CN108043445B - Protonated g-C3N4Preparation and application of bamboo stem carbon sphere-wrapped composite catalyst - Google Patents
Protonated g-C3N4Preparation and application of bamboo stem carbon sphere-wrapped composite catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
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- 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
- C02F2101/38—Organic compounds containing nitrogen
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- 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
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Abstract
The invention belongs to the technical field of preparation of environmental materials, and particularly relates to protonated g-C3N4Preparation and application of the composite catalyst coated with bamboo stem carbon balls. Preparation of protonated g-C in accordance with the invention3N4The method for wrapping the bamboo stem carbon ball composite catalyst comprises the following specific steps: first of all, the preparation of protonated g-C by calcination of melamine3N4(ii) a Then, taking bamboo stems as raw materials, and preparing bamboo stem carbon balls by adopting twice hydrothermal reactions; finally, using bamboo stem carbon ball, g-C3N4PEG solution is used as raw material, and water bath oscillation is carried out to prepare protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst; and the composite catalyst is used for degrading tetracycline. The bamboo stem raw material adopted by the invention has rich resources, low cost and simple, green and environment-friendly preparation method, and solves the problems of waste of a large amount of resources and environmental pollution caused by the waste of the resources; the synthesized catalyst has excellent performance on photocatalytic degradation of tetracycline, and has wide application prospect in the field of degradation of tetracycline wastewater.
Description
Technical Field
The invention belongs to the technical field of preparation of environmental materials, and particularly relates to protonated g-C3N4Preparation and application of the composite catalyst coated with bamboo stem carbon balls.
Background
A large amount of biomass is generated in the world every year, and is derived from agricultural and forestry waste, animal manure, organic waste generated in industrial and urban life and the like. Some of them are decomposed by nature into natural fertilizers, some are utilized by human beings, and most are directly incinerated, especially in developing countries and rural areas. These resources are not only wasted, but also the CO produced by combustion2Dust, etc. cause serious damage to the environment. Therefore, how to reasonably and effectively enrich the resources and the priceThe conversion of cheap, green and nontoxic biomass into products such as carbon materials with higher value has great practical significance.
At present, bismuth-based photocatalytic materials, tantalates and other series photocatalytic materials all show good photocatalytic activity, but the catalysts all contain metals, and the residues can cause secondary pollution. Thus, a novel non-metallic semiconductor graphitic carbon nitride (g-C)3N4) The material is widely concerned by researchers, and the carbon nitride has the excellent characteristics of good visible light responsiveness, stable chemical property, no metal and the like, so that the carbon nitride has wide attention in the fields of photocatalytic degradation of organic pollutants, photocatalytic water hydrogen production and the like. However, as a single semiconductor material, g-C in bulk phase3N4The recombination rate of the photo-generated electron-hole pair is often high, and the photocatalytic efficiency is low. The biochar has rich functional groups, so that the bonding force between materials can be increased, and the good electron transmission capacity of the carbon material can increase the catalytic activity of the material. Organism-carried g-C3N4As an aldehyde inorganic catalyst, compared with metal and other catalysts, the catalyst has the advantages of greenness, no toxicity and the like.
Generally, the environmental science field is widely concerned about the problem of organic pollution and treatment of heavy metals such as Cd, Cu, Hg and the like and pesticides and the like. Yet another class of biologically active chemical substances also has potential ecological risks, namely pharmaceuticals and personal care products. This class of chemicals has been widely used for a long time, but has only recently attracted attention. Tetracycline is a typical drug in tetracycline antibiotics, is a broad-spectrum antibiotic, has been widely used for the treatment of human and animal diseases, and has an action mechanism that the tetracycline tRNA is combined with the 30S subunit of the nucleoprotein of a receptor to prevent the aminophthalic tRNA from being combined with the nucleoprotein, so that the effect of inhibiting the growth of the receptor is achieved, and the treatment purpose is achieved. Later, the common pathogenic bacteria have been greatly limited in the clinical application of human due to the general rise of the drug resistance of the pathogenic bacteria to the medicines and the adverse reaction thereof. In the breeding industry, however, tetracycline has the characteristics of broad spectrum, high quality and low price, can promote the growth of livestock and poultry when being added at a low dose, and can be used for treating diseases when being used at a high dose, so that tetracycline is the great antibiotic with high production capacity and clinical use amount. However, tetracycline is released from the body of animals mostly along with physiological metabolic activity. In the using process, the water also directly enters the environment, such as aquaculture and the like. And thus, may cause residue in soil and water, thereby creating some potential ecological risk problems. Therefore, researches on establishment of tetracycline wastewater treatment technology are urgent and necessary.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, such as: bismuth-based, tantalate-based photocatalytic materials contain metal elements, are high in cost, and have secondary pollution caused by residues3N4The composite photocatalyst is prepared by coating the surface of the bamboo stem carbon ball and is used for treating tetracycline in wastewater pollutants.
