CN113318768B - Composite photocatalyst and preparation method thereof - Google Patents
Composite photocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN113318768B CN113318768B CN202110699747.0A CN202110699747A CN113318768B CN 113318768 B CN113318768 B CN 113318768B CN 202110699747 A CN202110699747 A CN 202110699747A CN 113318768 B CN113318768 B CN 113318768B
- Authority
- CN
- China
- Prior art keywords
- powder
- particles
- composite photocatalyst
- feooh
- powder particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910002588 FeOOH Inorganic materials 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 5
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 25
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 229910052742 iron Inorganic materials 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000002351 wastewater Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000019398 chlorine dioxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- -1 nitrogen containing organic compounds Chemical class 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- 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
Discloses a composite photocatalyst, which comprises the following raw materials in percentage by weight 3 N 4 Powder and FeOOH of iron oxyhydroxide, feOOH containing g-C 3 N 4 The powder is obtained by in-situ reaction in the dispersion liquid of the powder; wherein g-C 3 N 4 The powder particles are selected from nano g-C 3 N 4 Powder particles. In addition, a preparation method of the composite photocatalyst is also disclosed. The composite photocatalyst has higher catalytic effect; meanwhile, the dissolved iron content of the catalyst is low, so that the catalyst has better catalytic stability.
Description
Technical Field
The application belongs to the technical field of photocatalytic oxidation; in particular to a composite photocatalyst and a preparation method thereof.
Background
Along with the rapid development of industrialization in China, wastewater discharge becomes one of the main sources of environmental pollution. The relevant statistics indicate that organic wastewater is the first largest source of wastewater. The organic wastewater sources include coking plant wastewater, paper mill wastewater, pharmaceutical factory wastewater, printing and dyeing plant wastewater, domestic wastewater, and the like. The main organic pollutants in organic wastewater include agrochemicals, endocrine disruptors, organic dyes, aromatic compounds, and sulfur and nitrogen containing organic compounds. These organic compounds are often difficult to degrade effectively and can cause serious harm to human life health and natural environment after being discharged into rivers, lakes and seas.
Traditional water treatment techniques include three general categories, physical, chemical and biological. For organic wastewater, the traditional water treatment technologies are difficult to thoroughly decompose or degrade organic pollutants, and simultaneously, secondary pollution is easy to cause to the environment. Therefore, conventional water treatment techniques are not suitable for treating most refractory organic wastewater.
The solid-phase catalytic oxidation Advanced Oxidation (AOP) technology utilizes in-situ generation of strong oxidative hydroxyl free radical OH in wastewater, which can fully mineralize various refractory organic compounds, thereby converting the refractory organic compounds into inorganic compounds such as carbon dioxide, water and the like, and is an efficient and green water quality purification technology. In various AOP (ozone catalytic oxidation, hydrogen peroxide oxidation, chlorine dioxide oxidation, fenton method and the like), the ozone catalytic oxidation has the problems of high investment, high energy consumption, low efficiency and the like. The hydrogen peroxide oxidation method and the chlorine dioxide oxidation method have the problems of low degradation efficiency and the like. Fenton method (Fe 2 +H 2 O 2 ) The method is widely applied due to the characteristics of low cost, high efficiency and the like, but has the problems of narrow pH application range (2-4), iron mud solid waste generation and the like.
To solve the problem of solid waste of the generated pig iron sludge, jiang Shengtao et al prepared Si-FeOOH using an alkali precipitation method and sodium silicate. The result shows that the adding amount of the catalyst is 3g/L and H 2 O 2 The addition amount is 9.9mmol/L, and the degradation rate of the target compound is 90% under the conditions of pH=3.0 and room temperature. However, the catalyst still has the problems of narrow pH application range, low catalytic efficiency, easy crushing, high dissolved iron content of the catalyst and the like.
Wu Shuguo mixing melamine, lithium chloride, potassium chloride and ferric trichloride at a mass ratio of 1:9:11 (0-0.02), placing into a crucible, covering with a cover, placing into a muffle furnace, heating for 3-h, and cooling to room temperature; washing with deionized water, and drying to obtain the Fenton-like catalyst. Under the action of hydrogen peroxide, the Fenton catalyst has excellent degradation performance on organic wastewater containing tetracycline hydrochloride, and has good effect at pH value of 3-11, and the degradation rate can reach 98-99.5%.
