CN113333013A - Ag3PO4-CoFe2O4/g-C3N4Composite high-efficiency photocatalyst and preparation method thereof - Google Patents

Ag3PO4-CoFe2O4/g-C3N4Composite high-efficiency photocatalyst and preparation method thereof Download PDF

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CN113333013A
CN113333013A CN202110695767.0A CN202110695767A CN113333013A CN 113333013 A CN113333013 A CN 113333013A CN 202110695767 A CN202110695767 A CN 202110695767A CN 113333013 A CN113333013 A CN 113333013A
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mixing
microspheres
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龚福忠
余枫秋
王彦沣
杨启帆
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Guangxi University
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Abstract

The invention provides Ag3PO4‑CoFe2O4/g‑C3N4Composite high-efficiency photocatalyst and preparation method thereof. The method is characterized in that: mixing hollow Ag3PO4Microspheres, CoFe2O4And g-C3N4The three are mixed, ball-milled and then placed into a tubular furnace to be calcined for a certain time under the condition of introducing nitrogen, and the required target product Ag can be obtained3PO4‑CoFe2O4/g‑C3N4. The adopted technical scheme is as follows: first, hollow Ag is synthesized separately3PO4Microspheres, CoFe2O4And g-C3N4Mixing silver nitrate water solution, polystyrene emulsion, phosphate or acid phosphate water solution, calcining the precipitate in a tubular furnace to remove polystyrene and obtain the hollow Ag3PO4Microspheres; adjusting the pH of an ethanol aqueous solution of iron salt and cobalt salt to 10-11 by using ammonia water, and drying the precipitate to obtain CoFe2O4(ii) a Mixing and grinding melamine, thiourea and ammonium chloride in a crucible, and then heating by microwave to obtain g-C3N4(ii) a Finally, mixing the hollow Ag3PO4Microspheres, CoFe2O4And g-C3N4Mixing the raw materials according to a certain mass percentage, ball-milling the mixture, putting the mixture into a tube furnace, and calcining the mixture at 400-600 ℃ under the condition of introducing nitrogen to obtain H-Ag3PO4‑CoFe2O4/g‑C3N4A composite photocatalyst is provided.

Description

Ag3PO4-CoFe2O4/g-C3N4Composite high-efficiency photocatalyst and preparation method thereof
Technical Field
The invention relates to Ag3PO4-CoFe2O4/g-C3N4A composite high-efficiency photocatalyst and a preparation method thereof belong to the field of photocatalytic materials.
Background
Silver phosphate (Ag)3PO4) Has good visible light response capability and high photocatalytic performance under natural light irradiation. The preparation is simple and environment-friendly, so that the material is one of the materials with the greatest application prospects in the fields of photocatalytic degradation and photoelectrochemistry. But Ag3PO4Has poor self-stability and is easy to self-corrode in photocatalysis, namely Ag under photocatalysis conditions3PO4Gradually becomes simple substance Ag and finally completely becomes simple substance Ag, resulting in Ag3PO4The stability and the recycling performance of the resin are poor, and the recycling is difficult. For increasing Ag3PO4The stability and the recycling performance of the Ag are improved, and a plurality of researchers prepare the Ag3PO4/AgX (X＝Cl，Br，I)，Ag3PO4/TiO2，Ag3PO4/SnO2，Ag3PO4/CeO2，Ag/Ag3PO4/TiO2，Ag3PO4/In(OH)3， A3PO4Graphite oxideAlkene (GO), Ag3PO4/TiO2Graphene, Ag3PO4/Fe3O4，Ag3PO4/GO/ZnFe2O4， Ag3PO4/C3N4And the composite photocatalysts improve Ag to a certain extent3PO4Stability and cyclability of (B), but with pure Ag3PO4In contrast, the photocatalytic performance is reduced. In addition, some dopants such as Graphene Oxide (GO) have large specific surface area and good conductivity, and can effectively promote the separation of photo-generated electron-hole pairs, but the cost is high and the recycling is very difficult. Moreover, many of the composite photocatalysts are prepared by a high-temperature hydrothermal method, a high-temperature solvothermal method or a sol-gel method, and are limited by equipment conditions, so that the methods are difficult to realize industrial large-scale production.
Graphene-like g-C3N4Can form a highly delocalized pi conjugated system consisting of triazine ring units, and has ideal electronic structure and stability. And thus has received a great deal of attention in visible light catalysis applications. But due to g-C3N4The interlayer is mainly interacted by weak van der waals force, which is not beneficial to the transfer of electrons, thereby causing the low photocatalytic efficiency.
