CN102408713A - Preparation method for PANI-TiO2-ATP composite material - Google Patents
Preparation method for PANI-TiO2-ATP composite material Download PDFInfo
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- CN102408713A CN102408713A CN201110289497XA CN201110289497A CN102408713A CN 102408713 A CN102408713 A CN 102408713A CN 201110289497X A CN201110289497X A CN 201110289497XA CN 201110289497 A CN201110289497 A CN 201110289497A CN 102408713 A CN102408713 A CN 102408713A
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- tio
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Abstract
The invention discloses a preparation method for PANI-TiO2-ATP composite material, belonging to the technical field of conductive polymer composite material preparation, wherein the method comprises the following steps: preparing TiO2-ATP powdered material firstly and then preparing polyaniline (PANI); mixing the prepared TiO2-ATP powdered material with polyaniline powder, wherein contents of TiO2-ATP in the composite material PANI-TiO2-ATP are respectively 2%, 5%, 10%, 15%, 20% and so on to obtain samples with different contents; symmetrically putting the mixed powder into a planet ball mill and milling it for 1 h, and taking it outer after fully mixing the powder; tabletting by a tabletting press to form to obtain composite material block material with a diameter of 20 mm and a thickness of 10 mm.
Description
Technical field
The invention belongs to the conductive polymer composite preparing technical field, refer in particular to a kind of PANI-TiO
2The preparation method of-ATP matrix material.
Background technology
In conjugated polymers, polyaniline (PANI) is considered to be hopeful most to obtain at present the conductive polymers of practical application with its higher specific conductivity, cheap, the good stability of raw material.Nano titanium oxide (nano-TiO
2) be to use one of the widest material in the nano material, compare with other nano materials, have that chemicalstability is good, photoetch take place after the illumination, resistance to acids and bases is strong, price is low, advantage such as nontoxic, simultaneously, nano-TiO
2Also have photocatalytic activity efficiently, can under UV-light even radiation of visible light, degrade all kinds of chemical substances or kill bacteria, thus receive increasing concern.
Attapulgite clay mineral; After purifying, be called ATP; Attribute with nano material; Be natural nano structure mineral material,, therefore be widely used as sorbent material, support of the catalyst and antiseptic-germicide carrier etc. because they have very large specific surface area and certain ion exchangeable with nanochannel structure.Attapulgite clay has unique physical and chemical performances such as absorption, decolouring, suspension, thixotroping, colloid, filling, rheological, thermostability and salt resistance, is described as " king of thousand soil, ten thousand kinds use soil ".Recent decades, recessed soil has obtained in fields such as oil, chemical industry, food-processing, environmental protection, light textile, agricultural chemicals using widely.Data shows, with TiO
2The matrix material that-ATP nanoparticle and PANI process, its electroconductibility, optical property etc. are compared all with PANI and are increased.
The ball milling blending method is the direct dispersion method of nanoparticle.This method is the nanoparticle that at first synthesizes various forms, again with itself and organic polymer mechanically mixing.The advantage of blending method is the preparation of nanoparticle and the synthetic proceed step by step of material, the form of may command nanoparticle, size.The present invention develops a kind of PANI-TiO
2The preparation method of-ATP matrix material.
Summary of the invention
The objective of the invention is to develop a kind of PANI-TiO
2The preparation method of-ATP matrix material is characterized by, and at first prepares TiO
2-ATP powder body material, concrete technology is following: (1) is measured the 10mL tetrabutyl titanate and is dissolved in the 30mL absolute ethyl alcohol, adds the 2mL trolamine, and stirring at room gets shallow yellow transparent solution A; (2) 10mL absolute ethyl alcohol, 2mL deionized water and 1.5mL nitric acid are mixed with solution B; (3) solution A stirs, and whole B drips of solution are added in the A liquid, forms the orange-yellow colloidal sol of homogeneous transparent; (4) A, the mixed solution of B are ultrasonicly being added that slowly to be added drop-wise to total amount under the condition of stirring be 80mL, containing in the aqueous solution of ATP20%, dripping off continued ultrasonic adding to stir 1 hour; (5) with pure water with TiO
2The presoma of-ATP material cleans and centrifugal 3 times; (6) again 80 ℃ dry 12 hours down, grind then, the powder that obtains 450 ℃ of calcinings 2 hours down, can be obtained TiO
2-ATP powder body material.