Yali et al first prepared graphite-phase carbon nitride (g-C) 3 N 4 ) Then the mixed solution of sulfuric acid and nitric acid is used for acid stripping, and the pale yellow g-C is prepared by a hydrothermal method 3 N 4 A quantum dot solution; then g-C 3 N 4 And pale yellow g-C 3 N 4 Mixing quantum dot solution, and adding hexahydrate trichloroDissolving iron, and preparing into 0D/2D g-C by in-situ reaction 3 N 4 FeOOH composite material.
However, the above catalyst still has problems of low catalytic efficiency, high amount of dissolved iron of the catalyst, and the like. Thus, there is still an urgent need to find a composite photocatalyst with higher catalytic effect and lower dissolved iron content of the catalyst, and a preparation method thereof.
Disclosure of Invention
The application aims to provide a composite photocatalyst with higher catalytic effect and lower dissolved iron content of the catalyst and a preparation method thereof.
In order to achieve the above purpose, on one hand, the present application adopts the following technical scheme: a composite photocatalyst is prepared from g-C 3 N 4 Powder and FeOOH of iron oxyhydroxide, feOOH containing g-C 3 N 4 The powder is obtained by in-situ reaction in the dispersion liquid of the powder; characterized in that the g-C 3 N 4 The powder particles are selected from nano g-C 3 N 4 Powder particles.
The composite photocatalyst according to the present application, wherein the nano g-C 3 N 4 The powder particles are composed of g-C 3 N 4 Powder and HNO 3 The solution is prepared by a hydrothermal method after mixing.
The composite photocatalyst according to the present application, wherein HNO 3 The concentration of the solution is 0.5-1.5mol/L.
Preferably HNO 3 The concentration of the solution is 0.8-1.2mol/L.
The composite photocatalyst according to the present application, wherein g-C 3 N 4 Powder and HNO 3 The weight-to-volume ratio of the solution is 1g: (20-80) mL.
Preferably g-C 3 N 4 Powder and HNO 3 The weight-to-volume ratio of the solution is 1g: (40-60) mL.
The composite photocatalyst according to the present application, wherein the reaction conditions of the hydrothermal method are: the reaction temperature is 140-170 ℃; the reaction time is 2-12h.
Preferably, the reaction conditions of the hydrothermal method are: the reaction temperature is 150-160 ℃; the reaction time is 4-8h.
The composite photocatalyst according to the present application, wherein the hydrothermal method further comprises a step of washing with deionized water and ethanol.
The composite photocatalyst according to the present application, wherein the dispersion further contains spherical nano ZnO particles.
The composite photocatalyst according to the present application, wherein the spherical nano ZnO particles have an average particle diameter of 10 to 40nm.
Preferably, the average particle diameter of the spherical nano ZnO particles is 20-30nm.
The composite photocatalyst according to the present application, wherein the nano g-C 3 N 4 The weight ratio of the powder particles to the spherical nano ZnO particles is (60-90): (40-10).
Preferably, the nano g-C 3 N 4 The weight ratio of the powder particles to the spherical nano ZnO particles is (70-85): (30-15).
The composite photocatalyst according to the present application, wherein FeOOH consists of the following components in a molar ratio of 1:3 and ammonium bicarbonate in situ.
The composite photocatalyst according to the present application, wherein the nano g-C 3 N 4 The sum of the weights of the powder particles and the spherical nano ZnO particles is (3-5) of FeOOH theoretical weight: 1.
preferably, the nano g-C 3 N 4 The sum of the weights of the powder particles and the spherical nano ZnO particles is (3.5-4.5) of FeOOH theoretical weight: 1.
in another aspect, the present application further provides a method for preparing the foregoing composite photocatalyst, including:
obtaining nano g-C 3 N 4 Powder particles and optionally spherical nano ZnO particles;
subjecting the nano g-C 3 N 4 Dispersing powder particles and optional spherical nano ZnO particles in an alcohol solvent to obtain a dispersion liquid;
in-situ reacting in the dispersion to obtain FeOOH;
the solvent was removed.
Compared with the prior art, the composite photocatalyst has higher catalytic effect; meanwhile, the dissolved iron content of the catalyst is low, so that the catalyst has better catalytic stability.