The invention provides an Ag composite photocatalyst for overcoming the defects of the existing silver phosphate composite photocatalyst and a preparation method thereof3PO4-CoFe2O4/g-C3N4A composite high-efficiency photocatalyst and a preparation method thereof. The invention firstly synthesizes hollow Ag respectively3PO4Microspheres, CoFe2O4And g-C3N4Then the three are mixed, ball-milled and put into a tube furnace to be calcined for a certain time under the condition of introducing nitrogen, and the required target product Ag can be obtained3PO4-CoFe2O4/g-C3N4. The adopted technical scheme is as follows: (1) hollow Ag3PO4And (3) synthesis of microspheres: adding a certain concentration of silver nitrate aqueous solution and a certain amount of solid content into a 500mL beaker with stirringThe method comprises the steps of adding 10% of polystyrene (template) emulsion, dropwise adding a phosphate or acid phosphate aqueous solution with a certain concentration, continuously reacting for 0.5-1 h after dropwise adding, filtering, washing a filter cake for 3 times by using deionized water, and finally calcining the filter cake in a 500 ℃ tubular furnace for 3-6 h to remove the template polystyrene to obtain golden hollow Ag3PO4Microspheres, denoted as H-Ag3PO4；(2)CoFe2O4The synthesis of (2): dissolving a certain amount of iron salt and cobalt salt (Fe/Co is 2: 1, the amount ratio of the substances) in 100mL of 50% ethanol aqueous solution, and dropwise adding 1 mol.L-1Adjusting the pH value of the ammonia water solution to 10-11, continuing to magnetically stir for 1-2 h, filtering, washing the filter cake with deionized water for 3 times, and drying the obtained filter cake at 120 ℃ for 1-2 h to obtain CoFe2O4；(3) g-C3N4The synthesis of (2): weighing a certain amount of melamine, thiourea and ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven, and heating for 20-60 min under 800W power to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing H-Ag3PO4Microspheres, CoFe2O4And g-C3N4Mixing according to a certain mass percentage, ball-milling for 1-3H, placing in a tube furnace, introducing nitrogen, calcining for 2-5H at 400-600 ℃ to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
H-Ag as described above3PO4In the preparation of (1), AgNO3The concentration of (A) is as follows: 0.1 to 0.3 mol.L-1。
H-Ag as described above3PO4In the preparation, the usage amount of the adopted polystyrene emulsion with the solid content of 10 percent is 1.0-3.0 percent of the total volume of the silver nitrate aqueous solution.
H-Ag as described above3PO4In the preparation of (1), the phosphate or acid phosphate used is sodium phosphate [ Na ]3PO4]Ammonium phosphate [ (NH)4)3PO4]Diammonium hydrogen phosphate [ (NH)4)2HPO4]Ammonium dihydrogen phosphate [ NH ]4H2PO4]Disodium hydrogen phosphate [ Na ]2HPO4]Sodium dihydrogen phosphate [ NaH ]2PO4]Dipotassium hydrogen phosphate [ K ]2HPO4]Potassium dihydrogen phosphate [ KH ]2PO4]Or a mixture thereof, etc., phosphate radical (PO)4 3-) The concentration ranges are as follows: 0.3 to 0.9 mol.L-1。
CoFe as described above2O4In the preparation of (1), the iron salt used is ferric chloride (FeCl)3) Ferrous chloride (FeCl)2) Iron nitrate [ Fe (NO)3)3]Iron sulfate [ Fe ]2(SO4)3]Or their hydrated salts (e.g. FeCl)3·6H2O，FeCl2·4H2O， Fe(NO3)3·9H2O，Fe2(SO4)3·9H2O), etc., iron ion (Fe)3+) Or ferrous ion (Fe)2+) The concentration is 0.1 to 0.5 mol.L-1。
CoFe as described above2O4In the preparation of (1), the cobalt salt used is cobalt chloride (CoCl)2) Cobalt nitrate [ Co (NO)3)2]Cobalt sulfate or their hydrated salts (e.g. CoCl)2·6H2O，Co(NO3)2·6H2O)，CoSO4·7H2O), cobalt ion (Co)2+) Has a concentration of 0.05 to 0.25 mol.L-1。
g-C as described above3N4In the synthesis of (3), the mass ratio of melamine, thiourea and ammonium chloride is 1: 1-2.
