CN110975942A - Preparation method of composite photocatalyst - Google Patents
Preparation method of composite photocatalyst Download PDFInfo
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- CN110975942A CN110975942A CN201911353810.4A CN201911353810A CN110975942A CN 110975942 A CN110975942 A CN 110975942A CN 201911353810 A CN201911353810 A CN 201911353810A CN 110975942 A CN110975942 A CN 110975942A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004793 Polystyrene Substances 0.000 claims abstract description 18
- 229920002223 polystyrene Polymers 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 44
- 239000012065 filter cake Substances 0.000 claims description 35
- 239000012074 organic phase Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000002041 carbon nanotube Substances 0.000 claims description 31
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 27
- 239000012071 phase Substances 0.000 claims description 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000006866 deterioration Effects 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 2
- 238000005057 refrigeration Methods 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 abstract description 4
- 238000006277 sulfonation reaction Methods 0.000 abstract 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 36
- 239000000243 solution Substances 0.000 description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/33—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a preparation method of a composite photocatalyst, which relates to the technical field of photocatalysts, and is characterized in that embedded AgI, multi-walled carbon nanotubes and polystyrene photocatalysts are prepared and then subjected to sulfonation reaction.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a preparation method of a composite photocatalyst.
Background
The photocatalytic principle is based on the oxidation-reduction capability of a photocatalyst under the condition of illumination, so that the purposes of purifying pollutants, synthesizing and converting substances and the like can be achieved.
The photocatalyst developed at present has poor dispersion effect in water and poor substrate adsorption effect on the surface, so that photo-generated carriers transferred to the surface of a material cannot be rapidly captured, and the interface transfer probability in the photocatalytic process is reduced.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a preparation method of a composite photocatalyst.
In order to achieve the purpose, the invention is implemented according to the following technical scheme:
a preparation method of a composite photocatalyst comprises the following steps:
s1, using 5% KOH solution to remove styrene in three times, standing for better layering, then separating, and then washing with deionized water to be neutral; the mass ratio of the KOH solution to the styrene is 8-12: 1;
s2, aqueous phase: taking polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in 90% ethanol solution under the condition of stirring, and pouring the water phase into a flask; the mass ratio of the ethanol solution to the polyvinylpyrrolidone is 160-200: 1;
s3, adding AgI and carbon nanotubes into the flask in the step S2, gradually increasing the rotation speed of the flask from the beginning of standing, and slowly dispersing the AgI and the carbon nanotubes into a water phase;
s4, organic phase: adding azodiisobutyronitrile and divinylbenzene into the styrene subjected to the resistance removal in the step S1, and stirring to dissolve and uniformly disperse the azodiisobutyronitrile and the divinylbenzene to obtain an organic phase;
s5, dropwise adding the organic phase in the step S4 into the flask in the step S2;
s6, mixing the organic phase and the water phase and stirring for 30 min; then heating to 80 ℃, reacting for 6 hours, keeping stirring, continuously heating to 98 ℃, reacting for 4 hours, keeping stirring, and burning deionized water 5 minutes ahead of time for later use;
s7, after the reaction is finished, flushing the product with the burnt deionized water, standing and cooling to room temperature; after being uniformly stirred, the mixture is centrifuged, washed for three times, and then dried in a 60 ℃ forced air drying oven for 12 hours to obtain a polystyrene AgI and carbon nanotube doped material;
s8, placing the polystyrene AgI and carbon nanotube doped material prepared in the step S7 into a container, adding 1, 2-dichloroethane into the container to swell for 5 hours, wherein the mass ratio of the polystyrene AgI and carbon nanotube doped material to the 1, 2-dichloroethane is 1:16-18, after swelling, taking concentrated sulfuric acid, slowly adding into the container, the mass ratio of the styrene AgI and carbon nanotube doped material to the concentrated sulfuric acid is 1:6, stirring for 30 minutes, starting heating to 85 ℃, reacting at 85 ℃ for 6 hours at constant temperature, then heating to 98 ℃, reacting at 98 ℃ for 2 hours at constant temperature, collecting a product, and centrifuging once to obtain a filter cake;