Detailed Description
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods described and claimed herein are made and evaluated, and are intended to be merely exemplary and are not intended to limit the scope of what the inventors regard as their application. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for.
Unless otherwise indicated, parts are parts by weight, temperatures are expressed in degrees celsius or at ambient temperature, and pressures are at or near atmospheric. There are numerous variations and combinations of reaction conditions (e.g., component concentrations, solvents needed, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
Example 1
10g of melamine was placed in a 100mL ceramic crucible and placed in a muffle furnace. In an air atmosphere, the temperature is programmed to 550 ℃ at a heating rate of 3 ℃/min, and the calcination is carried out for 2 hours at constant temperature. Then stopping heating, naturally cooling to room temperature, taking out the crucible to obtain yellowish solid, namely g-C 3 N 4 . Grinding and sieving the mixture for standby.
Will 1g g-C 3 N 4 The powder was added to 50mL of 1mol/L HNO 3 The solution was stirred for 30min. It is then transferred to a hydrothermal reaction kettle. The hydrothermal reaction kettle is placed in a blast drying box, subjected to hydrothermal reaction for 6 hours at 155 ℃, and cooled to room temperature. Centrifuging to obtain precipitate, washing with deionized water for 3 times, washing with ethanol for 1 time, oven drying at 80deg.C for 10 hr, and cooling to obtain nanometer g-C 3 N 4 Powder particles. SEM pictures confirm 90% g-C 3 N 4 The particle size of the powder particles varies from tens to hundreds of nanometers.
284.5mg of nano g-C 3 N 4 The powder particles were dispersed in 50mL of absolute ethanol, and then 71.1mg of spherical nano ZnO particles (product No. Z713, available from Guangzhou Hongwu materials science and technology Co., ltd.) having an average particle diameter of 20-30nm were added thereto, and were uniformly dispersed by ultrasonic waves. Then 270.3mg of ferric trichloride hexahydrate and 237.2mg of ammonium bicarbonate are added, stirring is continued for 8 hours, centrifugal separation is carried out, and drying is carried out, thus obtaining the composite photocatalyst.
Example 2
10g of melamine was placed in a 100mL ceramic crucible and placed in a muffle furnace. In an air atmosphere, the temperature is programmed to 550 ℃ at a heating rate of 3 ℃/min, and the calcination is carried out for 2 hours at constant temperature. Then stopping heating, naturally cooling to room temperature, taking out the crucible to obtain yellowish solid, namely g-C 3 N 4 . Grinding and sieving the mixture for standby.
Will 1g g-C 3 N 4 The powder was added to 50mL of 1mol/L HNO 3 The solution was stirred for 30min. It is then transferred to a hydrothermal reaction kettle. The hydrothermal reaction kettle is placed in a blast drying box, subjected to hydrothermal reaction for 6 hours at 155 ℃, and cooled to room temperature. Centrifuging to obtain precipitate, washing with deionized water for 3 times, washing with ethanol for 1 time, oven drying at 80deg.C for 10 hr, and cooling to obtain nanometer g-C 3 N 4 Powder particles. SEM pictures confirm 90% g-C 3 N 4 The particle size of the powder particles varies from tens to hundreds of nanometers.
248.9mg of nano g-C 3 N 4 The powder particles were dispersed in 50mL of absolute ethanol, and 106.7mg of spherical nano ZnO particles (product No. Z713, available from Guangzhou Hongwu materials science and technology Co., ltd.) having an average particle diameter of 20-30nm were further added thereto, and were uniformly dispersed by ultrasonic waves. Then 270.3mg of ferric trichloride hexahydrate and 237.2mg of ammonium bicarbonate are added, stirring is continued for 8 hours, centrifugal separation is carried out, and drying is carried out, thus obtaining the composite photocatalyst.
Example 3
10g of melamine was placed in a 100mL ceramic crucible and placed in a muffle furnace. In an air atmosphere, at 3 ℃/minIs programmed to 550 ℃, and is calcined for 2 hours at constant temperature. Then stopping heating, naturally cooling to room temperature, taking out the crucible to obtain yellowish solid, namely g-C 3 N 4 . Grinding and sieving the mixture for standby.