H-Ag as described above3PO4-CoFe2O4/g-C3N4In the synthesis of the composite photocatalyst, the mass fractions of the three are respectively as follows: H-Ag3PO4(15～30％)，CoFe2O4(5～20％)，g-C3N4(50～80％)。
The H-Ag prepared by the invention3PO4-CoFe2O4/g-C3N4The composite photocatalyst has excellent photocatalytic performance. When the solid-to-liquid ratio (namely the mass of the photocatalyst/the volume of the aqueous solution) is 20mg/100mL, the aqueous solution with the concentration of 10mg/L methylene blue is irradiated by simulated sunlight, the decoloring rate reaches over 99 percent when the irradiation time is 3min, the aqueous solution of rhodamine B or methyl orange is irradiated, the decoloring rate reaches over 90 percent when the irradiation time is 30min, and the degradation effect is better than that of pure Ag3PO4The photocatalyst was good and no Ag was observed3PO4Self-etching phenomenon of changing into simple substance Ag. When the photocatalyst is used for degrading tetracycline wastewater, the removal rate of tetracycline is over 90 percent when the photocatalyst is irradiated for 30min by simulated sunlight. The prepared composite photocatalyst can be recycled after simple suction filtration and can be recycled for 10 times.
Detailed Description
The invention is further illustrated by the following examples, but is not limited thereto.
Example 1
(1)H-Ag3PO4And (3) synthesis of microspheres: 100mL of 0.1 mol. L was added to a 500mL beaker with stirring-1AgNO3Aqueous solution and 1.0mL of polystyrene (template) emulsion having a solid content of 10%, followed by dropwise addition of 0.3 mol. L-1Na of (2)3PO4After the water solution is dripped, the reaction is continued for 0.5H and then the water solution is filtered, the filter cake is washed by deionized water for 3 times, and finally the filter cake is placed in a 500 ℃ tubular furnace to be calcined for 3H to remove the template agent polystyrene, thus obtaining golden yellow H-Ag3PO4Microspheres; (2) CoFe2O4The synthesis of (2): 100mL of 50% ethanol aqueous solution was added to a 250mL beaker with stirring, followed by addition of 0.2mol of ferric chloride and 0.1mol of cobalt chloride (Fe/Co: 2: 1, ratio of the amounts of the substances), and after complete dissolution, 1 mol. L was added dropwise-1Adjusting the pH value of the solution to 10-11 by using an ammonia water solution, continuing to magnetically stir for 1-2 h, filtering, washing the filter cake for 3 times by using deionized water, and drying the obtained filter cake for 1-2 h at 120 ℃ to obtain CoFe2O4；(3)g-C3N4The synthesis of (2): weighing 20g of melamine, 20g of thiourea and 20g of ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven under the power of 800WHeating for 20min to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing 3.0g H-Ag3PO4Microspheres, 1.0g CoFe2O4And 16.0 g-C3N4Mixing according to a certain mass percentage, ball-milling for 1H, placing in a tube furnace, introducing nitrogen, calcining for 2H at 400-600 ℃ to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
Example 2
(1)H-Ag3PO4And (3) synthesis of microspheres: 100mL of 0.2 mol.L are added into a 500mL beaker with stirring-1AgNO3Aqueous solution and 2.0mL of polystyrene (template) emulsion having a solid content of 10%, followed by dropwise addition of 0.6 mol. L-1Na of (2)2HPO4After the water solution is dripped, the reaction is continued for 0.5H and then the water solution is filtered, the filter cake is washed by deionized water for 3 times, and finally the filter cake is placed in a 500 ℃ tubular furnace to be calcined for 3H to remove the template agent polystyrene, thus obtaining golden yellow H-Ag3PO4Microspheres;