s9, adding 2.5mol/L sodium hydroxide solution into a beaker, adding a magnetic stirrer to enable the solution to be in a stirring state, then completely adding the filter cake prepared in the step S8 into the beaker, stirring for 3 minutes, detecting the pH value of the centrifugate by using a pH test paper after centrifugation, if the centrifugate is still acidic, continuing neutralizing by using the sodium hydroxide solution until the centrifugate is alkaline, and centrifuging to obtain a filter cake;
s10, putting deionized water into a beaker, putting the beaker on a magnetic stirrer to enable the magnetic stirrer to be in a stirring state, then completely adding the filter cake prepared in the step S9 into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, if the centrifugate is alkaline, continuing repeating the above operation by using the deionized water until the centrifugate is neutral, and centrifuging to obtain the filter cake;
s11, placing absolute ethyl alcohol into a beaker, placing the beaker on a magnetic stirrer to enable the magnetic stirrer to be in a stirring state, then completely adding the filter cake prepared in the step 10 into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, if the centrifugate is alkaline, continuing to repeat the above operation by using the absolute ethyl alcohol until the centrifugate is neutral, placing the filter cake into a drying box at 80 ℃ after centrifuging, and drying for 12 hours to obtain a product;
preferably, in step S5, the dropping time of the organic phase into the flask containing the aqueous phase is 5min, the azobisisobutyronitrile cannot be completely dissolved, the oil phase is sucked out as soon as possible when being dropped into the flask, the stirring speed is not too fast or is slow in the dropping process to reduce loss, and the organic phase is prevented from sticking to the wall of the flask;
preferably, in step S4, the prepared azobisisobutyronitrile and divinylbenzene should be stored under refrigeration to prevent deterioration before styrene is well deblocked;
preferably, in step S6, the mixing speed of the organic phase and the aqueous phase is 180 r/min, and when the temperature is increased to 80 ℃ and 98 ℃, the mixing speed is maintained at 350 r/min; carefully observing the polymerization condition of the polystyrene in the temperature rising process, and gradually accelerating the polymerization condition, wherein the aim is to uniformly stir the mixture and prevent the carbon nano tube and AgI from being adhered to the wall;
preferably, in step S7, the centrifuge tube has a centrifuge speed of 10000 r/min and a centrifuge time of 5 minutes.
Compared with the prior art, the preparation method of the composite photocatalyst has the following beneficial effects:
1. the photocatalyst combines AgI and hydrophilic sulfonated polystyrene, and the dispersion effect in water is obviously superior to that of the traditional photocatalyst;
2. the sulfonated polystyrene has strong adsorption capacity, and promotes the adsorption of the composite photocatalyst to substrates in water;
3. the conductivity of the material doped with the multi-walled carbon nanotube is improved, and the separation and migration of photogenerated electrons and holes are facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a graph showing the absorption of phenol in water by the composite photocatalyst of example 1 according to the present invention;
FIG. 2 is a bar graph of the electrical conductivity of the different components making up the composite of example 1 of the present invention;
FIG. 3 is a graph showing the photodegradation properties of the composite photocatalyst of example 1 of the present invention with respect to phenol.
Detailed Description
The invention will be further described with reference to the drawings and specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1
Removing 11mL of styrene by using 100mL of 5% KOH solution for three times, wherein the three dosages are 40mL, 35mL and 25mL respectively, standing for better layering and then separating under 100 times of removal of the oscillation, then washing with deionized water to be neutral, and using 40mL of deionized water for each time; taking 0.605g of polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in a mixed solution of 99ml of ethanol and 11ml of distilled water under the stirring condition, and pouring the water phase into a flask; adding AgI and carbon nano tubes into a flask, gradually increasing the rotating speed of the flask from the beginning of standing, and slowly dispersing the AgI and the carbon nano tubes into a water phase; organic phase: adding 0.275g of azobisisobutyronitrile and 2.75mL of divinylbenzene into 11mL of styrene with the resistance removed, stirring to dissolve and uniformly disperse the mixture to obtain an organic phase; before the resistance of the styrene is not removed, the prepared azodiisobutyronitrile and divinylbenzene should be refrigerated for preventing deterioration; dropwise adding the organic phase into the flask; the dropping time of the organic phase into the flask containing the water phase is 5min, the azobisisobutyronitrile cannot be