The present invention provides a protonated g-C3N4The preparation method of the bamboo stem carbon ball-wrapped composite catalyst specifically comprises the following steps:
(1) preparation of protonated g-C3N4：
Weighing melamine and calcining at a certain temperature; naturally cooling, fully grinding the calcined product, immersing the calcined product into a hydrochloric acid solution, stirring, centrifuging the obtained mixture, washing to be neutral, and drying to obtain protonated g-C3N4And ultrasonically dispersing the precursor in deionized water to prepare protonated g-C3N4A solution;
(2) preparing bamboo stem carbon balls:
weighing bamboo stem powder, dispersing in deionized water, and transferring into a reaction kettle for a first hydrothermal reaction; naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, performing a second hydrothermal reaction, naturally cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain bamboo stem carbon balls;
(3) preparation of protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst:
ultrasonically dispersing bamboo stem carbon spheres in waterAdding PEG solution, stirring, and adding protonated g-C dropwise3N4Oscillating the solution in water bath for a period of time, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
Wherein the mass of the melamine in the step (1) is 5.0 g; the calcining temperature is 500 ℃, and the calcining time is 4 hours; the concentration of hydrochloric acid was 18.5 wt%; configuration of protonated g-C3N4The concentration of the solution was 1 mg/mL.
Wherein, the dosage ratio of the bamboo stem powder to the deionized water in the step (2) is 0.5-1.5 g: 10 mL; the first hydrothermal reaction temperature is 200 ℃ and 230 ℃, and the reaction time is 6-10 h; the temperature of the second hydrothermal reaction is 170-190 ℃, and the reaction time is 3-6 h.
Wherein, the bamboo stem carbon ball and protonated g-C in the step (3)3N4The dosage ratio of the solution is 0.01 g: 1.5-3 mL; the concentration of the PEG solution was 7 wt%; the water bath temperature is 70-90 deg.C, and the water bath time is 60-180 min.
The invention prepares a protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst, preparing the composite photocatalyst according to the steps, and protonating g-C3N4Wrapping the bamboo stem carbon ball surface with particle size of 5-7 μm; wherein protonated g-C3N4The composite photocatalyst accounts for 10-30% of the mass ratio of the composite photocatalyst.
The invention also provides a protonated g-C3N4The application of the composite photocatalyst coated with the bamboo stem carbon spheres is that the composite photocatalyst obtained by the preparation method is applied to the degradation of tetracycline in antibiotic wastewater, and the degradation rate reaches 80%.
The raw material of the bamboo stem powder used in the present invention is from the university of Jiangsu; other reagents melamine, hydrochloric acid and PEG2000 are purchased from national chemical reagent company Limited; tetracycline is purchased from Shanghai Aladdin reagents, Inc.;
compared with the prior art, the invention has the following beneficial effects:
(1) the invention takes bamboo as raw material, and adopts the simple processThe two-step hydrothermal method successfully prepares a carbon sphere material and combines the material with protonated g-C3N4And combining to prepare the composite photocatalyst wrapping the bamboo stem carbon spheres for degrading antibiotic wastewater. Compared with other carbon sources, the bamboo wood as the carbon source is cheaper and more easily obtained, and compared with other plants, the bamboo wood has the advantages of short growth period and high propagation speed. Compared with a high-temperature cracking method, the method for synthesizing the biological carbon material by the hydrothermal method saves more energy, wherein the first step of hydrothermal reaction is to decompose cellulose, the shape of the carbon sphere is regulated, and the second step of hydrothermal reaction is to further obtain the carbon sphere material with purer shape.
(2) Most of the traditional biological carbon materials have no fixed morphology, but the invention successfully prepares the spherical biological carbon material, improves the specific surface of the material and is protonated g-C3N4More binding sites are provided and the synthesized composite material has more reactive active sites. From FIG. 1 it can be seen that pure protonated g-C3N4The degradation rate of the material is about 20 percent, and the protonated g-C3N4The degradation rate of the composite catalyst wrapping the bamboo stem carbon ball can reach 80 percent, thereby showing that the composite catalyst effectively improves protonated g-C3N4The separation efficiency of electron-hole pairs.
(3) The invention successfully converts the biological material into the carbon material with higher value, not only solves the waste of a large amount of resources and the environmental pollution caused by the waste, but also ensures that the synthesized catalyst has good catalytic activity and further solves the environmental pollution. The biological material is used as a carbon source with most abundant resources, and is effectively converted into the carbon material, so that a new idea is provided for the synthesis of the carbon material, and more references are added for the conversion of the biological material.
Drawings
FIG. 1 is a representation of protonated g-C prepared in accordance with the present invention3N4Degradation diagram of composite catalyst coated with bamboo stem carbon spheres, wherein (a) is protonated g-C3N4The others (b-l) are protonated g-C corresponding to examples 1-11, respectively3N4Wrapping the bamboo stem carbon balls;
FIG. 2 (a) is an SEM image of a bamboo culm carbon sphere of the present invention, and (b) is a protonated g-C of the present invention3N4SEM picture of the composite catalyst wrapped by bamboo stem carbon spheres;
FIG. 3 is an XRD pattern of the material prepared by the present invention, (a) is bamboo shoot carbon sphere, (b) is protonated g-C3N4Wrapping bamboo stem carbon ball composite catalyst, wherein (C) is protonated g-C3N4。
Detailed Description
The invention is further illustrated by the following examples.
Protonated g-C prepared in the present invention3N4And (3) evaluating the photocatalytic activity of the bamboo stem carbon ball-wrapped composite catalyst: the reaction was carried out in a DW-01 type photochemical reactor (available from technologies, Inc., university of Yangzhou, city, 100W of a tungsten-iodine lamp, 100mL of tetracycline-simulated wastewater was charged into the reactor and the initial value thereof was measured, and then 50 mg of the prepared protonated g-C was added3N4Wrapping the bamboo stem carbon ball composite catalyst, keeping the catalyst in a suspension or floating state by magnetic stirring, carrying out dark adsorption for half an hour, then sampling and analyzing at an interval of 10 min in the process of illumination, taking supernatant after centrifugal separation, measuring absorbance by using a spectrophotometer, and passing through a formula: ƞ = [ (1-C)t/C0)]x100% to calculate the degradation rate, where C0Absorbance of the tetracycline solution to reach adsorption equilibrium, CtThe absorbance of the tetracycline solution was determined for the timed samples.
Example 1:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixture, washing to be neutral, and drying to obtain protonated g-C3N4(ii) a Protonating g-C3N4Ultrasonically dispersing in water solution to prepare solution with concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out first hydrothermal reaction at 210 ℃ for 6 hours; and naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction for 3 hours at 170 ℃, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N4Oscillating the solution in water bath at 70 ℃ for 60min with 1.5 mL of the solution, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 74% within 80 min.
Example 2:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixture, washing to be neutral, and drying to obtain protonated g-C3N4(ii) a Protonating g-C3N4Ultrasonically dispersing in water solution to prepare solution with concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 6 hours; and naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction for 3 hours at 180 ℃, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in 70 ℃ water bath for 60min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 80% within 80 min.
Example 3:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixed product, washing to be neutral, and drying to obtain protonated g-C3N4The mixture was ultrasonically dispersed in an aqueous solution to prepare a solution having a concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 230 ℃ for 6 hours; and naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out secondary hydrothermal reaction at 190 ℃ for 3 hours, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N4Shaking the solution in water bath at 70 deg.C for 60min, centrifuging, washing, and oven drying to obtainTo protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 75% within 80 min.
Example 4:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixed product, washing to be neutral, and drying to obtain protonated g-C3N4The mixture was ultrasonically dispersed in an aqueous solution to prepare a solution having a concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 6 hours; naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction at 180 ℃ for 3 hours, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in water bath at 80 ℃ for 60min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon ball composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring the photocatalyst pairThe degradation rate of tetracycline reaches 74% within 80 min.
Example 5:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixed product, washing to be neutral, and drying to obtain protonated g-C3N4The mixture was ultrasonically dispersed in an aqueous solution to prepare a solution having a concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 6 hours; naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction at 180 ℃ for 3 hours, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in water bath at 90 ℃ for 60min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 75% within 80 min.
Example 6:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product in 18.5 wt% hydrochloric acid solution, stirring, and mixingCentrifuging the obtained mixed product, washing to neutrality, and drying to obtain protonated g-C3N4The mixture was ultrasonically dispersed in an aqueous solution to prepare a solution having a concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 6 hours; and naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction for 3 hours at 180 ℃, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in 70 ℃ water bath for 120 min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 76% within 80 min.