Prepare that polyaniline is raw materials used to do, aniline (An), ammonium persulphate (APS), hydrochloric acid, absolute ethyl alcohol all are analytical pure.The technology of preparation polyaniline is following: light is met in the pre-treatment of (1) aniline, aniline or air is prone to oxidation and is yellow, needs distillation to purify before therefore using.100g aniline is added concuss in the Erlenmeyer flask that fills the 40g Calcium Chloride Powder Anhydrous, leave standstill 24 hours to absorb moisture wherein.After water distilling apparatus mixes up, pour aniline into matrass, add the 15g zinc powder and prevent the aniline oxidation, add the 25g zeolite and prevent bumping, begin heating and regulate heating rate, 5 ℃/min of heating rate, 183～185 ℃ of Heating temperatures produce small bubbles equably.Colorless oil cut between collecting 183～185 ℃, when the vapor temperature big ups and downs, distillation finishes, and stops heating.After treating the device cooling, take out distillate, repeat above-mentioned steps, carry out second distillation.Transferring in the brown bottle, preserve at last at shady place through the aniline of second distillation.(2) preparation of former doped polyaniline, compound concentration are the aqueous hydrochloric acid of 1mol/L.Pretreated 10ml aniline monomer is dissolved in the hydrochloric acid soln of 240ml hydrochloric 15%, and is transferred to three-necked bottle, stir.Taking by weighing with the aniline monomer mol ratio is 1: 1 ammonium persulphate (NH
4)
2S
2O
8) be dissolved in the 250ml hydrochloric acid, and be transferred to tap funnel.With ammonium persulphate (NH
4)
2S
2O
8) hydrochloric acid soln slowly be added drop-wise in the three-necked bottle, that solution is become by water white transparency very soon is light green-light blue-dark blue-purplish red.Dripped 1.5 hours continued stirring reactions 5 hours, stopped reaction, suction filtration.Filter cake is cleaned to colourless with hydrochloric 15% hydrochloric acid soln, absolute ethyl alcohol successively repeatedly, and vacuum-drying promptly obtained blackish green chromogen doped polyaniline (PANI) powder in 24 hours under 333K at last.
With the TiO for preparing
2-ATP powder body material mixes with polyaniline powder, wherein TiO
2-ATP is at matrix material PANI-TiO
2Content among the-ATP is respectively 2%, 5%, 10%, 15%, 20%, obtains the sample of heterogeneity.Above-mentioned mixed material was put into the planetary ball mill ball milling 1 hour symmetrically, take out after making the powder thorough mixing, use the tabletting machine compression molding, obtain diameter and be 20mm, thickly be the matrix material bulk of 10mm.
With BS 124S type electronic balance to powder weighing; Dry grind with the QM-ISP04 planetary ball mill, adopt the Al of diameter 4～6mm
2O
3Ceramic Balls is as abrading-ball; (SEM) observes the pattern of matrix material with the HITCH3000-N type; Measure its electroconductibility with the eddy current conductivity apparatus.
Table 1TiO
2-ATP content is to PANI-TiO
2The influence of-ATP electroconductibility
TiO
2The add-on of-ATP powder body material is to PANI-TiO
2Table 1 is seen in the influence of-ATP electroconductibility.Can find out by table 1, along with TiO
2The increase of-ATP powder body material massfraction, PANI-TiO
2The electroconductibility of-ATP matrix material constantly increased before this, after being increased to 10%, begins again to descend, and be TiO through analyzing the highest point of this electroconductibility
2-ATP powder body material massfraction is 10%.
Description of drawings
Fig. 1 PANI-TiO
2The SEM figure of-ATP
Fig. 1 is PANI-TiO
2(wherein the content of PANI is 90% to-ATP, TiO
2The content of-ATP is 10%) electron scanning micrograph.As can be seen from Figure 1 PANI-TiO
2Occurred club among the-ATP, this is ATP, and can find out obviously that there is the layer of even small-particle on the surface, and these uniform small-particles are PANI and the TiO that are dispersed on the ATP
2Particle.In addition, as can be seen from the figure, except that bar-shaped ATP, PANI and TiO
2Mix and be difficult to differentiate, but that surface particles distributes is more even.
