g-C co-modified by iron phthalocyanine and tungsten oxide3N4Catalyst and preparation method thereof
阅读说明：本技术 一种酞菁铁和氧化钨共修饰的g-C3N4催化剂及其制备方法 (g-C co-modified by iron phthalocyanine and tungsten oxide3N4Catalyst and preparation method thereof ) 是由 任惠如 鞠美庭 钱恒力 候其东 赵莹 付学颖 王艳双 于 2021-01-12 设计创作，主要内容包括：本发明涉及一种酞菁铁和氧化钨共修饰的g-C-3N-4催化剂的制备方法,其包括以下步骤：a.将偏钨酸铵和g-C-3N-4前驱体机械混合,球磨至200目。b.将a步骤所得的混合物在500℃～600℃下焙烧3～5h。c.将b步骤的产物和酞菁铁加入乙醇中,超声分散60min,抽滤,真空干燥。d.将c步骤的产物在400℃～500℃下焙烧1～4h,得到酞菁铁和氧化钨共修饰的g-C-3N-4催化剂。本发明提供的酞菁铁和氧化钨共修饰的g-C-3N-4催化剂具有催化活性高,稳定性好的优点。(The invention relates to g-C co-modified by iron phthalocyanine and tungsten oxide 3 N 4 A method for preparing a catalyst comprising the steps of: a. mixing ammonium metatungstate with g-C 3 N 4 The precursors are mechanically mixed and ball-milled to 200 meshes. b. And c, roasting the mixture obtained in the step a for 3-5 hours at 500-600 ℃. c. And c, adding the product obtained in the step b and iron phthalocyanine into ethanol, performing ultrasonic dispersion for 60min, performing suction filtration, and performing vacuum drying. d. Roasting the product obtained in the step C at 400-500 ℃ for 1-4 h to obtain g-C co-modified by iron phthalocyanine and tungsten oxide 3 N 4 A catalyst. The invention provides g-C co-modified by iron phthalocyanine and tungsten oxide 3 N 4 The catalyst has the advantages of high catalytic activity and good stability.)
1. g-C co-modified by iron phthalocyanine and tungsten oxide3N4The catalyst and the preparation method thereof comprise the following steps:
a. mixing ammonium metatungstate with g-C3N4Mechanical mixing of precursors, ammonium metatungstate and g-C3N4The mass ratio of the precursors is 1: 20-50, and ball milling is carried out until the particle size is 200 meshes, so as to obtain a solid phase mixture A.
b. And c, roasting the mixture A obtained in the step a at 500-600 ℃ for 3-5 h, wherein the heating rate is 2-5 ℃/min, and thus obtaining a product B.
c. And C, adding the product B obtained in the step B and iron phthalocyanine into ethanol, performing ultrasonic dispersion for 60min, performing suction filtration, and performing vacuum drying to obtain a product C.
d. Roasting the product C obtained in the step C at 400-500 ℃ for 1-4 h; the heating rate is 5-10 ℃/min, and g-C co-modified by iron phthalocyanine and tungsten oxide is obtained3N4A catalyst.
Further, the carbon nitride precursor is one or more of dicyandiamide, melamine and urea.
Further, in the step b, the heating rate is 2 ℃/min, and finally the temperature is kept constant at the preset temperature for 2-6 h.
Further, the mass ratio of the product B, the iron phthalocyanine and the ethanol in the step c is 1: 0.2-0.5: 200.
furthermore, a sand core funnel is selected for operation in the suction filtration process in the step c, and a 0.45 micron filter membrane is matched.
Further, in the step d, the heating rate is 5 ℃/min, and the temperature is kept for 1-4 hours at the preset temperature.
Further, the roasting atmosphere in the step d is nitrogen.
2. The co-modified g-C of iron phthalocyanine and tungsten oxide according to claim 13N4Catalyst and process for preparing sameThe preparation method is characterized by comprising the following steps: the carbon nitride precursor is one or more of dicyandiamide, melamine and urea.
3. The co-modified g-C of iron phthalocyanine and tungsten oxide according to claim 13N4The catalyst and the preparation method thereof are characterized in that: and (c) in the step (b), raising the temperature at a rate of 2 ℃/min, and finally keeping the temperature at the preset temperature for 2-6 h.
4. The co-modified g-C of iron phthalocyanine and tungsten oxide according to claim 13N4The catalyst and the preparation method thereof are characterized in that: in the step c, the mass ratio of the product B to the iron phthalocyanine to the ethanol is 1: 0.2-0.5: 200.
5. the co-modified g-C of iron phthalocyanine and tungsten oxide according to claim 13N4The catalyst and the preparation method thereof are characterized in that: and c, selecting a sand core funnel for the suction filtration process in the step c, and matching with a 0.45 micron filter membrane.
6. The co-modified g-C of iron phthalocyanine and tungsten oxide according to claim 13N4The catalyst and the preparation method thereof are characterized in that: and d, keeping the temperature at a preset temperature for 1-4 h, wherein the heating rate in the step d is 5 ℃/min.
7. The co-modified g-C of iron phthalocyanine and tungsten oxide according to claim 13N4The catalyst and the preparation method thereof are characterized in that: the roasting atmosphere in the step d is nitrogen.
Technical Field
The invention belongs to the field of environment-friendly materials, and particularly relates to g-C co-modified by iron phthalocyanine and tungsten oxide3N4A catalyst and a preparation method thereof.
Background
The Fenton technology has mild reaction conditions, simple process and strong oxidizing capability, and can completely mineralize organic pollutants into CO2And H2O, is a very potential contaminant elimination process. It is known that the efficiency of homogeneous Fenton reaction catalyzed by iron ions is higher than that of heterogeneous Fenton reaction catalyzed by solid-supported iron. However, the traditional Fenton oxidation technology generally has the defects of serious iron loss and Fe2+A technical bottleneck that the regeneration is difficult. Therefore, the search for an efficient heterogeneous Fenton catalyst becomes the key for treating organic wastewater. Among a plurality of emerging technologies based on Fenton principle, the heterogeneous photo-Fenton technology has wide pH application range, does not generate iron mud and has higher Fe3+/Fe2+The circulation efficiency and other advantages are attracted wide attention. However, the heterogeneous photo-fenton technique still suffers from low catalytic efficiency, poor catalyst stability, the need for uv light intervention, and the like. Therefore, it is of great significance to develop a heterogeneous photo-fenton agent which is efficient and stable and can use visible light or sunlight as a driving light source.
The invention content is as follows:
the invention aims to provide g-C co-modified by iron phthalocyanine and tungsten oxide3N4The preparation method of the catalyst comprises the following steps:
a. mixing ammonium metatungstate with g-C3N4Mechanical mixing of precursors, ammonium metatungstate and g-C3N4The mass ratio of the precursors is 1: 20-50, and ball milling is carried out until the particle size is 200 meshes, so as to obtain a solid phase mixture A.
b. And c, roasting the mixture A obtained in the step a at 500-600 ℃ for 3-5 h, wherein the heating rate is 2-5 ℃/min, and thus obtaining a product B.
c. And C, adding the product B obtained in the step B and iron phthalocyanine into ethanol, performing ultrasonic dispersion for 60min, performing suction filtration, and performing vacuum drying to obtain a product C.
d. Roasting the product C obtained in the step C at 400-500 ℃ for 1-4 h at the heating rate of 5-10 ℃/min to obtain the g-C co-modified by iron phthalocyanine and tungsten oxide3N4A catalyst.
Further, the carbon nitride precursor is one or more of dicyandiamide, melamine and urea.
Further, in the step b, the heating rate is 2 ℃/min, and finally the temperature is kept constant at the preset temperature for 2-6 h.
Further, the mass ratio of the product B, the iron phthalocyanine and the ethanol in the step c is 1: 0.2-0.5: 200.
furthermore, a sand core funnel is selected for operation in the suction filtration process in the step c, and a 0.45 micron filter membrane is matched.
Further, in the step d, the heating rate is 5 ℃/min, and the temperature is kept for 1-4 hours at the preset temperature.
Further, the roasting atmosphere in the step d is nitrogen.
Drawings
FIG. 1 is a transmission electron microscope image of the microstructure of example 1.
Detailed Description
The present invention is further described in the following examples, but the technical content described in the examples is illustrative and not restrictive, and the scope of the present invention should not be limited thereby.
Example 1
a. And (2) mechanically mixing 0.14g of ammonium metatungstate and 4.20g of dicyandiamide, wherein the mass ratio of the ammonium metatungstate to the dicyandiamide is 1:30, and performing ball milling to 200 meshes to obtain a solid-phase mixture A.
b. And c, roasting the mixture A obtained in the step a at 550 ℃ for 4h, wherein the heating rate is 2 ℃/min, and obtaining a product B.
c. Adding 0.70g of the product B and 0.35g of iron phthalocyanine into 140.00g of ethanol, ultrasonically dispersing for 60min, filtering, and drying in vacuum to obtain a product C.
d. Roasting the product C obtained in the step C for 2h at 400 ℃ in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and obtaining g-C co-modified by iron phthalocyanine and tungsten oxide3N4A catalyst.
Evaluating g-C co-modified by iron phthalocyanine and tungsten oxide by adopting PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofely company3N4The performance of the catalyst is that 100ml of 1-butyl-3-methylimidazolium acetic acid aqueous solution with the concentration of hydrogen peroxide of 10mmol/L is taken as a target pollutant. 50mg of the prepared catalyst is taken, and under the irradiation of a xenon lamp, T90 (the time that the conversion rate of ibuprofen is more than 90 percent) is 15 min.
Example 1 microscopic Structure of Transmission Electron microscopy image As shown in FIG. 1, it can be seen that nano-scale tungsten oxide particles and flake iron phthalocyanine pairs g-C are present on the catalyst3N4The nano-sheet is well modified.
Example 2
a. And (2) mechanically mixing 0.14g of ammonium metatungstate and 2.80g of dicyandiamide, wherein the mass ratio of the ammonium metatungstate to the dicyandiamide is 1:20, and performing ball milling to 200 meshes to obtain a solid-phase mixture A.
b. And c, roasting the mixture A obtained in the step a at 500 ℃ for 5h, wherein the heating rate is 2 ℃/min, and thus obtaining a product B.
c. Adding 0.70g of the product B and 0.14g of iron phthalocyanine into 140.00g of ethanol, ultrasonically dispersing for 60min, filtering, and drying in vacuum to obtain a product C.
d. Roasting the product C obtained in the step C for 1h at 400 ℃ in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus obtaining g-C co-modified by iron phthalocyanine and tungsten oxide3N4A catalyst.
Evaluating g-C co-modified by iron phthalocyanine and tungsten oxide by adopting PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofely company3N4The performance of the catalyst is that 100ml of 1-butyl-3-methylimidazolium acetic acid aqueous solution with the concentration of hydrogen peroxide of 10mmol/L is taken as a target pollutant. Taking 50mg of the prepared catalyst, under the irradiation of a xenon lamp, the T90 (the time that the ibuprofen conversion rate is more than 90 percent) is20min。
Example 3
a. 0.14g of ammonium metatungstate and 7.00g of melamine are mechanically mixed, the mass ratio of the ammonium metatungstate to the melamine is 1:50, and the mixture is ball-milled to 200 meshes to obtain a solid phase mixture A.
b. And c, roasting the mixture A obtained in the step a at 600 ℃ for 3h, wherein the heating rate is 2 ℃/min, and thus obtaining a product B.
c. Adding 0.70g of the product B and 0.35g of iron phthalocyanine into 140.00g of ethanol, ultrasonically dispersing for 60min, filtering, and drying in vacuum to obtain a product C.
d. Roasting the product C obtained in the step C for 4 hours at the temperature of 500 ℃ in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and obtaining g-C co-modified by iron phthalocyanine and tungsten oxide3N4A catalyst.
Evaluating g-C co-modified by iron phthalocyanine and tungsten oxide by adopting PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofely company3N4The performance of the catalyst is that 100ml of 1-butyl-3-methylimidazolium acetic acid aqueous solution with the concentration of hydrogen peroxide of 10mmol/L is taken as a target pollutant. 50mg of the prepared catalyst is taken, and under the irradiation of a xenon lamp, T90 (the time that the conversion rate of ibuprofen is more than 90 percent) is 20 min.
Example 4
a. 0.14g of ammonium metatungstate and 7.00g of urea are mechanically mixed, the mass ratio of the ammonium metatungstate to the urea is 1:30, and the mixture is ball-milled to 200 meshes to obtain a solid phase mixture A.
b. And c, roasting the mixture A obtained in the step a at 600 ℃ for 5h, wherein the heating rate is 2 ℃/min, and thus obtaining a product B.
c. Adding 0.70g of the product B and 0.14g of iron phthalocyanine into 140.00g of ethanol, ultrasonically dispersing for 60min, filtering, and drying in vacuum to obtain a product C.
d. Roasting the product C obtained in the step C for 1h at 500 ℃ in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and thus g-C co-modified by iron phthalocyanine and tungsten oxide is obtained3N4A catalyst.
Evaluating g-C co-modified by iron phthalocyanine and tungsten oxide by adopting PLS-SXE300 (xenon lamp) photocatalytic reaction system of Beijing Pofely company3N4The catalyst performance, in 100ml,20mg/L of 1-butyl-3-methylimidazolium acetic acid aqueous solution is taken as a target pollutant, wherein the hydrogen peroxide concentration is 10 mmol/L. 50mg of the prepared catalyst is taken, and under the irradiation of a xenon lamp, T90 (the time that the conversion rate of ibuprofen is more than 90 percent) is 30 min.