Will 1g g-C 3 N 4 The powder was added to 50mL of 1mol/L HNO 3 The solution was stirred for 30min. It is then transferred to a hydrothermal reaction kettle. The hydrothermal reaction kettle is placed in a blast drying box, subjected to hydrothermal reaction for 6 hours at 155 ℃, and cooled to room temperature. Centrifuging to obtain precipitate, washing with deionized water for 3 times, washing with ethanol for 1 time, oven drying at 80deg.C for 10 hr, and cooling to obtain nanometer g-C 3 N 4 Powder particles. SEM pictures confirm 90% g-C 3 N 4 The particle size of the powder particles varies from tens to hundreds of nanometers.
302.3mg of nano g-C 3 N 4 The powder particles were dispersed in 50mL of absolute ethanol, and 53.3mg of spherical nano ZnO particles (product No. Z713, available from Guangzhou Hongwu materials science and technology Co., ltd.) having an average particle diameter of 20-30nm were further added thereto, and were uniformly dispersed by ultrasonic waves. Then 270.3mg of ferric trichloride hexahydrate and 237.2mg of ammonium bicarbonate are added, stirring is continued for 8 hours, centrifugal separation is carried out, and drying is carried out, thus obtaining the composite photocatalyst.
Comparative example 1
10g of melamine was placed in a 100mL ceramic crucible and placed in a muffle furnace. In an air atmosphere, the temperature is programmed to 550 ℃ at a heating rate of 3 ℃/min, and the calcination is carried out for 2 hours at constant temperature. Then stopping heating, naturally cooling to room temperature, taking out the crucible to obtain yellowish solid, namely g-C 3 N 4 . Grinding and sieving the mixture for standby.
284.5mg of g-C which was not further treated 3 N 4 Dispersing in 50mL absolute ethanol, adding 71.1mg spherical nano ZnO particles (product No. Z713, available from Guangzhou Hongwu materials science and technology Co., ltd.) with average particle size of 20-30nm, and ultrasonic dispersing. Then 270.3mg of ferric trichloride hexahydrate and 237.2mg of ammonium bicarbonate are added, stirring is continued for 8 hours, centrifugal separation is carried out, and drying is carried out, thus obtaining the composite photocatalyst.
Comparative example 2
10g of melamine are reactedPlaced in a 100mL ceramic crucible and placed in a muffle furnace. In an air atmosphere, the temperature is programmed to 550 ℃ at a heating rate of 3 ℃/min, and the calcination is carried out for 2 hours at constant temperature. Then stopping heating, naturally cooling to room temperature, taking out the crucible to obtain yellowish solid, namely g-C 3 N 4 . Grinding and sieving the mixture for standby.
Will 1g g-C 3 N 4 The powder was added to 50mL of 1mol/L HNO 3 The solution was stirred for 30min. It is then transferred to a hydrothermal reaction kettle. The hydrothermal reaction kettle is placed in a blast drying box, subjected to hydrothermal reaction for 6 hours at 155 ℃, and cooled to room temperature. Centrifuging to obtain precipitate, washing with deionized water for 3 times, washing with ethanol for 1 time, oven drying at 80deg.C for 10 hr, and cooling to obtain nanometer g-C 3 N 4 Powder particles. SEM pictures confirm 90% g-C 3 N 4 The particle size of the powder particles varies from tens to hundreds of nanometers.
355.6mg of nano g-C 3 N 4 The powder particles were dispersed in 50mL of absolute ethanol and sonicated to make them uniformly dispersed. Then 270.3mg of ferric trichloride hexahydrate and 237.2mg of ammonium bicarbonate are added, stirring is continued for 8 hours, centrifugal separation is carried out, and drying is carried out, thus obtaining the composite photocatalyst.
Evaluation of composite photocatalyst wastewater treatment performance
Bisphenol A (BPA) solution with the concentration of 10mg/L is prepared, and 50mL of the prepared BPA solution is placed in a transparent glass cuvette. Then adding 0.6g/L of composite photocatalyst, placing into a stirrer, and placing into a photocatalytic reactor to start reaction. The light source adopts a 500W xenon lamp, and the UVCUT420nm cut-off type filter is utilized to ensure that the passed light is visible light. Firstly, carrying out dark adsorption reaction for 30min under dark condition, when the reaction reaches adsorption equilibrium, starting a light source and simultaneously adding 0.5mL of H with the concentration of 2mM 2 O 2 And (3) performing a photoreaction, and closing the photocatalytic reactor after 30 minutes to finish the reaction. After the reaction was completed, the water sample was filtered using a 0.22 μm filter to obtain a supernatant, which was placed in a liquid phase vial for determining the residual concentration of BPA. Using η= (1-C t /C 0 ) 100% calculated degradation rate of BPA.