Embodiment
Embodiment 1
At first prepare TiO
2-ATP powder body material, concrete technology is following: (1) is measured the 10mL tetrabutyl titanate and is dissolved in the 30mL absolute ethyl alcohol, adds the 2mL trolamine, and stirring at room gets shallow yellow transparent solution A; (2) 10mL absolute ethyl alcohol, 2mL deionized water and 1.5mL nitric acid are mixed with solution B; (3) solution A stirs, and whole B drips of solution are added in the A liquid, forms the orange-yellow colloidal sol of homogeneous transparent; (4) A, the mixed solution of B are ultrasonicly being added that slowly to be added drop-wise to total amount under the condition of stirring be 80mL, containing in the aqueous solution of ATP20%, dripping off continued ultrasonic adding to stir 1 hour; (5) with pure water with TiO
2The presoma of-ATP material cleans and centrifugal 3 times; (6) again 80 ℃ dry 12 hours down, grind then, the powder that obtains 450 ℃ of calcinings 2 hours down, can be obtained TiO
2-ATP powder body material.
Prepare that polyaniline is raw materials used to do, aniline (An), ammonium persulphate (APS), hydrochloric acid, absolute ethyl alcohol all are analytical pure.The technology of preparation polyaniline is following: light is met in the pre-treatment of (1) aniline, aniline or air is prone to oxidation and is yellow, needs distillation to purify before therefore using.100g aniline is added concuss in the Erlenmeyer flask that fills the 40g Calcium Chloride Powder Anhydrous, leave standstill 24 hours to absorb moisture wherein.After water distilling apparatus mixes up, pour aniline into matrass, add the 15g zinc powder and prevent the aniline oxidation, add the 25g zeolite and prevent bumping, begin heating and regulate heating rate, 5 ℃/min of heating rate, 183～185 ℃ of Heating temperatures produce small bubbles equably.Colorless oil cut between collecting 183～185 ℃, when the vapor temperature big ups and downs, distillation finishes, and stops heating.After treating the device cooling, take out distillate, repeat above-mentioned steps, carry out second distillation.Transferring in the brown bottle, preserve at last at shady place through the aniline of second distillation.(2) preparation of former doped polyaniline, compound concentration are the aqueous hydrochloric acid of 1mol/L.Pretreated 10ml aniline monomer is dissolved in the hydrochloric acid soln of 240ml hydrochloric 15%, and is transferred to three-necked bottle, stir.Taking by weighing with the aniline monomer mol ratio is 1: 1 ammonium persulphate (NH
4)
2S
2O
8) be dissolved in the 250ml hydrochloric acid, and be transferred to tap funnel.With ammonium persulphate (NH
4)
2S
2O
8) hydrochloric acid soln slowly be added drop-wise in the three-necked bottle, that solution is become by water white transparency very soon is light green-light blue-dark blue-purplish red.Dripped 1.5 hours continued stirring reactions 5 hours, stopped reaction, suction filtration.Filter cake is cleaned to colourless with hydrochloric 15% hydrochloric acid soln, absolute ethyl alcohol successively repeatedly, and vacuum-drying promptly obtained blackish green chromogen doped polyaniline (PANI) powder in 24 hours under 333K at last.
With the TiO for preparing
2-ATP powder body material mixes with polyaniline powder, wherein TiO
2-ATP is at matrix material PANI-TiO
2Content among the-ATP is 2%.Above-mentioned mixed powder was put into the planetary ball mill ball milling 1 hour symmetrically, take out after making the powder thorough mixing, use the tabletting machine compression molding, obtain diameter and be 20mm, thickly be the matrix material bulk of 10mm.This moment PANI-TiO
2The specific conductivity of-ATP matrix material (S/cm) is 0.9.
Embodiment 2
At first prepare TiO
2-ATP powder body material, concrete technology is following: (1) is measured the 10mL tetrabutyl titanate and is dissolved in the 30mL absolute ethyl alcohol, adds the 2mL trolamine, and stirring at room gets shallow yellow transparent solution A; (2) 10mL absolute ethyl alcohol, 2mL deionized water and 1.5mL nitric acid are mixed with solution B; (3) solution A stirs, and whole B drips of solution are added in the A liquid, forms the orange-yellow colloidal sol of homogeneous transparent; (4) A, the mixed solution of B are ultrasonicly being added that slowly to be added drop-wise to total amount under the condition of stirring be 80mL, containing in the aqueous solution of ATP20%, dripping off continued ultrasonic adding to stir 1 hour; (5) with pure water with TiO
2The presoma of-ATP material cleans and centrifugal 3 times; (6) again 80 ℃ dry 12 hours down, grind then, the powder that obtains 450 ℃ of calcinings 2 hours down, can be obtained TiO
2-ATP powder body material.