Example 7:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixed product, washing to be neutral, and drying to obtain protonated g-C3N4The mixture is ultrasonically dispersed in an aqueous solution to prepare a solution with the concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 1.5g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 6 hours; naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction at 180 ℃ for 3 hours, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in 70 ℃ water bath for 180min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 67 percent within 80 min.
Example 8:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixed product, washing to be neutral, and drying to obtain protonated g-C3N4The mixture is ultrasonically dispersed in an aqueous solution to prepare a solution with the concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 4.5 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 6 hours; and naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out secondary hydrothermal reaction for 4 hours at 180 ℃, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in 70 ℃ water bath for 60min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 69% within 80 min.
Example 9:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixed product, washing to be neutral, and drying to obtain protonated g-C3N4The mixture is ultrasonically dispersed in an aqueous solution to prepare a solution with the concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 6 hours; and naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction at 180 ℃ for 6 hours, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in 70 ℃ water bath for 60min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 67 percent within 80 min.
Example 10:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixed product, washing to be neutral, and drying to obtain protonated g-C3N4The mixture is ultrasonically dispersed in an aqueous solution to prepare a solution with the concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 8 hours; and naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction for 3 hours at 180 ℃, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in 70 ℃ water bath for 60min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 71% within 80 min.
Example 11:
(1) protonated g-C3N4The preparation of (1):
weighing 5.0 g of melamine, calcining at 500 ℃ for 4h, naturally cooling, fully grinding the calcined product, immersing the calcined product into 18.5 wt% hydrochloric acid solution, stirring, centrifuging the obtained mixed product, washing to be neutral, and drying to obtain protonated g-C3N4The mixture is ultrasonically dispersed in an aqueous solution to prepare a solution with the concentration of 1 mg/mL.
(2) Preparing bamboo stem carbon balls:
weighing 3 g of bamboo stem powder, mixing the bamboo stem powder in 30 mL of deionized water, transferring the mixture into a reaction kettle, and carrying out a first hydrothermal reaction at 200 ℃ for 10 hours; and naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, carrying out a second hydrothermal reaction for 3 hours at 180 ℃, centrifuging, washing with deionized water and ethanol, and drying to obtain the bamboo stem carbon balls.
(3) Protonated g-C3N4Preparing a bamboo stem carbon ball-wrapped composite catalyst:
weighing 0.01g of bamboo stem carbon ball, ultrasonically dispersing in water, adding 7 wt% of PEG solution, uniformly stirring, and dropwise adding protonated g-C3N42.5 mL of the solution, oscillating in 70 ℃ water bath for 60min, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst.
(4) Photocatalytic degradation test:
taking the protonated g-C prepared in step (3)3N4Wrapping the bamboo stem carbon sphere composite catalyst, performing a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 68% within 80 min.
FIG. 1 is a representation of protonated g-C prepared in accordance with the present invention3N4Degradation diagram of composite catalyst coated with bamboo stem carbon spheres, wherein (a) is protonated g-C3N4The product obtained in example 1, (c) the product obtained in example 2, (d) the product obtained in example 3, (e) the product obtained in example 4, (f) the product obtained in example 5, (g) the product obtained in example 6, (h) the product obtained in example 7,(i) the product obtained in example 8, (j) is the product obtained in example 9, (k) is the product obtained in example 10, and (l) is the product obtained in example 9. As can be seen from the figure, protonated g-C3N4The degradation rate is about 20%, but the degradation rate of the composite material reaches 65-80%, so that the performance of the material loaded on the surface of the carbon ball is obviously improved, the degradation effect of the product obtained in example 2 is the best, reaches 80%, the loading proportion of example 2 is proper, and the carbon material prepared from the biological material also has good performance. The effect of changing the degradation rate of the composite material obtained under the condition of unchanged load capacity is not changed greatly, which shows that the load ratio is a key factor influencing the material performance.
FIG. 2 (a) is an SEM image of a bamboo culm carbon sphere of the present invention, and (b) is a protonated g-C of the present invention3N4SEM picture of the composite catalyst wrapped by bamboo stem carbon balls. As can be seen from (a), a carbon sphere using bamboo as a raw material, which is smooth in surface and has a particle size of about 5 to 7 μm, is successfully prepared because of the complexity of components in the biomaterial, and the characteristic peaks of cellulose appear in the carbon sphere material as can be seen from XRD of FIG. 3. (b) As can be seen in the figure, a shell structure is loaded on the surface of a spherical organism, and the shell is formed by protonated g-C3N4Formed, indicating protonated g-C3N4The bamboo stem carbon sphere-wrapped composite catalyst is successfully prepared; due to the small thickness of the shell structure, the particle size of the composite catalyst is also about 5-7 μm.