Furthermore, for side evaluation of the amount of iron eluted from the photo-composited catalystThe following method was used for evaluation: and (3) separating, recycling and reutilizing different photo-composite catalysts after each photo-catalytic reaction experiment is completed. In order to improve the experimental accuracy, BPA possibly attached to the surface of the photocatalytic material in the previous experimental process is eliminated, the photocatalytic material is washed with absolute ethyl alcohol and deionized water for 2-3 times in sequence, and the photocatalytic material is dried to carry out the next round of circulating experiment. The cycle experiment is carried out for 4 times, and the degradation rate eta of BPA is recorded each time n . Using γ=η 4 /η 1 * The amount of dissolved iron in the photocatalyst was evaluated at 100%. The higher the gamma value, the lower the amount of dissolved iron of the photo-composited catalyst.
The results are shown in Table 1.
TABLE 1
As can be seen from table 1, the composite photocatalyst of example 1 of the present application was higher in not only catalytic effect than comparative examples 1-2; meanwhile, the dissolved iron content of the catalyst is low, so that the catalyst has better catalytic stability.
It should be understood that the description of the specific embodiments is merely illustrative of the principles and spirit of the application, and not in limitation thereof. Further, it should be understood that various changes, substitutions, omissions, modifications, or adaptations to the present application may be made by those skilled in the art after having read the present disclosure, and such equivalent embodiments are within the scope of the present application as defined in the appended claims.
Claims (2)
1. A composite photocatalyst for the photocatalytic reaction of bisphenol A is prepared from g-C 3 N 4 Powder and FeOOH of iron oxyhydroxide, feOOH containing g-C 3 N 4 The powder and the spherical nano ZnO particles are obtained by in-situ reaction in the dispersion liquid; characterized in that the g-C 3 N 4 The powder particles are selected from nano g-C 3 N 4 Powder particles; the average particle diameter of the spherical nano ZnO particles is 10-40nm;
the nanometer g-C 3 N 4 The weight ratio of the powder particles to the spherical nano ZnO particles is (60-90): (40-10);
FeOOH consists of the components in a molar ratio of 1:3, reacting ferric trichloride hexahydrate with ammonium bicarbonate in situ;
the nanometer g-C 3 N 4 The ratio of the sum of the weights of the powder particles and the spherical nano ZnO particles to the theoretical weight of FeOOH is (3-5): 1, a step of;
the nanometer g-C 3 N 4 The powder particles are composed of g-C 3 N 4 Powder and HNO 3 The solution is prepared by a hydrothermal method after being mixed;
wherein HNO is 3 The concentration of the solution is 0.5-1.5mol/L; g-C 3 N 4 Powder and HNO 3 The weight-to-volume ratio of the solution is 1g: (20-80) mL; the reaction conditions of the hydrothermal method are as follows: the reaction temperature is 140-170 ℃; the reaction time is 2-12h.
