing with PEDOT in proportion, dispersing in an organic solvent DMF after ultrasonic treatment for 30 minutes, adding PVP and a film material PVDF, stirring for 12 hours at 60 ℃, placing the completely dissolved film casting solution in a vacuum drying oven at 60 ℃ for standing and defoaming for 4 hours, pouring the film casting solution on a glass plate, and scraping the film by using an automatic film coater, wherein the height of a scraper is 0.25mm; immersing the film and the glass plate into deionized water to solidify and drop the film, and storing in deionized water to obtain Pd-TiO 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membrane.
Example 2
The procedure of this example was essentially the same as that of example 1, except that: in step c, pd-TiO 2 The addition ratio to PEDOT was 0.5:1.5. obtaining PT 0.5 PE 1.5 PVDF membrane.
Example 3
The procedure of this example was essentially the same as that of example 1, except that: in step c, pd-TiO 2 The addition ratio of the catalyst to PEDOT is 1:1. obtaining PT 1 PE 1 PVDF membrane.
Comparative example 1
This comparative example is identical to the procedure of example 1, except that: step b, step c and step d are omitted.
1000mg of TiO was added at room temperature 2 The nanoparticles were dispersed in 30mL of distilled water and sonicated in a 50mL round bottom flask for 20 minutes followed by adding the round bottom flask under magnetic stirring in an oil bath preset at 80 ℃, then adding 525mg PVP, 600mg AA and 1200mg KBr to the round bottom flask followed by K 2 PdCl 4 The solution is injected into the reaction solution, the reaction mixture is heated in the air at 80 ℃ for 3 hours, the sample is washed by water for several times, most AA and PVP are removed by centrifugation, and then the Pd-TiO is obtained by vacuum drying and heating at 80 ℃ for 12 hours 2 A photocatalyst.
Comparative example 2
This comparative example is substantially identical to the procedure of example 1, except that: step a, step c and step d are omitted.
3.8g of AOT were dissolved in 15ml of n-hexane solution, followed by addition of 10mol/L FeCl 3 .6H 2 O solution, and finally EDOT solution is added, the mixture is kept still and stirred for 12 hours at room temperature, the sample is washed by ethanol and water for several times, and then the mixture is dried and heated for 12 hours at 80 ℃ in vacuum, so that the PEDOT polymer is obtained.
Comparative example 3
This comparative example is substantially identical to the procedure of example 1, except that: step a and step b are omitted, pd-TiO is not added 2 And PEDOT, directly proceeding stepsAnd c, performing the operations of the step c and the step d. A PVDF film was obtained.
Comparative example 4
This comparative example is substantially identical to the procedure of example 1, except that: step b is omitted, and only Pd-TiO is added in step c 2 No PEDOT was added. Obtaining Pd-TiO 2 PVDF membrane.
Comparative example 5
This comparative example is substantially identical to the procedure of example 1, except that: step a is omitted, only PEDOT is added in step c, and Pd-TiO is not added 2 . A PEDOT/PVDF film was obtained.
Using the prepared Pd-TiO 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membrane: XRD structure analysis, structure ultraviolet visible diffuse reflection test, infrared and SEM morphology analysis and contact angle test; the interception rate test, the anti-pollution performance test and the photo-thermal performance test are as follows:
in the above examples, the X-ray diffraction (XRD) patterns of the samples of example 1 and comparative examples 1-2, as shown in FIG. 1, show that the sample prepared in comparative example 1 has anatase TiO 2 The sample prepared in example 1 showed diffraction peaks similar to those of comparative example 1, demonstrating successful preparation of Pd-TiO 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membranes.
FIG. 2 is a cross-sectional Scanning Electron Microscope (SEM) photograph of the sample prepared in example 1, and FIGS. 2b and 2c are partial enlarged photographs of FIG. 2a, as shown in FIGS. 2a, 2b and 2c, showing that the sample prepared in example 1 has a porous asymmetric structure, pd-TiO 2 And PEDOT is firmly supported in the pore canal of the membrane. FIG. 2d is a cross-sectional Scanning Electron Microscope (SEM) photograph of the sample prepared in comparative example 3, which shows that the addition of the catalyst to the sample prepared in example 1 did not damage the structure of the separation membrane itself.