FIG. 3 is an XRD pattern of the material prepared by the present invention, (a) is bamboo shoot carbon sphere, (b) is protonated g-C3N4Wrapping bamboo stem carbon ball composite catalyst, wherein (C) is protonated g-C3N4. From the graph (a), two peaks are observed, which is caused by the existence of cellulose, because bamboo contains a large amount of cellulose, the cellulose can enhance the stability of the material, and from the peak position and peak intensity of (C), protonated g-C3N4Was successfully prepared, and from the graph (b), it was found that g-C having both bamboo shoot carbon spheres and protonation3N4Two kinds of materialsThe peak of the material indicates that the composite material is successfully prepared; of these, protonated g-C is clearly seen3N4Indicates that the material contains protonated g-C3N4The material, but some reduction in strength, is due to the carbon material.
Claims (9)
1. Protonated g-C3N4The preparation method of the bamboo stem carbon sphere-wrapped composite catalyst is characterized in that the composite catalyst is spherical and has the particle size of 5-7 mu m; protonated g-C3N4The bamboo stem charcoal ball is wrapped on the surface of the bamboo stem charcoal ball, and the preparation method comprises the following steps:
(1) preparation of protonated g-C3N4: protonating the prepared g-C3N4Dispersed in deionized water to form protonated g-C3N4Solution for later use;
(2) preparing bamboo stem carbon balls:
weighing bamboo stem powder, dispersing in deionized water, and transferring into a reaction kettle for a first hydrothermal reaction; naturally cooling, filtering out solids in the mixed product, continuously transferring the obtained filtrate into a reaction kettle, performing a second hydrothermal reaction, naturally cooling, centrifuging, washing with deionized water and ethanol, and drying to obtain bamboo stem carbon balls;
(3) preparation of protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst:
ultrasonically dispersing bamboo stem carbon spheres in water, adding a PEG solution, uniformly stirring, and dropwise adding protonated g-C3N4Oscillating the solution in water bath for a period of time, centrifuging, washing and drying to obtain protonated g-C3N4Wrapping the bamboo stem carbon ball composite catalyst; bamboo shoot carbon spheres and protonated g-C3N4The dosage ratio of the solution is 0.01 g: 1.5-3 mL.
2. Protonated g-C according to claim 13N4The preparation method of the bamboo stem carbon ball-wrapped composite catalyst is characterized in that in the step (1), protonated g-C3N4The concentration of the solution was 1 mg/mL.
3. Protonated g-C according to claim 13N4The preparation method of the bamboo stem carbon ball-wrapped composite catalyst is characterized in that in the step (2), the dosage ratio of the bamboo stem powder to the deionized water is 0.5-1.5 g: 10 mL.
4. Protonated g-C according to claim 13N4The preparation method of the bamboo stem carbon sphere-wrapped composite catalyst is characterized in that in the step (2), the temperature of the first hydrothermal reaction is 200-; the temperature of the second hydrothermal reaction is 170-190 ℃, and the reaction time is 3-6 h.
5. Protonated g-C according to claim 13N4The preparation method of the bamboo stem carbon sphere-wrapped composite catalyst is characterized in that in the step (3), the concentration of the PEG solution is 7 wt%.
6. Protonated g-C according to claim 13N4The preparation method of the bamboo stem carbon ball-wrapped composite catalyst is characterized in that in the step (3), the water bath temperature is 70-90 ℃, and the water bath time is 60-180 min.
7. Protonated g-C according to claim 13N4The preparation method of the bamboo stem carbon sphere-wrapped composite catalyst is characterized in that in the step (2), the temperature of the first hydrothermal reaction is 200 ℃, and the reaction time is 6 hours; the temperature of the second hydrothermal reaction is 180 ℃, and the reaction time is 3 h.
8. Protonated g-C according to claim 13N4The preparation method of the bamboo stem carbon ball-wrapped composite catalyst is characterized in that in the step (3), the water bath temperature is 70 ℃, and the water bath time is 60 min.
9. Protonated g-C prepared according to the preparation method of any one of claims 1 ~ 83N4The bamboo stem carbon sphere coated composite catalyst is used for catalyzing and degrading tetracycline.
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