2. A method of preparing the composite photocatalyst of claim 1, comprising:
obtaining nano g-C 3 N 4 Powder particles and spherical nano ZnO particles;
subjecting the nano g-C 3 N 4 Dispersing powder particles and spherical nano ZnO particles in an alcohol solvent to obtain a dispersion liquid;
in-situ reacting in the dispersion to obtain FeOOH;
the solvent was removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110699747.0A CN113318768B (en) | 2021-06-23 | 2021-06-23 | Composite photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110699747.0A CN113318768B (en) | 2021-06-23 | 2021-06-23 | Composite photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113318768A CN113318768A (en) | 2021-08-31 |
| CN113318768B true CN113318768B (en) | 2023-10-03 |
Family
ID=77424376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110699747.0A Active CN113318768B (en) | 2021-06-23 | 2021-06-23 | Composite photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113318768B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113713754B (en) * | 2021-09-08 | 2022-12-27 | 南华大学 | Preparation method and application of graphite-phase carbon nitride/magnetic goethite composite material |
| CN113828310A (en) * | 2021-10-13 | 2021-12-24 | 太原科技大学 | FeOOH/Cu2O composite microsphere photocatalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106964386A (en) * | 2017-02-23 | 2017-07-21 | 江苏大学 | A kind of preparation method of visible-light response type composite photo-catalyst |
| CN108339560A (en) * | 2017-04-01 | 2018-07-31 | 济南大学 | A kind of amorphous FeOOHg-C3N4Composite nano materials and the preparation method and application thereof |
-
2021
- 2021-06-23 CN CN202110699747.0A patent/CN113318768B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106964386A (en) * | 2017-02-23 | 2017-07-21 | 江苏大学 | A kind of preparation method of visible-light response type composite photo-catalyst |
| CN108339560A (en) * | 2017-04-01 | 2018-07-31 | 济南大学 | A kind of amorphous FeOOHg-C3N4Composite nano materials and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴思展等.类石墨氮化碳（g-C3N4）的合成、加工处理、修饰及其光催化性能的研究.《中国博士学位论文全文数据库工程科技Ⅰ辑》.2015,(第undefined期),第B014-98页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113318768A (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113318768B (en) | Composite photocatalyst and preparation method thereof | |
| CN108129524B (en) | Method for preparing fulvic acid salt by activating low-rank coal through composite photocatalyst | |
| CN112023878A (en) | Preparation method of magnetic porous tea residue biochar for removing tetracycline in water body | |
| CN110624566A (en) | CuInS2Preparation method and application of quantum dot/NiAl-LDH composite photocatalyst | |
| CN112156764A (en) | Nano TiO (titanium dioxide)2Modified graphene oxide/organic bentonite composite material and preparation method thereof | |
| CN109622055B (en) | Iron-manganese bimetallic catalyst based on iron carbide-based MOFS (metal oxide semiconductor) and preparation method thereof | |
| CN109821574B (en) | Europium-based metal organic framework material Eu-MOF, preparation method thereof and Congo red dye photocatalytic degradation method | |
| CN109364924B (en) | Magnetic nano ozone catalyst CoFe2O4And preparation method and application thereof | |
| CN110918099A (en) | Method for treating hexavalent chromium-containing wastewater through photocatalytic reduction of nickel oxide-nickel cobaltate-black titanium dioxide composite | |
| CN114950522A (en) | Boron nitride/indium zinc sulfide composite photocatalyst and preparation method and application thereof | |
| Ding et al. | Investigation of the boosted persulfate activation in the degradation of bisphenol A over MOF-derived cerium-doped Fe 3 O 4 clusters with different shapes: the role of coordinatively unsaturated metal sites | |
| CN108671956B (en) | Preparation method of ion-filled graphite-phase carbon nitride nanosheet | |
| CN107987283B (en) | Method for extracting fulvic acid salt by activating lignite with photocatalyst | |
| CN115970693B (en) | Microalgae modified ferric oxide photo-Fenton catalyst and preparation method and application thereof | |
| CN113120977A (en) | Method for preparing nickel ferrite nano material from nickel-containing iron electroplating wastewater and application | |
| CN111617760A (en) | Mn-TiO2Composite photocatalytic material and preparation method and application thereof | |
| CN111545211A (en) | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof | |
| CN115041168B (en) | Red mud-based photo-Fenton catalyst for water treatment and preparation method and application thereof | |
| CN108083860B (en) | Method for activating lignite | |
| CN113318791B (en) | Preparation method and application of amino-modified Fe/Cu-MOF photocatalyst | |
| CN113244929B (en) | Iron bismuth oxide Bi 2 Fe 4 O 9 Preparation method and application in organic wastewater treatment | |
| CN113649009B (en) | Application of NaNi3O5(OH) 2. H2O/MgNiO2 in photocatalyst | |
| CN112316963B (en) | SiC-based photocatalyst prepared based on waste photovoltaic silicon chips, and synthesis method and application thereof | |
| CN110975809B (en) | Tangerine-based biochar and application thereof | |
| CN112844432A (en) | Ternary magnetic composite nano material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |