CN113318768A - Composite photocatalyst and preparation method thereof - Google Patents
Composite photocatalyst and preparation method thereof Download PDFInfo
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- CN113318768A CN113318768A CN202110699747.0A CN202110699747A CN113318768A CN 113318768 A CN113318768 A CN 113318768A CN 202110699747 A CN202110699747 A CN 202110699747A CN 113318768 A CN113318768 A CN 113318768A
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910002588 FeOOH Inorganic materials 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 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
- 239000002105 nanoparticle Substances 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
- 239000000203 mixture Substances 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 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 8
- 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
- 239000002904 solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- 238000001816 cooling Methods 0.000 description 13
- 239000002351 wastewater Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000001035 drying 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 150000002894 organic compounds Chemical class 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
- 238000007664 blowing Methods 0.000 description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 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
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- 238000010170 biological method Methods 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
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 hydroxyl free radical Chemical class 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000053 physical method Methods 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
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 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
- 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 g-C as raw material3N4Powder and iron oxyhydroxide FeOOH, the FeOOH containing g-C3N4The powder is obtained by in-situ reaction in dispersion liquid of the powder; wherein g-C3N4The powder particles are selected from the group consisting of nanoparticles g-C3N4Powder particles. In addition, a preparation method of the composite photocatalyst is also disclosed. The composite photocatalyst has higher catalytic effect; meanwhile, the amount of iron dissolved out by the catalyst is low, so that the catalyst has better catalytic stability.
Description
Technical Field
The invention belongs to the technical field of photocatalytic oxidation; in particular to a composite photocatalyst and a preparation method thereof.
Background
With the rapid development of industrialization in China, wastewater discharge becomes one of the main sources of environmental pollution. Relevant statistical data indicate that organic wastewater is the first major source of wastewater. The organic wastewater sources comprise coking plant wastewater, paper mill wastewater, pharmaceutical factory wastewater, printing and dyeing mill wastewater, domestic wastewater and the like. The main organic pollutants in organic wastewater include agricultural chemicals, endocrine disruptors, organic dyes, aromatic compounds, and sulfur-and nitrogen-containing organic compounds. These organic compounds are often difficult to degrade effectively and after being discharged into rivers, lakes and seas, they can cause serious harm to human life health and natural environment.
The traditional water treatment technology comprises three main categories of physical method, chemical method and biological method. For organic wastewater, the traditional water treatment technologies are difficult to completely decompose or degrade organic pollutants, and are easy to cause secondary pollution to the environment. Therefore, conventional water treatment techniques are not suitable for treating most refractory organic wastewater.
The advanced oxidation technology (AOP) of the solid-phase catalytic oxidation method utilizes strong oxidative hydroxyl free radical OH generated in situ in wastewater, can completely mineralize various refractory organic compounds so as to convert the refractory organic compounds into inorganic compounds such as carbon dioxide, water and the like, and is a high-efficiency 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 large 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+H2O2) 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), generation of iron mud solid waste and the like.
In order to solve the problem of generating iron mud solid waste, Jiangtao et al prepared Si-FeOOH by alkali precipitation and sodium silicate. The results show that the catalyst is added in an amount of 3g/L and H2O2The target compound was degraded at 90% at pH 3.0 and room temperature in an amount of 9.9 mmol/L. However, the catalyst still has the problems of narrow pH application range, low catalytic efficiency, easy breakage, high iron dissolving amount of the catalyst and the like.
Wushu et al uniformly mix melamine, lithium chloride, potassium chloride and ferric trichloride according to a mass ratio of 1:9:11 (0-0.02), put into a crucible, cover the crucible, put into a muffle furnace, heat for 3-h, and cool to room temperature; washing with deionized water, and drying to obtain the Fenton-like catalyst. The Fenton catalyst has excellent degradation performance on organic wastewater containing tetracycline hydrochloride under the action of hydrogen peroxide, and has a good effect under the condition that the pH value is 3-11, and the degradation rate can reach 98-99.5%.
