CN111701587A - Core-shell structure catalysis-photocatalysis composite material and preparation method and application thereof - Google Patents

Core-shell structure catalysis-photocatalysis composite material and preparation method and application thereof Download PDF

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CN111701587A
CN111701587A CN202010581886.9A CN202010581886A CN111701587A CN 111701587 A CN111701587 A CN 111701587A CN 202010581886 A CN202010581886 A CN 202010581886A CN 111701587 A CN111701587 A CN 111701587A
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zinc
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付少海
翟世民
李敏
王冬
张丽平
王春霞
田安丽
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Jiangnan University
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

Hair brushThe invention discloses a core-shell structure catalysis-photocatalysis composite material, a preparation method and application thereof, and belongs to the technical field of materials. The invention takes biomass as a carbon source, prepares the carbon sphere material by dehydration and carbonization under the hydrothermal condition, and respectively wraps MgO/ZnO and Ag/TiO on the surface of the carbon sphere material by related processes2Preparing a crystal shell, and preparing the catalytic-photocatalytic material with the core double-shell structure. The material obtained by the invention has the advantages of large specific surface area, high catalytic efficiency and repeated use, can efficiently remove dyes and organic pollutants in wastewater, and realizes resource utilization of waste biomass.

Description

Core-shell structure catalysis-photocatalysis composite material and preparation method and application thereof
Technical Field
The invention discloses a core-shell structure catalysis-photocatalysis composite material and a preparation method and application thereof, belonging to the technical field of materials.
Background
The catalytic material has the characteristics of high efficiency, no toxicity and good stability when decomposing organic pollutants, and along with the improvement of energy cost and the increase of environmental pollution problems, the application of the catalytic material in the aspect of environmental management attracts more and more attention. The catalytic materials can be classified into photocatalytic materials (e.g., TiO) according to their principle of action2、C3N4Etc.) and non-photocatalytic materials (e.g., MgO), in which TiO is present2Is a typical photocatalytic material which can be excited under the irradiation of ultraviolet light and has good catalytic degradation effect on organic pollutants, however, the ultraviolet light only accounts for about 4 percent of sunlight, and TiO is2The wider energy band gap limits the efficiency of its use of sunlight. The reduction of the energy band gap of titanium dioxide by doping and modification is the main method for improving the catalytic efficiency of titanium dioxide, such as Ag2WO4/AgBr/TiO2、C3N4-TiO2And Ag-C/N-TiO2And the like. MgO is a good non-photocatalytic material, nano MgO particles have good adsorption and catalysis effects on pollutants in water, and MgO crystals can change electron distribution and molecular polarity in organic molecules and realize electron transfer and chemical bondBreaking to degrade organic matters; the ZnO crystal is doped in the MgO crystal, so that the Lewis acidity of the MgO crystal can be increased, the attraction capacity of the MgO crystal to electrons is improved, and the activation energy of the MgO crystal for catalyzing organic matters is reduced, thereby improving the degradation capacity of the MgO crystal to the organic matters.
At present, methods for improving catalytic performance of catalytic materials mainly comprise: the contact area of the material and light is increased by controlling the particle size of the catalytic material; the efficiency of light energy utilization is improved by extending the range of wavelengths of the absorbed light. However, the degradation capability of the material prepared by the existing method is limited, and the development of a catalytic material with better catalytic degradation efficiency is urgently needed.
In addition, a support or template is often used during the preparation of the catalytic material. The nano-scale carbon microsphere has the characteristics of high specific surface area, surface modification, controllable morphology and the like, and has more applications in gas storage, catalytic carriers and chemical templates. The main methods for synthesizing the nano-scale carbon microspheres at present include a polycondensation method, a liquid phase method, chemical vapor deposition, a hydrothermal method, ultrasonic spray pyrolysis and the like. The polycondensation method is mainly used for preparing mesocarbon microbeads, such as: the method comprises the steps of carrying out thermal polycondensation on asphalt serving as a raw material to obtain mesophase asphalt, separating to obtain mesophase asphalt microspheres, and carrying out preoxidation and carbonization on the asphalt microspheres to obtain a carbon microsphere product. The polycondensation method is a main method for modern industrial preparation, has the characteristics of simple preparation conditions, easy operation and the like, but has uneven particle size distribution and low yield of the prepared microspheres, and limits the further development of the technology for preparing the carbon microspheres by the polycondensation method; the liquid phase method is a preparation method of a reaction system with a main phase as a liquid phase, and comprises the following steps: an emulsification method and a suspension method, wherein the suspension method is a method that mesophase pitch is dissolved in an organic solvent, a surfactant and water or other solvents are utilized to form a suspension, the suspension is stirred strongly at a certain temperature to enable the mesophase pitch to be spherical, then the organic solvent is removed by heating, and the mesophase carbon microspheres are obtained after cooling, leaching, pre-oxidation and carbonization treatment, and the preparation process is complex, and a large amount of organic solvents are used, so that the problem of environmental pollution is easily caused, and the application scale is limited; the Chemical Vapor Deposition (CVD) method is a method for forming a material by forming basic particles through chemical reaction in a gas phase by utilizing a gas raw material and performing nucleation and growth, the prepared synthetic temperature gradient is high, the synthetic particles have large particles and are easy to agglomerate, but the preparation application prospect is wide, and the chemical vapor deposition method can become a main method for industrially producing the carbon microspheres in the future after further improvement and research. At present, the main raw materials for preparing the nano carbon microspheres comprise asphalt, pyrolytic graphite, glucose, phenolic resin, carbon tetrachloride and the like, and the problems of high raw material cost, low preparation conversion rate, more byproducts, pollution and the like exist.
Disclosure of Invention
In order to solve the problems, the invention researches the relationship between the distribution condition of each component on the multi-component composite catalytic material and the catalytic performance of the multi-component composite catalytic material; according to the optical properties of the photocatalytic material and the non-photocatalytic material, the distribution of the photocatalytic material on the light receiving surface and the backlight surface of the composite catalytic material is reasonably controlled, and the catalytic performance of the composite catalytic material is effectively improved.
Meanwhile, the invention adopts the waste biomass as the raw material, utilizes the components of polysaccharide, pentose and the like in the waste biomass to prepare the nano carbon microspheres by carbonization, can greatly reduce the cost of the raw material and realize the resource utilization of the waste biomass. In agricultural production and life, large amounts of waste biomass are produced, such as: the traditional incineration treatment of straws, biological sludge, waste peel, bamboo wood, marine algae and the like can bring about a serious problem of atmospheric pollution, is forbidden by environmental protection departments, and the biomass is crushed and returned to the field for treatment, so that insect pests are easily caused.
The invention synthesizes the carbon sphere template by utilizing components such as soluble polysaccharide, pentose and the like in the waste biomass, and realizes the resource utilization of the waste biomass. After the surface of the carbon sphere template is modified, MgO-ZnO and TiO are respectively coated2An Ag shell structure, and finally removing the carbon sphere template to form an inner layer with a non-photocatalytic material (MgO-ZnO) on the backlight surface and an outer layer with a photocatalytic material on the light receiving surfaceMaterial (TiO)2-Ag) to realize the compounding and the concerted catalysis of the non-photocatalytic material and the photocatalytic material, increase the light irradiation area of the photocatalytic material and the contact area of the non-photocatalytic material and the organic pollutants, improve the catalytic degradation efficiency of the composite material, and realize the high-efficiency adsorption-catalytic degradation of the organic pollutants in water.
The first purpose of the invention is to provide a catalytic-photocatalytic composite material, and the preparation method of the composite material comprises the following steps:
(1) carbonizing a carbon source to prepare carbon spheres (BM);
(2) mixing the obtained carbon spheres (BM) with an anion modifier for anion modification, and adding the prepared Mg2 +/Zn2+Carrying out reaction on the sol; after the reaction is finished, carrying out solid-liquid separation, collecting the precipitate, and calcining to obtain a precursor material (CSM);
(3) adding the obtained precursor material to TiO2Carrying out reaction in the sol, carrying out solid-liquid separation after the reaction is finished, collecting the precipitate, and calcining; adding the calcined product into a silver ion solution for hydrothermal reaction, carrying out solid-liquid separation after the reaction is finished, collecting the precipitate, and drying to obtain the composite material (DSM).
In one embodiment of the present invention, the carbon source in step (1) is a biomass material; the biomass material is one or a combination of more of moso bamboo, crop straws, fruit peels (waste fruit peels), residual sludge of sewage treatment plants, wood (waste wood), and organic waste organisms of marine algae.
In one embodiment of the present invention, the carbonization in the step (1) is performed in a hydrothermal reaction. The carbonization temperature is 180-260 ℃, and the carbonization time is 12-36 h. Wherein the carbonization is carried out at a programmed temperature rise rate of 0.5-2.5 ℃/min.
In one embodiment of the present invention, the negative ion modifier in step (2) is one or more of sodium poly (p-styrene sulfonate), sodium p-styrene sulfonate, sodium dodecyl sulfonate, sodium ethylene diamine tetracetate, and alpha-sulfo monocarboxylic acid ester.
In one embodiment of the present invention, the mass ratio of the carbon spheres to the negative ion modifier in the step (2) is (1-4): (0.5-2).
In one embodiment of the present invention, the temperature of the modification in the step (2) is 50 to 80 ℃; the time is 12-36 h.