The infrared spectra (FTIR) of the samples prepared in examples 1-3 and comparative examples 3-5 are shown in connection with FIG. 3. Comparative example 3 consists of alpha, beta and gamma phases. And the samples prepared in examples 1-3 exhibited similar spectra to comparative examples 3-5. It can thus be demonstrated that the loading of the catalyst into the membrane structure by the phase inversion method does not significantly alter the chemical properties of the membrane.
The raman spectra of the samples prepared in examples 1-2 and comparative examples 4-5 are shown in connection with fig. 4. The characteristic diffraction peak of the sample prepared in comparative example 5 was PEDOT, and the characteristic diffraction peak of the sample prepared in comparative example 4 was TiO 2 . Example 1 shows PEDOT and Pd-TiO 2 Loaded in the separation membrane.
The contact angle photographs of the samples prepared in example 1 and comparative examples 3-5, respectively, are shown in FIG. 5, showing that the original PVDF film was coated on Pd-TiO 2 Or PEDOT, the hydrophilicity of which is improved. At the same time load Pd-TiO 2 And PEDOT, the hydrophilicity is further improved, thereby being beneficial to the improvement of the anti-pollution performance.
Referring to FIG. 6, the ultraviolet-visible absorption spectra of the samples prepared in examples 1-3 and comparative examples 3-5 show that the samples prepared in examples 1-3 significantly enhance the light absorption capacity, increase the light energy utilization ratio, and promote the photocatalytic activity compared with the samples prepared in comparative examples 3-5.
The temperature changes of the samples prepared in examples 1-3 and comparative examples 3-4 under 808nm infrared light irradiation are shown in FIG. 7, respectively. FIG. 7 shows that all the samples have certain photocatalytic activity and photo-thermal properties, and examples 1-3 have better photo-thermal properties than comparative examples 3-4.
The samples prepared in examples 1-3 and comparative examples 3-4 were imaged in IR thermal imaging and temperature change, respectively, as shown in FIG. 8. Examples 1 to 3 and comparative example 4 each had a gradually increasing temperature with the increase of the light irradiation time. And examples 1 to 3 have better light-heat conversion performance than comparative examples 3 to 4.
Referring to FIG. 9, the humic acid retention properties of the samples prepared in examples 1 to 3 and comparative example 3, respectively, show that the original PVDF film was loaded with mixed Pd-TiO 2 After the nano particles are mixed with PEDOT, the uniform dispersion of the nano particles enriches the pore size distribution of the membrane, so that the pore size is more uniform, the retention rate of humic acid is further improved, and the retention rate of the example 1 is optimal.
The contamination resistance of the samples prepared in examples 1-3 and comparative examples 3-5, respectively, is shown in FIG. 10Can be used. The result shows that Pd-TiO under the irradiation of simulated sunlight 2 Or the relative water flux decrease trend of the PEDOT-supported PVDF membrane is smaller than that of the PVDF membrane without the supported catalyst, which indicates Pd-TiO 2 And PEDOT is effective in degrading contaminants on the film surface. Mixing Pd-TiO at the same time 2 And after PEDOT, pd-TiO 2 The relative water flux of the PEDOT photocatalysis-photo-thermal PVDF ultrafiltration membrane shows an ascending trend, which shows that Pd-TiO is mixed simultaneously 2 And PEDOT can further improve the hydrophilicity of the separation membrane and enhance the anti-fouling performance, and TiO 2 The photocatalytic activity can be greatly improved after the surface is loaded with the noble metal Pd, and the noble metal effect can accelerate the photo-generated free electron resonance to quickly convert the light energy into heat energy. PEDOT is added, and due to good conductivity and thermal effect, it can timely transfer electrons to Pd-TiO when irradiated with light 2 The thermal effect aggravates the transmission speed of electrons so as to induce more effective local photo-thermal heating and accelerate the dynamics and efficiency of photo-excitation, thereby enhancing the photo-catalytic capability, being beneficial to the photo-thermal enhancement, embodying the photo-catalytic-photo-thermal synergistic performance, degrading pollutants more effectively and maintaining stable water flux.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (10)
1. A preparation method of an ultrafiltration membrane with photocatalysis-photo-thermal synergistic performance is characterized in that,
by combining Pd-TiO 2 The photocatalyst and the PEDOT polymer are mixed and dispersed in polyvinylidene fluoride (PVDF) film after ultrasonic treatment to prepare Pd-TiO 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membranes.
2. The method of manufacturing according to claim 1, comprising the steps of:
a) Preparation of Pd-TiO by reduction 2 A photocatalyst;
b) Preparing a PEDOT polymer by a one-pot method;
c) Pd-TiO to be prepared 2 The photocatalyst and PEDOT polymer powder are mixed and dispersed in PVDF casting solution in proportion, and the casting solution is scraped into a film by a phase inversion method.
3. The preparation method according to claim 2, wherein the step a is specifically:
proper amount of TiO 2 Ultrasonically dispersing the nano particles into distilled water, and adding polyvinylpyrrolidone (PVP), L-Ascorbic Acid (AA) and KBr and 0.5-1.0mmol/L K into the dispersion liquid according to the proportion 2 PdCl 4 The solution undergoes a reduction reaction, and Pd-TiO is obtained after washing and drying 2 A photocatalyst.
4. The preparation method according to claim 2, wherein the step b is specifically:
dissolving sodium 2-ethylhexyl succinate sulfonate (AOT) in n-hexane, and sequentially adding 1-10 mol/L FeCl 3 .6H 2 And (3) carrying out polymerization reaction on the O solution and the 3, 4-Ethylenedioxythiophene (EDOT) solution, washing and drying to obtain the PEDOT polymer.
5. The preparation method according to claim 2, wherein step c is specifically:
the prepared Pd-TiO 2 Mixing photocatalyst and PEDOT polymer powder in proportion, ultrasonic dispersing in organic solvent, adding quantitative polyvinylpyrrolidone (PVP) pore-forming agent and film material PVDF powder, heating, vacuum standing, defoaming to obtain uniform casting solution, pouring the casting solution onto glass plate, scraping to obtain film by using automatic film coater, immersing the film and glass plate in deionized water to solidify and fall off, and storing in deionized water to obtain stable Pd-TiO 2 PEDOT photocatalytic-photothermal PVDF ultrafiltration membranes.
6. The method according to claim 5, wherein,
Pd-TiO in the casting solution 2 The mixed addition amount of the catalyst and PEDOT is 1.0 to 3.0 weight percent, and Pd-TiO 2 The mixing ratio of the PEDOT and the PEDOT is between 0.5 and 1.8:0.2 to 1.5.
7. The method according to claim 5 or 6, wherein,
PVP in the casting film liquid has a molecular weight of 5000-13800 and an addition amount of 3.0wt%; and/or the number of the groups of groups,
the adding amount of PVDF in the casting solution is 10-15 wt%; and/or the number of the groups of groups,
the water bath temperature for curing the film was 25℃and the doctor blade height of the automatic film coater was 0.25mm.
8. An ultrafiltration membrane with photocatalysis-photo-thermal synergistic performance, which is characterized in that the ultrafiltration membrane is prepared by adopting the preparation method of any one of claims 1 to 7.
9. The ultrafiltration membrane with photocatalytic-photothermal synergistic performance according to claim 8, wherein the Pd-TiO 2 The PEDOT photocatalysis-photothermal PVDF ultrafiltration membrane has photocatalysis activity under the whole wave band; and
the Pd-TiO 2 PEDOT photocatalysis-photo-thermal PVDF ultrafiltration membrane is a hydrophilic membrane.
10. The use of an ultrafiltration membrane with photocatalytic-photothermal synergy according to claim 8 or 9, for the synergistic removal of contaminants in a body of water by photocatalytic-photothermal-membrane separation.
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