Diazilian et al first prepared graphite phase carbon nitride (g-C) using a two-stage calcination process3N4) Acid stripping is carried out by using a mixed solution of sulfuric acid and nitric acid, and yellowish g-C is prepared by a hydrothermal method3N4A quantum dot solution; then g-C is added3N4And pale yellow g-C3N4Mixing the quantum dot solution, adding ferric trichloride hexahydrate, and reacting in situ to obtain 0D/2D g-C3N4The composite material of/FeOOH.
However, the above catalysts still have problems such as low catalytic efficiency and high amount of iron eluted from the catalyst. Therefore, a composite photocatalyst with higher catalytic effect and lower iron dissolution amount of the catalyst and a preparation method thereof are still urgently needed to be found.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a composite photocatalyst with a higher catalytic effect and a lower amount of iron dissolved out from the catalyst, and a preparation method thereof.
In order to achieve the purpose, on one hand, the invention adopts the following technical scheme: a composite photocatalyst is prepared from g-C3N4Powder and iron oxyhydroxide FeOOH, the FeOOH containing g-C3N4The powder is obtained by in-situ reaction in dispersion liquid of the powder; characterized in that said g-C3N4The powder particles are selected from the group consisting of nanoparticles g-C3N4Powder particles.
The composite photocatalyst is characterized in that the nano g-C3N4The powder particles consist of g-C3N4Powder and HNO3The solution was mixed and prepared by a hydrothermal method.
The composite photocatalyst is prepared from HNO3The concentration of the solution is 0.5-1.5 mol/L.
Preferably, HNO3The concentration of the solution is 0.8-1.2 mol/L.
The composite photocatalyst of the invention is characterized in that g-C3N4Powder with HNO3The weight volume ratio of the solution is 1 g: (20-80) mL.
Preferably, g-C3N4Powder with HNO3The weight volume ratio of the solution is 1 g: (40-60) mL.
The composite photocatalyst provided by the invention is prepared by a hydrothermal method under the reaction conditions: the reaction temperature is 140 ℃ and 170 ℃; the reaction time is 2-12 h.
Preferably, the reaction conditions of the hydrothermal process are: the reaction temperature is 150 ℃ and 160 ℃; the reaction time is 4-8 h.
The composite photocatalyst provided by the invention, wherein the hydrothermal method further comprises a step of washing with deionized water and ethanol.
The composite photocatalyst further comprises spherical nano ZnO particles.
The composite photocatalyst provided by the invention is characterized in that the average particle size of the spherical nano ZnO particles is 10-40 nm.
Preferably, the average particle diameter of the spherical nano ZnO particles is 20-30 nm.
The composite photocatalyst is characterized in that the nano g-C3N4The weight ratio of the powder particles to the spherical nano ZnO particles is (60-90): (40-10).
Preferably, the nano g-C3N4The weight ratio of the powder particles to the spherical nano ZnO particles is (70-85): (30-15).
The composite photocatalyst is prepared from FeOOH and a compound of an organic compound and an inorganic compound, wherein the mol ratio of FeOOH is 1: 3 ferric trichloride hexahydrate and ammonium bicarbonate.
The composite photocatalyst according to the present invention, wherein,the nano g-C3N4The sum of the weight of the powder particles and the spherical nano ZnO particles is (3-5) of the theoretical weight of FeOOH: 1.
preferably, the nano g-C3N4The sum of the weight of the powder particles and the spherical nano ZnO particles is (3.5-4.5) of the theoretical weight of FeOOH: 1.
in another aspect, the invention further provides a preparation method of the composite photocatalyst, which includes:
obtaining nano g-C3N4Powder particles and optionally spherical nano ZnO particles;
mixing the nano g-C3N4Dispersing the powder particles and optional spherical nano ZnO particles in an alcohol solvent to obtain a dispersion liquid;
performing in-situ reaction in the dispersion liquid to obtain FeOOH;
the solvent was removed.
Compared with the prior art, the composite photocatalyst has higher catalytic effect; meanwhile, the amount of iron dissolved out by 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 purely exemplary and are not intended to limit the scope of what the inventors regard as their invention. 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 in degrees Celsius or at ambient temperature, and pressures are at or near atmospheric. There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, 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 the air atmosphere, the temperature is programmed to 550 ℃ at the temperature rise speed of 3 ℃/min, and the constant-temperature calcination is carried out for 2 h. Stopping heating, naturally cooling to room temperature, taking out the crucible to obtain a light yellow solid which is g-C3N4. Grinding and sieving the mixture for later use.
1g g-C3N4Adding 50mL of 1mol/L HNO into the powder3The solution was stirred for 30 min. And then transferred to a hydrothermal reaction kettle. And (3) placing the hydrothermal reaction kettle in an air-blowing drying oven, carrying out hydrothermal reaction for 6h at 155 ℃, and cooling to room temperature. Centrifuging to obtain precipitate, washing with deionized water for 3 times, washing with ethanol for 1 time, oven drying at 80 deg.C for 10 hr, and cooling to obtain nanometer g-C3N4Powder particles. SEM picture confirmed 90% of g-C3N4The particle size of the powder particles varies from tens to hundreds of nanometers.
284.5mg of nano g-C3N4The powder particles were dispersed in 50mL of anhydrous ethanol, and 71.1mg of spherical nano ZnO particles (Cat. No. Z713, available from Guangzhou Hongwu materials science and technology Co., Ltd.) having an average particle diameter of 20 to 30nm were added thereto and uniformly dispersed by ultrasonic waves. Then 270.3mg of ferric chloride hexahydrate and 237.2mg of ammonium bicarbonate are added, the mixture is continuously stirred for 8 hours, and the composite photocatalyst is obtained after centrifugal separation and drying.
Example 2
10g of melamine was placed in a 100mL ceramic crucible and placed in a muffle furnace. In the air atmosphere, the temperature is programmed to 550 ℃ at the temperature rise speed of 3 ℃/min, and the constant-temperature calcination is carried out for 2 h. Stopping heating, naturally cooling to room temperature, taking out the crucible to obtain a light yellow solid which is g-C3N4. Grinding and sieving the mixture for later use.
1g g-C3N4Adding 50mL of 1mol/L HNO into the powder3The solution was stirred for 30 min. And then transferred to a hydrothermal reaction kettle. And (3) placing the hydrothermal reaction kettle in an air-blowing drying oven, carrying out hydrothermal reaction for 6h at 155 ℃, and cooling to room temperature. Centrifuging to obtain precipitate, washing with deionized water for 3 times,washing with ethanol for 1 time, oven drying at 80 deg.C for 10 hr, and cooling to obtain nanometer g-C3N4Powder particles. SEM picture confirmed 90% of g-C3N4The particle size of the powder particles varies from tens to hundreds of nanometers.
248.9mg of nano g-C3N4The powder particles were dispersed in 50mL of anhydrous ethanol, and 106.7mg of spherical nano ZnO particles (Cat. No. Z713, available from Guangzhou Hongwu materials science and technology Co., Ltd.) having an average particle diameter of 20 to 30nm were added thereto and uniformly dispersed by ultrasonic waves. Then 270.3mg of ferric chloride hexahydrate and 237.2mg of ammonium bicarbonate are added, the mixture is continuously stirred for 8 hours, and the composite photocatalyst is obtained after centrifugal separation and drying.
Example 3
10g of melamine was placed in a 100mL ceramic crucible and placed in a muffle furnace. In the air atmosphere, the temperature is programmed to 550 ℃ at the temperature rise speed of 3 ℃/min, and the constant-temperature calcination is carried out for 2 h. Stopping heating, naturally cooling to room temperature, taking out the crucible to obtain a light yellow solid which is g-C3N4. Grinding and sieving the mixture for later use.
1g g-C3N4Adding 50mL of 1mol/L HNO into the powder3The solution was stirred for 30 min. And then transferred to a hydrothermal reaction kettle. And (3) placing the hydrothermal reaction kettle in an air-blowing drying oven, carrying out hydrothermal reaction for 6h at 155 ℃, and cooling to room temperature. Centrifuging to obtain precipitate, washing with deionized water for 3 times, washing with ethanol for 1 time, oven drying at 80 deg.C for 10 hr, and cooling to obtain nanometer g-C3N4Powder particles. SEM picture confirmed 90% of g-C3N4The particle size of the powder particles varies from tens to hundreds of nanometers.
302.3mg of nano g-C3N4The powder particles were dispersed in 50mL of anhydrous ethanol, and 53.3mg of spherical nano ZnO particles (Cat. No. Z713, available from Guangzhou Hongwu materials science and technology Co., Ltd.) having an average particle diameter of 20 to 30nm were added thereto and uniformly dispersed by ultrasonic waves. Then 270.3mg of ferric chloride hexahydrate and 237.2mg of ammonium bicarbonate are added, the mixture is continuously stirred for 8 hours, and the composite photocatalyst is obtained after centrifugal separation and drying.
Comparative example 1
Trimerizing 10gCyanamide was placed in a 100mL ceramic crucible and placed in a muffle furnace. In the air atmosphere, the temperature is programmed to 550 ℃ at the temperature rise speed of 3 ℃/min, and the constant-temperature calcination is carried out for 2 h. Stopping heating, naturally cooling to room temperature, taking out the crucible to obtain a light yellow solid which is g-C3N4. Grinding and sieving the mixture for later use.
284.5mg of g-C without further treatment3N4Dispersing in 50mL of absolute ethanol, adding 71.1mg of spherical nanometer ZnO particles (Cat No. Z713, from Guangzhou Hongwu materials science and technology Co., Ltd.) with average particle diameter of 20-30nm, and ultrasonically dispersing. Then 270.3mg of ferric chloride hexahydrate and 237.2mg of ammonium bicarbonate are added, the mixture is continuously stirred for 8 hours, and the composite photocatalyst is obtained after centrifugal separation and drying.
Comparative example 2
10g of melamine was placed in a 100mL ceramic crucible and placed in a muffle furnace. In the air atmosphere, the temperature is programmed to 550 ℃ at the temperature rise speed of 3 ℃/min, and the constant-temperature calcination is carried out for 2 h. Stopping heating, naturally cooling to room temperature, taking out the crucible to obtain a light yellow solid which is g-C3N4. Grinding and sieving the mixture for later use.
1g g-C3N4Adding 50mL of 1mol/L HNO into the powder3The solution was stirred for 30 min. And then transferred to a hydrothermal reaction kettle. And (3) placing the hydrothermal reaction kettle in an air-blowing drying oven, carrying out hydrothermal reaction for 6h at 155 ℃, and cooling to room temperature. Centrifuging to obtain precipitate, washing with deionized water for 3 times, washing with ethanol for 1 time, oven drying at 80 deg.C for 10 hr, and cooling to obtain nanometer g-C3N4Powder particles. SEM picture confirmed 90% of g-C3N4The particle size of the powder particles varies from tens to hundreds of nanometers.
355.6mg of Nanog-C3N4The powder particles are dispersed in 50mL of absolute ethyl alcohol and uniformly dispersed by ultrasonic. Then 270.3mg of ferric chloride hexahydrate and 237.2mg of ammonium bicarbonate are added, the mixture is continuously stirred for 8 hours, and the composite photocatalyst is obtained after centrifugal separation and drying.
Evaluation of wastewater treatment performance of composite photocatalyst
The preparation concentration is 10mg50mL of the prepared BPA solution was placed in a cuvette made of clear glass. Then 0.6g/L of composite photocatalyst is added, and the mixture is placed in a photocatalytic reactor to start reaction after a stirrer is placed. The light source used was a 500W xenon lamp, and the light passed was secured to visible light by a UVCUT420nm cut-off filter. Firstly, dark adsorption reaction is carried out for 30min under dark condition, when the reaction reaches adsorption equilibrium, a light source is started and 0.5mL of 2mM H is added2O2And carrying out a light reaction, and closing the photocatalytic reactor after 30min to finish the reaction. After the reaction, the water sample was filtered through a 0.22 μm filter to obtain a supernatant, which was placed in a liquid phase vial for determination of the residual concentration of BPA. Using eta ═ 1-Ct/C0) Calculate degradation rate of BPA by 100%.
In addition, for lateral evaluation of the amount of iron eluted from the photocatalyst, the following method was used for evaluation: and (3) separating and recycling different photo-composite catalysts respectively after finishing a photo-catalytic reaction experiment. In order to improve the experimental accuracy and eliminate BPA possibly adhered to the surface of the photocatalytic material in the previous experimental process, the BPA is washed by absolute ethyl alcohol and deionized water for 2 to 3 times in sequence and dried so as to carry out the next cycle experiment. The cycle experiment is carried out for 4 times, and the degradation rate eta of BPA in each time is recordedn. Using gamma-eta4/η1Evaluation of the amount of iron eluted from the photo-composite catalyst was performed at 100%. The higher the value of γ, the lower the amount of iron eluted from the photocatalyst.
See table 1 for results.
TABLE 1
As can be seen from Table 1, the composite photocatalyst of example 1 of the present application has a higher catalytic effect than that of comparative examples 1-2; meanwhile, the amount of iron dissolved out by the catalyst is low, so that the catalyst has better catalytic stability.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (10)
1. A composite photocatalyst is prepared from g-C3N4Powder and iron oxyhydroxide FeOOH, the FeOOH containing g-C3N4The powder is obtained by in-situ reaction in dispersion liquid of the powder; characterized in that said g-C3N4The powder particles are selected from the group consisting of nanoparticles g-C3N4Powder particles.
2. The composite photocatalyst of claim 1, wherein the nanog-C is3N4The powder particles consist of g-C3N4Powder and HNO3The solution was mixed and prepared by a hydrothermal method.
3. The composite photocatalyst of claim 2, wherein HNO3The concentration of the solution is 0.5-1.5 mol/L; and/or, g-C3N4Powder with HNO3The weight volume ratio of the solution is 1 g: (20-80) mL.
4. The composite photocatalyst of claim 2, wherein the reaction conditions of the hydrothermal method are as follows: the reaction temperature is 140 ℃ and 170 ℃; the reaction time is 2-12 h.
5. The composite photocatalyst of claim 1 or 2, wherein the dispersion further comprises spherical nano ZnO particles.
6. The composite photocatalyst of claim 5, wherein the spherical nano ZnO particles have an average particle size of 10-40 nm.
7. The composite photocatalyst of claim 5 or 6, wherein the nanog-C is3N4The weight ratio of the powder particles to the spherical nano ZnO particles is (60-90): (40-10).
8. The composite photocatalyst of claim 1 or 2, wherein the FeOOH is formed from a mixture of the two components in a molar ratio of 1: 3 ferric trichloride hexahydrate and ammonium bicarbonate.
9. The composite photocatalyst of claim 5 or 6, wherein the nanog-C is3N4The sum of the weight of the powder particles and the spherical nano ZnO particles is (3-5) of the theoretical weight of FeOOH: 1.
10. a method of preparing a composite photocatalyst as claimed in any one of claims 1 to 9, comprising:
obtaining nano g-C3N4Powder particles and optionally spherical nano ZnO particles;
mixing the nano g-C3N4Dispersing the powder particles and optional spherical nano ZnO particles in an alcohol solvent to obtain a dispersion liquid;
performing in-situ reaction in the dispersion liquid to obtain FeOOH;
the solvent was removed.
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| CN113713754A (en) * | 2021-09-08 | 2021-11-30 | 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 |
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| 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 |
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| CN113713754A (en) * | 2021-09-08 | 2021-11-30 | 南华大学 | Preparation method and application of graphite-phase carbon nitride/magnetic goethite composite material |
| 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 |
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