(2)CoFe2O4the synthesis of (2): 100mL of 50% ethanol aqueous solution was added to a 250mL beaker with stirring, followed by addition of 0.2mol of ferric chloride and 0.1mol of cobalt chloride (Fe/Co: 2: 1, ratio of the amounts of the substances), and after complete dissolution, 1 mol. L was added dropwise-1Adjusting the pH value of the solution to 10-11 by using an ammonia water solution, continuing to magnetically stir for 1-2 h, filtering, washing the filter cake for 3 times by using deionized water, and drying the obtained filter cake for 1-2 h at 120 ℃ to obtain CoFe2O4；(3)g-C3N4The synthesis of (2): weighing 20g of melamine, 20g of thiourea and 30g of ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven, and heating for 30min under 800W power to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing 4.0g H-Ag3PO4Microspheres, 2.0g CoFe2O4And 14.0g-C3N4Mixing according to a certain mass percentage, ball-milling for 1.5h, and placing in a tube furnaceIntroducing nitrogen, calcining at 400-600 ℃ for 3H to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
Example 3
(1)H-Ag3PO4And (3) synthesis of microspheres: 100mL of 0.3 mol. L was added to a 500mL beaker with stirring-1AgNO3Aqueous solution and 3.0mL of polystyrene (template) emulsion having a solid content of 10%, followed by dropwise addition of 0.9 mol. L-1NaH (a)2PO4After the water solution is added dropwise, the reaction is continued for 1H, then the water solution is filtered, the filter cake is washed by deionized water for 3 times, finally the filter cake is placed in a 500 ℃ tubular furnace to be calcined for 3H to remove the template agent polystyrene, and golden yellow H-Ag can be obtained3PO4Microspheres; (2) CoFe2O4The synthesis of (2): 100mL of 50% aqueous ethanol solution was added to a 250mL beaker with stirring, followed by addition of 0.2mol of ferric chloride and 0.1mol of cobalt nitrate (Fe/Co: 2: 1, ratio of the amounts of the substances) and, after complete dissolution, 1 mol. L.was added dropwise-1Adjusting the pH value of the solution to 10-11 by using an ammonia water solution, continuing to magnetically stir for 2h, filtering, washing the filter cake for 3 times by using deionized water, and drying the obtained filter cake for 1-2 h at 120 ℃ to obtain CoFe2O4；(3)g-C3N4The synthesis of (2): weighing 20g of melamine, 20g of thiourea and 40g of ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven, and heating for 60min under 800W power to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing 6.0g H-Ag3PO4Microspheres, 4.0g CoFe2O4And 10.0g-C3N4Mixing according to a certain mass percentage, ball-milling for 1H, placing in a tube furnace, introducing nitrogen, calcining for 4H at 400-600 ℃ to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
Example 4
(1)H-Ag3PO4And (3) synthesis of microspheres: 100mL of 0.2 mol.L are added into a 500mL beaker with stirring-1AgNO3Aqueous solution and 2.0mL of a polystyrene (template) emulsion having a solid content of 10%, followed by dropwise addition of 0.6 mol. L-1(NH)4)2HPO4After the water solution is added dropwise, the reaction is continued for 1H, then the water solution is filtered, the filter cake is washed by deionized water for 3 times, finally the filter cake is placed in a 500 ℃ tubular furnace to be calcined for 3H to remove the template agent polystyrene, and golden yellow H-Ag can be obtained3PO4Microspheres; (2) CoFe2O4The synthesis of (2): 100mL of 50% ethanol aqueous solution was added to a 250mL beaker with stirring, followed by addition of 0.2mol of ferric chloride and 0.1mol of cobalt chloride (Fe/Co: 2: 1, ratio of the amounts of the substances), and after complete dissolution, 1 mol. L was added dropwise-1Adjusting the pH value of the solution to 10-11 by using an ammonia water solution, continuing to magnetically stir for 2h, filtering, washing the filter cake for 3 times by using deionized water, and drying the obtained filter cake for 1-2 h at 120 ℃ to obtain CoFe2O4；(3)g-C3N4The synthesis of (2): weighing 20g of melamine, 20g of thiourea and 40g of ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven, and heating for 60min under 800W power to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing 6.0g H-Ag3PO4Microspheres, 4.0g CoFe2O4And 10.0g-C3N4Mixing according to a certain mass percentage, ball-milling for 1H, placing in a tube furnace, introducing nitrogen, calcining for 5H at 400-600 ℃ to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
Example 5