completely dissolved, the oil phase is sucked out as soon as possible when being dropped and is added into the flask, the stirring speed is not too fast or is slow in the dropping process, and the organic phase is prevented from being stuck on the wall of the flask; mixing the organic phase and the water phase, and stirring for 30 min; then heating to 80 ℃, reacting for 6 hours, keeping stirring, continuously heating to 98 ℃, reacting for 4 hours, keeping stirring, wherein the stirring speed for mixing the organic phase and the water phase is 150 r/min, and when heating to 80 ℃ and 98 ℃, keeping the stirring speed at 300 r/min; carefully observing the polymerization condition of the polystyrene in the temperature rising process, and gradually accelerating the polymerization condition, wherein the aim is to uniformly stir the mixture and prevent the carbon nano tube and AgI from being adhered to the wall; the rotating speed can not be directly increased, so that the material is thrown onto the wall of a flask, and deionized water is burnt for later use 5 minutes in advance; after the reaction is finished, flushing out the product by using the burnt deionized water, standing and cooling to room temperature; centrifuging after uniformly stirring, washing with water for three times at the centrifugal speed of 10000 r/min and the centrifugal time of 5 minutes, and then drying in a 60 ℃ blast drying oven for 12 hours to obtain the polystyrene AgI and carbon nanotube doped material; putting 4g of prepared polystyrene AgI and carbon nanotube doped material into a container, adding 70 ml of 1, 2-dichloroethane into the container to swell for 5 hours, after swelling, taking concentrated sulfuric acid, slowly adding into the container, wherein the mass ratio of the styrene AgI and carbon nanotube doped material to the concentrated sulfuric acid is 1:6, stirring for 30 minutes, starting heating to 85 ℃, reacting at 85 ℃ for 6 hours at constant temperature, then heating to 98 ℃, reacting at 98 ℃ for 2 hours at constant temperature, collecting the product, and centrifuging once to obtain a filter cake; adding 50mL of 2.5mol/L sodium hydroxide solution into a beaker, adding a magnetic stirrer to enable the solution to be in a stirring state, completely adding the prepared filter cake into the beaker, stirring for 3 minutes, detecting the pH value of the centrifugate by using a pH test paper after centrifugation, continuously neutralizing the centrifugate by using 50mL of sodium hydroxide solution if the centrifugate is still acidic until the centrifugate is alkaline, and centrifuging to obtain the filter cake; putting 50mL of deionized water into a beaker, putting the beaker on a magnetic stirrer in a stirring state, completely adding the prepared filter cake into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, continuously repeating the above operation by using the deionized water if the centrifugate is alkaline until the centrifugate is neutral, and centrifuging to obtain the filter cake; and (3) placing 50mL of absolute ethyl alcohol in a beaker, placing the beaker on a magnetic stirrer in a stirring state, completely adding the prepared filter cake into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, if the centrifugate is alkaline, continuously repeating the above operation by using the absolute ethyl alcohol until the centrifugate is neutral, placing the filter cake in a drying box at 80 ℃ after centrifuging, and drying for 12 hours to obtain the product.
Example 2
Removing the damping of 9mL of styrene by using 100mL of 5% KOH solution for three times, wherein the three dosages are 40mL, 35mL and 25mL respectively, standing for better layering and then separating under 100 times of damping vibration removal, and then washing with deionized water to be neutral, wherein 40mL of deionized water is used for each time; taking 0.7g of polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in 140 mL of 90% ethanol solution under the condition of stirring, and pouring the water phase into a flask; adding AgI and carbon nano tubes into a flask, gradually increasing the rotating speed of the flask from the beginning of standing, and slowly dispersing the AgI and the carbon nano tubes into a water phase; adding 0.35g of azobisisobutyronitrile and 3.5mL of divinylbenzene into 9mL of styrene with the resistance removed, stirring to dissolve and uniformly disperse the mixture to obtain an organic phase; before the resistance of the styrene is not removed, the prepared azodiisobutyronitrile and divinylbenzene should be refrigerated for preventing deterioration; dropwise adding the organic phase into the flask; the dropping time of the organic phase into the flask containing the water phase is 5min, the azobisisobutyronitrile cannot be completely dissolved, the oil phase is sucked out as soon as possible when being dropped and is added into the flask, the stirring speed is not too fast or is slow in the dropping process, and the organic phase is prevented from being stuck on the wall of the flask; mixing the organic phase and the water phase, and stirring for 30 min; heating to 80 ℃, reacting for 6 hours, keeping stirring, continuously heating to 98 ℃, reacting for 4 hours, keeping stirring, keeping the stirring speed of the organic phase and the water phase at 180 r/min, and keeping the stirring speed at 350 r/min when heating to 80 ℃ and 98 ℃; carefully observing the polymerization condition of the polystyrene in the temperature rising process, and gradually accelerating the polymerization condition, wherein the aim is to uniformly stir the mixture and prevent the carbon nano tube and AgI from being adhered to the wall; the rotating speed can not be directly increased, so that the material is thrown onto the wall of a flask, and deionized water is burnt for later use 5 minutes in advance; after the reaction is finished, flushing out the product by using the burnt deionized water, standing and cooling to room temperature; centrifuging after uniformly stirring, washing with water for three times at the centrifugal speed of 10000 r/min and the centrifugal time of 5 minutes, and then drying in a 60 ℃ blast drying oven for 12 hours to obtain the polystyrene AgI and carbon nanotube doped material; putting 4g of prepared polystyrene AgI and carbon nanotube doped material into a container, adding 70 ml of 1, 2-dichloroethane into the container to swell for 5 hours, after swelling, taking concentrated sulfuric acid, slowly adding into the container, wherein the mass ratio of the styrene AgI and carbon nanotube doped material to the concentrated sulfuric acid is 1:6, stirring for 30 minutes, starting heating to 85 ℃, reacting at 85 ℃ for 6 hours at constant temperature, then heating to 98 ℃, reacting at 98 ℃ for 2 hours at constant temperature, collecting the product, and centrifuging once to obtain a filter cake; taking 50mL of 2.5mol/L sodium hydroxide solution into a beaker, placing the beaker on a magnetic stirrer in a stirring state, completely adding the prepared filter cake into the beaker, stirring for 3 minutes, detecting the pH value of the centrifugate by using a pH test paper after centrifugation, continuously neutralizing the centrifugate by using 50mL of sodium hydroxide solution if the centrifugate is still acidic until the centrifugate is alkaline, and centrifuging to obtain the filter cake; putting 50mL of deionized water into a beaker, putting the beaker on a magnetic stirrer to enable the beaker to be in a stirring state, then completely adding the prepared filter cake into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, if the centrifugate is alkaline, continuing repeating the above operation by using the deionized water until the centrifugate is neutral, and centrifuging to obtain the filter cake; and (3) placing 50mL of absolute ethyl alcohol in a beaker, placing the beaker on a magnetic stirrer in a stirring state, completely adding the prepared filter cake into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, if the centrifugate is alkaline, continuously repeating the above operation by using the absolute ethyl alcohol until the centrifugate is neutral, placing the filter cake in a drying box at 80 ℃ after centrifuging, and drying for 12 hours to obtain the product.
Example 3
Using 80mL of 5% KOH solution to remove 10mL of styrene by three times, wherein the three dosages are 35mL, 30mL and 15mL respectively, standing for better layering and then separating under 100-degree removal shock each time, then washing with deionized water to be neutral, and using 30mL of deionized water each time; taking 0.5g of polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in 80mL of 90% ethanol solution under the condition of stirring, and pouring the water phase into a flask; adding AgI and carbon nano tubes into a flask, gradually increasing the rotating speed of the flask from the beginning of standing, and slowly dispersing the AgI and the carbon nano tubes into a water phase; adding 0.22g of azobisisobutyronitrile and 2.2mL of divinylbenzene into 10mL of styrene with the resistance removed, stirring to dissolve and uniformly disperse the mixture to obtain an organic phase; before the resistance of the styrene is not removed, the prepared azodiisobutyronitrile and divinylbenzene should be refrigerated for preventing deterioration; dropwise adding the organic phase into the flask; the dropping time of the organic phase into the flask containing the water phase is 5min, the azobisisobutyronitrile cannot be completely dissolved, the oil phase is sucked out as soon as possible when being dropped and is added into the flask, the stirring speed is not too fast or is slow in the dropping process, and the organic phase is prevented from being stuck on the wall of the flask; mixing the organic phase and the water phase, and stirring for 30 min; heating to 80 ℃, reacting for 6 hours, keeping stirring, continuously heating to 98 ℃, reacting for 4 hours, keeping stirring, wherein the stirring speed for mixing the organic phase and the water phase is 120 r/min, and when heating to 80 ℃ and 98 ℃, keeping the stirring speed at 250 r/min; carefully observing the polymerization condition of the polystyrene in the temperature rising process, and gradually accelerating the polymerization condition, wherein the aim is to uniformly stir the mixture and prevent the carbon nano tube and AgI from being adhered to the wall; the rotating speed can not be directly increased, so that the material is thrown onto the wall of a flask, and deionized water is burnt for later use 5 minutes in advance; after the reaction is finished, flushing out the product by using the burnt deionized water, standing and cooling to room temperature; centrifuging after uniformly stirring, washing with water for three times at the centrifugal speed of 10000 r/min and the centrifugal time of 5 minutes, and then drying in a 60 ℃ blast drying oven for 12 hours to obtain the polystyrene AgI and carbon nanotube doped material; putting 4g of prepared polystyrene AgI and carbon nanotube doped material into a container, adding 70 ml of 1, 2-dichloroethane into the container to swell for 5 hours, after swelling, taking concentrated sulfuric acid, slowly adding into the container, wherein the mass ratio of the styrene AgI and carbon nanotube doped material to the concentrated sulfuric acid is 1:6, stirring for 30 minutes, starting heating to 85 ℃, reacting at 85 ℃ for 6 hours at constant temperature, then heating to 98 ℃, reacting at 98 ℃ for 2 hours at constant temperature, collecting the product, and centrifuging once to obtain a filter cake; taking 50mL of 2.5mol/L sodium hydroxide solution into a beaker, placing the beaker on a magnetic stirrer in a stirring state, completely adding the prepared filter cake into the beaker, stirring for 3 minutes, detecting the pH value of the centrifugate by using a pH test paper after centrifugation, continuously neutralizing the centrifugate by using 50mL of sodium hydroxide solution if the centrifugate is still acidic until the centrifugate is alkaline, and centrifuging to obtain the filter cake; putting 50mL of deionized water into a beaker, putting the beaker on a magnetic stirrer in a stirring state, completely adding the prepared filter cake into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, continuously repeating the above operation by using the deionized water if the centrifugate is alkaline until the centrifugate is neutral, and centrifuging to obtain the filter cake; and (3) placing 50mL of absolute ethyl alcohol in a beaker, placing the beaker on a magnetic stirrer in a stirring state, completely adding the prepared filter cake into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, if the centrifugate is alkaline, continuously repeating the above operation by using the absolute ethyl alcohol until the centrifugate is neutral, placing the filter cake in a drying box at 80 ℃ after centrifuging, and drying for 12 hours to obtain the product.
The dispersion effect of the products obtained by the three embodiments of the invention in water is obviously improved, silver iodide exists at the bottom of water in a precipitation form before the silver iodide is compounded with sulfonated polystyrene in the experimental process, and the composite photocatalyst prepared by the method of the invention can be uniformly dispersed in water.
FIG. 1 is a graph showing the absorption curve of the composite photocatalyst of example 1 of the present invention for phenol in water; it can be clearly found from the curve that the adsorption effect of the composite photocatalyst of example 1 on phenol is obviously better than that of the single AgI photocatalyst, the composite photocatalyst adsorbs phenol at 15 minutes with C/Co =0.33, and the single AgI with C/Co = 0.95.
Fig. 2 is a bar graph of the conductivity of the different components constituting the composite material of example 1 of the present invention, and it can be seen from the figure that the conductivity of the material is significantly improved after the AgI is compounded with sulfonated polystyrene and doped with multi-walled carbon nanotubes, which facilitates the migration of photo-generated electrons and holes in the semiconductor.
Fig. 3 shows the photodegradable performance of the phenol in example 1 of the present invention, and it can be seen from the figure that the composite photocatalyst degrades phenol with C/Co =0.064 when illuminated for 120 minutes, and the AgI alone degrades phenol with C/Co =0.42, so that the performance of degrading phenol by photocatalysis is significantly enhanced after the AgI is compounded with sulfonated polystyrene doped with multi-walled carbon nanotubes.
Table one is a table comparing the photocatalytic oxidation performance of three examples of the invention and AgI alone:
| C/Co adsorbing phenol at 15 min | C/Co for degrading phenol when being illuminated for 120 minutes | |
| Example 1 | 0.33 | 0.064 |
| Example 2 | 0.30 | 0.06 |
| Example 3 | 0.27 | 0.057 |
| AgI alone | 0.95 | 0.42 |
TABLE 1
As can be seen from Table 1, the adsorption effect of the composite photocatalyst prepared by the method on phenol is obviously better than that of a single AgI photocatalyst, and the performance of the composite photocatalyst for degrading phenol through photocatalysis is also obviously enhanced.
The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.
Claims (5)
1. A preparation method of the composite photocatalyst is characterized by comprising the following steps:
s1, using 5% KOH solution to remove styrene in three times, standing for better layering, then separating, and then washing with deionized water to be neutral; the mass ratio of the KOH solution to the styrene is 8-12: 1;
s2, aqueous phase: taking polyvinylpyrrolidone, completely dissolving the polyvinylpyrrolidone in 90% ethanol solution under the condition of stirring, and pouring the water phase into a flask; the mass ratio of the ethanol solution to the polyvinylpyrrolidone is 160-200: 1;
s3, adding AgI and carbon nanotubes into the flask in the step S2, gradually increasing the rotation speed of the flask from the beginning of standing, and slowly dispersing the AgI and the carbon nanotubes into a water phase;
s4, organic phase: adding azodiisobutyronitrile and divinylbenzene into the styrene subjected to the resistance removal in the step S1, and stirring to dissolve and uniformly disperse the azodiisobutyronitrile and the divinylbenzene to obtain an organic phase;
s5, dropwise adding the organic phase in the step S4 into the flask in the step S2;
s6, mixing the organic phase and the water phase and stirring for 30 min; then heating to 80 ℃, reacting for 6 hours, keeping stirring, continuously heating to 98 ℃, reacting for 4 hours, keeping stirring, and burning deionized water 5 minutes ahead of time for later use;
s7, after the reaction is finished, flushing the product with the burnt deionized water, standing and cooling to room temperature; after being uniformly stirred, the mixture is centrifuged, washed for three times, and then dried in a 60 ℃ forced air drying oven for 12 hours to obtain a polystyrene AgI and carbon nanotube doped material;
s8, placing the polystyrene AgI and carbon nanotube doped material prepared in the step S7 into a container, adding 1, 2-dichloroethane into the container to swell for 5 hours, wherein the mass ratio of the polystyrene AgI and carbon nanotube doped material to the 1, 2-dichloroethane is 1:16-18, after swelling, taking concentrated sulfuric acid, slowly adding into the container, the mass ratio of the styrene AgI and carbon nanotube doped material to the concentrated sulfuric acid is 1:6, stirring for 30 minutes, starting heating to 85 ℃, reacting at 85 ℃ for 6 hours at constant temperature, then heating to 98 ℃, reacting at 98 ℃ for 2 hours at constant temperature, collecting a product, and centrifuging once to obtain a filter cake;
s9, putting 2.5mol/L sodium hydroxide solution into a beaker, putting the beaker on a magnetic stirrer to enable the beaker to be in a stirring state, then completely adding the filter cake prepared in the step S8 into the beaker, stirring for 3 minutes, detecting the pH value of the centrifugate by using a pH test paper after centrifugation, if the centrifugate is still acidic, continuing neutralizing by using the sodium hydroxide solution until the centrifugate is alkaline, and centrifuging to obtain a filter cake;
s10, putting deionized water into a beaker, putting the beaker on a magnetic stirrer to enable the magnetic stirrer to be in a stirring state, then completely adding the filter cake prepared in the step S9 into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, if the centrifugate is alkaline, continuing repeating the above operation by using the deionized water until the centrifugate is neutral, and centrifuging to obtain the filter cake;
s11, placing absolute ethyl alcohol into a beaker, placing the beaker on a magnetic stirrer to enable the mixture to be in a stirring state, then completely adding the filter cake prepared in the step 10 into the beaker, stirring for 3 minutes, centrifuging, detecting the pH value of the centrifugate by using a pH test paper, if the centrifugate is alkaline, continuing to repeat the above operation by using the absolute ethyl alcohol until the centrifugate is neutral, placing the filter cake into a drying box at 80 ℃ after centrifuging, and drying for 12 hours to obtain the product.
2. The method for preparing the composite photocatalyst as claimed in claim 1, wherein in step S5, the dropping time of the organic phase into the flask containing the aqueous phase is 5min, the azobisisobutyronitrile cannot be completely dissolved, the oil phase is sucked out as soon as possible and added into the flask when being dropped, so that the stirring speed is not too fast or is slow during the dropping process, and the organic phase is prevented from sticking to the wall of the flask.
3. The method for preparing a composite photocatalyst as claimed in claim 1, wherein in step S4, the prepared azobisisobutyronitrile and divinylbenzene should be stored under refrigeration to prevent deterioration before styrene is unblocked.
4. The method for preparing the composite photocatalyst as claimed in claim 1, wherein in the step S6, the mixing speed of the organic phase and the aqueous phase is 180 r/min, and when the temperature is raised to 80 ℃ and 98 ℃, the mixing speed is maintained at 350 r/min and 250-; the polymerization of polystyrene is carefully observed during the temperature rise process, and the polymerization speed is gradually increased.
5. The method for preparing the composite photocatalyst as claimed in claim 1, wherein in step S7, the centrifuge tube is centrifuged at 10000 r/min for 5 minutes.
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