Prepare that polyaniline is raw materials used to do, aniline (An), ammonium persulphate (APS), hydrochloric acid, absolute ethyl alcohol all are analytical pure.The technology of preparation polyaniline is following: light is met in the pre-treatment of (1) aniline, aniline or air is prone to oxidation and is yellow, needs distillation to purify before therefore using.100g aniline is added concuss in the Erlenmeyer flask that fills the 40g Calcium Chloride Powder Anhydrous, leave standstill 24 hours to absorb moisture wherein.After water distilling apparatus mixes up, pour aniline into matrass, add the 15g zinc powder and prevent the aniline oxidation, add the 25g zeolite and prevent bumping, begin heating and regulate heating rate, 5 ℃/min of heating rate, 183～185 ℃ of Heating temperatures produce small bubbles equably.Colorless oil cut between collecting 183～185 ℃, when the vapor temperature big ups and downs, distillation finishes, and stops heating.After treating the device cooling, take out distillate, repeat above-mentioned steps, carry out second distillation.Transferring in the brown bottle, preserve at last at shady place through the aniline of second distillation.(2) preparation of former doped polyaniline, compound concentration are the aqueous hydrochloric acid of 1mol/L.Pretreated 10ml aniline monomer is dissolved in the hydrochloric acid soln of 240ml hydrochloric 15%, and is transferred to three-necked bottle, stir.Taking by weighing with the aniline monomer mol ratio is 1: 1 ammonium persulphate (NH
4)
2S
2O
8) be dissolved in the 250ml hydrochloric acid, and be transferred to tap funnel.With ammonium persulphate (NH
4)
2S
2O
8) hydrochloric acid soln slowly be added drop-wise in the three-necked bottle, that solution is become by water white transparency very soon is light green-light blue-dark blue-purplish red.Dripped 1.5 hours continued stirring reactions 5 hours, stopped reaction, suction filtration.Filter cake is cleaned to colourless with hydrochloric 15% hydrochloric acid soln, absolute ethyl alcohol successively repeatedly, and vacuum-drying promptly obtained blackish green chromogen doped polyaniline (PANI) powder in 24 hours under 333K at last.
With the TiO for preparing
2-ATP powder body material mixes with polyaniline powder, wherein TiO
2-ATP is at matrix material PANI-TiO
2Content among the-ATP is 10%.Above-mentioned mixed powder was put into the planetary ball mill ball milling 1 hour symmetrically, take out after making the powder thorough mixing, use the tabletting machine compression molding, obtain diameter and be 20mm, thickly be the matrix material bulk of 10mm.This moment PANI-TiO
2The specific conductivity of-ATP matrix material (S/cm) is 1.8, and electroconductibility is best.
Embodiment 3
At first prepare TiO
2-ATP powder body material, concrete technology is following: (1) is measured the 10mL tetrabutyl titanate and is dissolved in the 30mL absolute ethyl alcohol, adds the 2mL trolamine, and stirring at room gets shallow yellow transparent solution A; (2) 10mL absolute ethyl alcohol, 2mL deionized water and 1.5mL nitric acid are mixed with solution B; (3) solution A stirs, and whole B drips of solution are added in the A liquid, forms the orange-yellow colloidal sol of homogeneous transparent; (4) A, the mixed solution of B are ultrasonicly being added that slowly to be added drop-wise to total amount under the condition of stirring be 80mL, containing in the aqueous solution of ATP20%, dripping off continued ultrasonic adding to stir 1 hour; (5) with pure water with TiO
2The presoma of-ATP material cleans and centrifugal 3 times; (6) again 80 ℃ dry 12 hours down, grind then, the powder that obtains 450 ℃ of calcinings 2 hours down, can be obtained TiO
2-ATP powder body material.