(1)H-Ag3PO4And (3) synthesis of microspheres: 100mL of 0.2 mol.L are added into a 500mL beaker with stirring-1AgNO3Aqueous solution and 2.0mL of polystyrene (template) emulsion having a solid content of 1O%, and then 100 mL0.6mol. L was dropwise added-1(NH)4)H2PO4After the water solution is added dropwise, the reaction is continued for 1H, then the water solution is filtered, the filter cake is washed by deionized water for 3 times, finally the filter cake is placed in a 500 ℃ tubular furnace to be calcined for 3H to remove the template agent polystyrene, and golden yellow H-Ag can be obtained3PO4Microspheres； (2)CoFe2O4The synthesis of (2): 100mL of 50% ethanol aqueous solution was added to a 250mL beaker with stirring, followed by addition of 0.2mol of ferric chloride and 0.1mol of cobalt sulfate (Fe/Co: 2: 1, ratio of the amounts of the substances), and after complete dissolution, 1 mol. L was added dropwise-1Adjusting the pH value of the solution to 10-11 by using an ammonia water solution, continuing to magnetically stir for 2h, filtering, washing the filter cake for 3 times by using deionized water, and drying the obtained filter cake for 1-2 h at 120 ℃ to obtain CoFe2O4；(3)g-C3N4The synthesis of (2): weighing 20g of melamine, 20g of thiourea and 40g of ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven, and heating for 60min under 800W power to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing 6.0g H-Ag3PO4Microspheres, 4.0g CoFe2O4And 10.0g-C3N4Mixing according to a certain mass percentage, ball-milling for 1H, placing in a tube furnace, introducing nitrogen, calcining for 4H at 400-600 ℃ to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
Example 6
(1)H-Ag3PO4And (3) synthesis of microspheres: 100mL of 0.2 mol.L are added into a 500mL beaker with stirring-1AgNO3Aqueous solution and 2.0mL of polystyrene (template) emulsion having a solid content of 1O%, and then 100 mL0.6mol. L was dropwise added-1K of2HPO4After the water solution is dripped, the reaction is continued for 1H and then the water solution is filtered, the filter cake is washed by deionized water for 3 times, and finally the filter cake is placed in a 500 ℃ tubular furnace to be calcined for 3 hours to remove the template agent polystyrene, thus obtaining golden yellow H-Ag3PO4Microspheres; (2) CoFe2O4The synthesis of (2): 100mL of 50% ethanol aqueous solution was added to a 250mL beaker with stirring, 0.2mol of ferric nitrate and 0.1mol of cobalt chloride (Fe/Co: 2: 1, ratio of the amounts of the substances) were added thereto, and after completion of dissolution, 1 mol. L was added dropwise-1Adjusting the pH value of the solution to 10-11 by using an ammonia water solution, continuing to magnetically stir for 2h, filtering, washing the filter cake for 3 times by using deionized water, and drying the obtained filter cake at 120 DEG CDrying for 1-2 h to obtain CoFe2O4；(3)g-C3N4The synthesis of (2): weighing 20g of melamine, 20g of thiourea and 40g of ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven, and heating for 60min under 800W power to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing 6.0g H-Ag3PO4Microspheres, 4.0g CoFe2O4And 10.0g-C3N4Mixing according to a certain mass percentage, ball-milling for 1H, placing in a tube furnace, introducing nitrogen, calcining for 4H at 400-600 ℃ to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
Example 7
(1)H-Ag3PO4And (3) synthesis of microspheres: 100mL of 0.2 mol.L are added into a 500mL beaker with stirring-1AgNO3Aqueous solution and 2.0mL of polystyrene (template) emulsion with a solid content of 10%, and then 50 mL0.3mol.L is dropwise added-1Na of (2)2HPO4Aqueous solution and 50 mL0.3mol.L-1NaH (a)2PO4After the water solution is added dropwise, the reaction is continued for 1H, then the water solution is filtered, the filter cake is washed by deionized water for 3 times, finally the filter cake is placed in a 500 ℃ tubular furnace to be calcined for 3H to remove the template agent polystyrene, and golden yellow H-Ag can be obtained3PO4Microspheres; (2) CoFe2O4The synthesis of (2): 100mL of 50% ethanol aqueous solution was added to a 250mL beaker with stirring, followed by addition of 0.1mol of iron sulfate and 0.1mol of cobalt sulfate (Fe/Co: 2: 1, ratio of the amounts of the substances), and after complete dissolution, 1 mol. L was added dropwise-1Adjusting the pH value of the solution to 10-11 by using an ammonia water solution, continuing to magnetically stir for 2h, filtering, washing the filter cake for 3 times by using deionized water, and drying the obtained filter cake for 1-2 h at 120 ℃ to obtain CoFe2O4；(3)g-C3N4The synthesis of (2): weighing 20g of melamine, 20g of thiourea and 40g of ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven, and heating for 60min under 800W power to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing 6.0g H-Ag3PO4Microspheres, 4.0g CoFe2O4And 10.0g-C3N4Mixing according to a certain mass percentage, ball-milling for 1H, placing in a tube furnace, introducing nitrogen, calcining for 4H at 400-600 ℃ to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
Example 8
(1)H-Ag3PO4And (3) synthesis of microspheres: 100mL of 0.2 mol.L are added into a 500mL beaker with stirring-1AgNO3Aqueous solution and 2.0mL of polystyrene (template) emulsion with a solid content of 10%, and then 50 mL0.3mol.L is dropwise added-1Na of (2)2HPO4Aqueous solution and 50 mL0.3mol.L-1NH4H2PO4After the water solution is dripped, the reaction is continued for 1H and then the water solution is filtered, the filter cake is washed by deionized water for 3 times, and finally the filter cake is placed in a 500 ℃ tubular furnace to be calcined for 3 hours to remove the template agent polystyrene, thus obtaining golden yellow H-Ag3PO4Microspheres; (2) CoFe2O4The synthesis of (2): 100mL of 50% ethanol aqueous solution was added to a 250mL beaker with stirring, followed by addition of 0.2mol of ferric chloride and 0.1mol of cobalt sulfate (Fe/Co: 2: 1, ratio of the amounts of the substances), and after complete dissolution, 1 mol. L was added dropwise-1Adjusting the pH value of the solution to 10-11 by using an ammonia water solution, continuing to magnetically stir for 2h, filtering, washing the filter cake for 3 times by using deionized water, and drying the obtained filter cake for 1-2 h at 120 ℃ to obtain CoFe2O4； (3)g-C3N4The synthesis of (2): weighing 20g of melamine, 20g of thiourea and 30g of ammonium chloride, fully grinding and mixing in a crucible, putting into a microwave oven, and heating for 40min under 800W power to obtain g-C3N4A sample; (4) H-Ag3PO4-CoFe2O4/g-C3N4The synthesis of (2): mixing 6.0g H-Ag3PO4Microspheres, 4.0g CoFe2O4And 10.0g-C3N4Mixing according to a certain mass percentage, ball-milling for 1H, placing in a tube furnace, introducing nitrogen, calcining for 4H at 400-600 ℃ to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.

Claims (8)

1. Ag3PO4-CoFe2O4/g-C3N4The composite high-efficiency photocatalyst and the preparation method thereof are characterized in that: mixing hollow Ag3PO4Microspheres, CoFe2O4And g-C3N4The three are mixed, ball-milled and then placed into a tubular furnace to be calcined for a certain time under the condition of introducing nitrogen, and the required target product Ag can be obtained3PO4-CoFe2O4/g-C3N4. . The adopted technical scheme is as follows: first, hollow Ag is synthesized separately3PO4Microspheres, CoFe2O4And g-C3N4Mixing silver nitrate water solution, polystyrene emulsion, phosphate or acid phosphate water solution, calcining the precipitate in a tubular furnace to remove polystyrene and obtain the hollow Ag3PO4Microspheres; adjusting the pH of an ethanol aqueous solution of iron salt and cobalt salt to 10-11 by using ammonia water, and drying the precipitate to obtain CoFe2O4(ii) a Mixing and grinding melamine, thiourea and ammonium chloride in a crucible, and then heating by microwave to obtain g-C3N4(ii) a Finally, mixing the hollow Ag3PO4Microspheres, CoFe2O4And g-C3N4Mixing the raw materials according to a certain mass percentage, ball-milling the mixture, putting the mixture into a tube furnace, and calcining the mixture at 400-600 ℃ under the condition of introducing nitrogen to obtain H-Ag3PO4-CoFe2O4/g-C3N4A composite photocatalyst is provided.
2. The method of claim 1, wherein: H-Ag as described above3PO4In the preparation of (1), AgNO3The concentration of (A) is as follows: 0.1 to 0.3 mol.L-1。
3. The method of claim 1, wherein: H-Ag as described above3PO4In the preparation, the usage amount of the adopted polystyrene emulsion with the solid content of 10 percent is 1.0-3.0 percent of the total volume of the silver nitrate aqueous solution.
4. The method of claim 1, wherein: H-Ag as described above3PO4In the preparation of (1), the phosphate or acid phosphate used is sodium phosphate [ Na ]3PO4]Ammonium phosphate [ (NH)4)3PO4]Diammonium hydrogen phosphate [ (NH)4)2HPO4]Ammonium dihydrogen phosphate [ NH ]4H2PO4]Disodium hydrogen phosphate [ Na ]2HPO4]Sodium dihydrogen phosphate [ NaH ]2PO4]Dipotassium hydrogen phosphate [ K ]2HPO4]Potassium dihydrogen phosphate [ KH ]2PO4]Or a mixture thereof, etc., phosphate radical (PO)4 3-) The concentration ranges are as follows: 0.3 to 0.9 mol.L-1。
5. The method of claim 1, wherein: CoFe as described above2O4In the preparation of (1), the iron salt used is ferric chloride (FeCl)3) Ferrous chloride (FeCl)2) Iron nitrate [ Fe (NO)3)3]Iron sulfate [ Fe ]2(SO4)3]Or their hydrated salts (e.g. FeCl)3·6H2O，FeCl2·4H2O，Fe(NO3)3·9H2O，Fe2(SO4)3·9H2O), etc., iron ion (Fe)3+) Or ferrous ion (Fe)2+) The concentration is 0.1 to 0.5 mol.L-1。
6. The method of claim 1, wherein: CoFe as described above2O4In the preparation of (1), the cobalt salt used is cobalt chloride (CoCl)2) Cobalt nitrate [ Co (NO)3)2]Cobalt sulfate or their hydrated salts (e.g. CoCl)2·6H2O，Co(NO3)2·6H2O)，CoSO4·7H2O), cobalt ion (Co)2+) Has a concentration of 0.05 to 0.25 mol.L-1。
7. The method of claim 1, wherein: g-C as described above3N4In the synthesis of (3), the mass ratio of melamine, thiourea and ammonium chloride is 1: 1-2.
8. The method of claim 1, wherein: H-Ag as described above3PO4-CoFe2O4/g-C3N4In the synthesis of the composite photocatalyst, the mass fractions of the three are respectively as follows: H-Ag3PO4(15～30％)，CoFe2O4(5～20％)，g-C3N4(50～80％)。
CN202110695767.0A 2021-06-22 2021-06-22 Ag3PO4-CoFe2O4/g-C3N4Composite high-efficiency photocatalyst and preparation method thereof Pending CN113333013A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601266A (en) * 2015-12-16 2016-05-25 同济大学 Silver phosphate two-dimensional ordered nano net film prepared by gas-liquid interface method and method
CN106542509A (en) * 2016-10-19 2017-03-29 张家港市东大工业技术研究院 A kind of efficient method for preparing class Graphene carbonitride
CN111326810A (en) * 2018-12-13 2020-06-23 多氟多化工股份有限公司 Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece
CN111659450A (en) * 2020-07-13 2020-09-15 安徽汇泽通环境技术有限公司 Ag3PO4/g-C3N4@MoS2Composite photocatalytic material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601266A (en) * 2015-12-16 2016-05-25 同济大学 Silver phosphate two-dimensional ordered nano net film prepared by gas-liquid interface method and method
CN106542509A (en) * 2016-10-19 2017-03-29 张家港市东大工业技术研究院 A kind of efficient method for preparing class Graphene carbonitride
CN111326810A (en) * 2018-12-13 2020-06-23 多氟多化工股份有限公司 Method for photocatalytic degradation of organic matters in waste lithium ion battery pole piece and recovery method of current collector and active substances in pole piece
CN111659450A (en) * 2020-07-13 2020-09-15 安徽汇泽通环境技术有限公司 Ag3PO4/g-C3N4@MoS2Composite photocatalytic material and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHAO-SHENG ZHU ET AL: "Facile synthesis of porous Ag3PO4 particles and its application in MB wastewater degradation under visible light irradiation", ADVANCES IN ENGINEERING RESEARCH, pages 2 *
QIUSHI YANG ET AL.: "Engineering graphitic carbon nitride with expanded interlayer distance for boosting photocatalytic hydrogen evolution", CHINESE JOURNAL OF CATALYSIS, pages 2 *
朱鹏飞等: "g-C3N4-Ag3PO4/Fe3O4磁性光催化剂的制备及性能研究", 应用化工, vol. 49, no. 9, pages 2202 - 2203 *
陶虎春等: "磁性CoFe2O4/g-C3N4复合纳米材料对环丙沙星的光催化降解研究", 北京大学学报(自然科学版), vol. 57, no. 3, pages 1 *

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