Prepare that polyaniline is raw materials used to do, aniline (An), ammonium persulphate (APS), hydrochloric acid, absolute ethyl alcohol all are analytical pure.The technology of preparation polyaniline is following: light is met in the pre-treatment of (1) aniline, aniline or air is prone to oxidation and is yellow, needs distillation to purify before therefore using.100g aniline is added concuss in the Erlenmeyer flask that fills the 40g Calcium Chloride Powder Anhydrous, leave standstill 24 hours to absorb moisture wherein.After water distilling apparatus mixes up, pour aniline into matrass, add the 15g zinc powder and prevent the aniline oxidation, add the 25g zeolite and prevent bumping, begin heating and regulate heating rate, 5 ℃/min of heating rate, 183～185 ℃ of Heating temperatures produce small bubbles equably.Colorless oil cut between collecting 183～185 ℃, when the vapor temperature big ups and downs, distillation finishes, and stops heating.After treating the device cooling, take out distillate, repeat above-mentioned steps, carry out second distillation.Transferring in the brown bottle, preserve at last at shady place through the aniline of second distillation.(2) preparation of former doped polyaniline, compound concentration are the aqueous hydrochloric acid of 1mol/L.Pretreated 10ml aniline monomer is dissolved in the hydrochloric acid soln of 240ml hydrochloric 15%, and is transferred to three-necked bottle, stir.Taking by weighing with the aniline monomer mol ratio is 1: 1 ammonium persulphate (NH
4)
2S
2O
8) be dissolved in the 250ml hydrochloric acid, and be transferred to tap funnel.With ammonium persulphate (NH
4)
2S
2O
8) hydrochloric acid soln slowly be added drop-wise in the three-necked bottle, that solution is become by water white transparency very soon is light green-light blue-dark blue-purplish red.Dripped 1.5 hours continued stirring reactions 5 hours, stopped reaction, suction filtration.Filter cake is cleaned to colourless with hydrochloric 15% hydrochloric acid soln, absolute ethyl alcohol successively repeatedly, and vacuum-drying promptly obtained blackish green chromogen doped polyaniline (PANI) powder in 24 hours under 333K at last.
With the TiO for preparing
2-ATP powder body material mixes with polyaniline powder, wherein TiO
2-ATP is at matrix material PANI-TiO
2Content among the-ATP is 20%.Above-mentioned mixed powder was put into the planetary ball mill ball milling 1 hour symmetrically, take out after making the powder thorough mixing, use the tabletting machine compression molding, obtain diameter and be 20mm, thickly be the matrix material bulk of 10mm.The PANI-TiO of this moment
2The specific conductivity of-ATP matrix material (S/cm) is 0.8.
Claims (3)
1. PANI-TiO
2The preparation method of-ATP matrix material is characterized by, and at first prepares TiO
2-ATP powder body material, concrete technology is following: measure the 10mL tetrabutyl titanate and be dissolved in the 30mL absolute ethyl alcohol, add the 2mL trolamine, stirring at room gets shallow yellow transparent solution A; 10mL absolute ethyl alcohol, 2mL deionized water and 1.5mL nitric acid are mixed with solution B; Solution A stirs, and whole B drips of solution are added in the A liquid, forms the orange-yellow colloidal sol of homogeneous transparent; A, the mixed solution of B are ultrasonicly being added that slowly to be added drop-wise to total amount under the condition of stirring be 80mL, containing in the aqueous solution of ATP20%, dripping off continued ultrasonic adding to stir 1 hour; With pure water with TiO
2The presoma of-ATP material cleans and centrifugal 3 times; Again 80 ℃ dry 12 hours down, grind then, the powder that obtains 450 ℃ of calcinings 2 hours down, can be obtained TiO
2-ATP powder body material; Prepare that polyaniline is raw materials used to do, aniline (An), ammonium persulphate (APS), hydrochloric acid, absolute ethyl alcohol all are analytical pure; The technology of preparation polyaniline is following: light is met in the pre-treatment of aniline, aniline or air is prone to oxidation and is yellow, needs distillation to purify before therefore using; 100g aniline is added concuss in the Erlenmeyer flask that fills the 40g Calcium Chloride Powder Anhydrous, leave standstill 24 hours to absorb moisture wherein; After water distilling apparatus mixes up, pour aniline into matrass, add the 15g zinc powder and prevent the aniline oxidation, add the 25g zeolite and prevent bumping, begin heating and regulate heating rate, 5 ℃/min of heating rate, 183～185 ℃ of Heating temperatures produce small bubbles equably; Colorless oil cut between collecting 183～185 ℃, when the vapor temperature big ups and downs, distillation finishes, and stops heating.After treating the device cooling, take out distillate, repeat above-mentioned steps, carry out second distillation; Transferring in the brown bottle, preserve at last at shady place through the aniline of second distillation; The preparation of former doped polyaniline, compound concentration are the aqueous hydrochloric acid of 1mol/L; Pretreated 10ml aniline monomer is dissolved in the hydrochloric acid soln of 240ml hydrochloric 15%, and is transferred to three-necked bottle, stir; Taking by weighing with the aniline monomer mol ratio is 1: 1 ammonium persulphate (NH
4)
2S
2O
8) be dissolved in the 250ml hydrochloric acid, and be transferred to tap funnel; With ammonium persulphate (NH
4)
2S
2O
8) hydrochloric acid soln slowly be added drop-wise in the three-necked bottle, that solution is become by water white transparency very soon is light green-light blue-dark blue-purplish red; Dripped 1.5 hours continued stirring reactions 5 hours, stopped reaction, suction filtration; Filter cake is cleaned to colourless with hydrochloric 15% hydrochloric acid soln, absolute ethyl alcohol successively repeatedly, and vacuum-drying promptly obtained blackish green chromogen doping polyaniline powder in 24 hours under 333K at last.
2. according to the said a kind of PANI-TiO of claim 1
2The preparation method of-ATP matrix material is with the TiO for preparing
2-ATP powder body material mixes with polyaniline powder, wherein TiO
2-ATP is at matrix material PANI-TiO
2Content among the-ATP is respectively 2%, 5%, 10%, 15%, 20%, obtains the sample of heterogeneity; Above-mentioned mixed material was put into the planetary ball mill ball milling 1 hour symmetrically, take out after making the powder thorough mixing, use the tabletting machine compression molding, obtain diameter and be 20mm, thickly be the matrix material bulk of 10mm.
3. according to the said a kind of PANI-TiO of claim 2
2The preparation method of-ATP matrix material, TiO
2-ATP is at matrix material PANI-TiO
2Content among the-ATP is 10% o'clock, and electroconductibility is best, and specific conductivity S/cm reaches 1.8.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881378A (en) * | 2014-03-28 | 2014-06-25 | 常州纳欧新材料科技有限公司 | Preparation method of clay/titanium dioxide/polyaniline conductive composite material |
| CN104084241A (en) * | 2014-07-29 | 2014-10-08 | 吉林大学 | Titanium dioxide/polyaniline photocatalyst with 3D pattern structure and preparation method of titanium dioxide/polyaniline photocatalyst |
| CN113233532A (en) * | 2021-04-30 | 2021-08-10 | 浙江工业大学 | Low-cost photo-thermal material based on solar interface evaporation and preparation method thereof |
| CN113634279A (en) * | 2021-07-14 | 2021-11-12 | 浙江工业大学 | Oil-water amphiphilic titanium-based Ag/TiO2Preparation and application of @ PANI photocatalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881378A (en) * | 2014-03-28 | 2014-06-25 | 常州纳欧新材料科技有限公司 | Preparation method of clay/titanium dioxide/polyaniline conductive composite material |
| CN103881378B (en) * | 2014-03-28 | 2016-03-02 | 常州纳欧新材料科技有限公司 | A kind of preparation method of clay/titanium dioxide/polyaniline composite material |
| CN104084241A (en) * | 2014-07-29 | 2014-10-08 | 吉林大学 | Titanium dioxide/polyaniline photocatalyst with 3D pattern structure and preparation method of titanium dioxide/polyaniline photocatalyst |
| CN113233532A (en) * | 2021-04-30 | 2021-08-10 | 浙江工业大学 | Low-cost photo-thermal material based on solar interface evaporation and preparation method thereof |
| CN113233532B (en) * | 2021-04-30 | 2022-04-29 | 浙江工业大学 | Low-cost photo-thermal material based on solar interface evaporation and preparation method thereof |
| CN113634279A (en) * | 2021-07-14 | 2021-11-12 | 浙江工业大学 | Oil-water amphiphilic titanium-based Ag/TiO2Preparation and application of @ PANI photocatalyst |
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