In one embodiment of the present invention, Mg in the step (2)2+/Zn2+The preparation method of the sol comprises the following steps: dispersing a magnesium source and a zinc source in an organic solvent, then reacting at 50-80 ℃, standing and aging after the reaction is finished to obtain Mg2+/Zn2+And (3) sol.
In one embodiment of the present invention, the Mg2+/Zn2+The mass fraction of the magnesium source and the zinc source in the sol is 5 to 30 percent; the mass fraction of the organic solvent is 70-95%.
In one embodiment of the present invention, the Mg2+/Zn2+The mass ratio of the magnesium source to the zinc source in the sol is 1: 1-10: 1; preferably, the ratio of 2: 1-10: 1; further preferably 5: 1.
in one embodiment of the invention, the magnesium source is one or more of magnesium chloride, magnesium nitrate, magnesium acetate; the zinc source is one or more of zinc nitrate, zinc acetate and zinc chloride. The organic solvent is one or more of ethylene glycol monomethyl ether, triethanolamine, diethanolamine, monoethanolamine and ethanol.
In one embodiment of the present invention, the solid-liquid separation in step (2) is centrifugal separation; wherein the rotation speed of the centrifugation is 4000-10000r/min, and the time of the centrifugation is 5-30 min.
In one embodiment of the invention, the temperature of the reaction in the step (2) is 50-80 ℃; the reaction time is 4-24 h.
In one embodiment of the present invention, the calcination temperature in step (2) is 350-550 ℃, and the calcination time is 1-4 h.
In one embodiment of the present invention, the TiO in the step (2)2The preparation method of the sol comprises the following steps: mixing a titanium source, water and an organic solvent, then reacting at 60-90 ℃, standing and aging after the reaction is finished to obtain TiO2And (3) sol.
In one embodiment of the present invention, the volume ratio of the titanium source, water, and organic solvent is 10: (1-5): (50-100); wherein, the ratio of water: the volume ratio of the organic solvent is preferably 1: 50.
In one embodiment of the invention, the titanium source used is one or more of tetrabutyl titanate, tetraethyl titanate, diisopropyl bistitanate, tetrapropyl titanate. The organic solvent is one or more of ethanol, acetic acid, ethyl acetate, methanol, ethyl formate, propanol, propionic acid and ethyl propionate.
In one embodiment of the present invention, the precursor in step (3) is in TiO2The reaction temperature in the sol is 20-30 ℃; the reaction time is 4-24 h.
In one embodiment of the present invention, the calcination temperature in the step (3) is 350-550 ℃, and the calcination time is 1-4 h.
In one embodiment of the present invention, the preparation method specifically includes the following steps:
firstly, cutting waste biomass materials into fragments, cleaning and drying the fragments, then mixing and stirring the fragments and an initiator solution, carbonizing the mixture under a hydrothermal condition, finally removing sheet materials in the carbonized mixture, and centrifuging and separating the mixed solution to obtain a carbon Ball Material (BM);
secondly, carrying out negative ion modification on the carbon spheres (BM) after washing and drying with water and an organic solvent, and then adding the BM into Mg prepared from magnesium salt, zinc salt and the organic solvent2+/Zn2+Continuing the reaction in the sol, and after the reaction is finished, drying and carrying out high-temperature oxygen-free calcination on the separated carbon spheres to obtain a precursor material (CSM);
thirdly, the CSM is added into TiO composed of titanium salt and organic solvent2Reacting in sol, drying the centrifugally separated carbon spheres, calcining at high temperature under oxygen-free condition, adding into silver nitrate solution with certain concentration, heating for hydrolysis, centrifuging, and drying to obtain the catalytic-photocatalytic material (DSM) with the core-shell structure.
In one embodiment of the invention, the organic waste biomass is sheared into pieces with the size of 1-1.5cm multiplied by 1-2.5cm, the drying temperature is 60-105 ℃, and the drying time is 12-24 h.
In one embodiment of the invention, the concentration of the initiator solution is 5-10g/L, the mixing and stirring temperature is 50-80 ℃, and the stirring time is 20-60 min.
In one embodiment of the present invention, the initiator is one or more of sodium lignosulfonate, phloroglucinol, sodium oleate and sodium carboxymethylcellulose.
The second purpose of the invention is to apply the catalytic-photocatalytic composite material obtained as described above to the field of environmental remediation.
The application is to adsorb and degrade organic pollutants by the catalytic-photocatalytic composite material.
The organic contaminants include dye contaminants such as Methylene Blue (MB) and the like.
The invention has the beneficial effects that:
the invention selects the waste biomass as the raw material to prepare the carbon sphere template, realizes the resource utilization of the waste biomass, and coats MgO, ZnO and TiO2And Ag and the like to prepare the catalysis-photocatalysis material with the core-shell structure.
The core-shell structure catalytic-photocatalytic material has the advantages of large specific surface area, stable chemical property and photocatalytic component (TiO)2Ag) is arranged on the outer light receiving surface of the core-shell structure, the visible light utilization efficiency can be high in the catalysis process, the non-photocatalytic component (MgO-ZnO) is arranged on the inner layer of the core-shell structure, the irradiation of a light source is not received, and the high-efficiency catalytic degradation of organic pollutants in water can be realized through the synergistic effect of the components.
Drawings
FIG. 1A is a TEM image of HCMs; B-F are Mapping graphs of elements O, Mg, Ti, Zn and Ag respectively;
FIG. 2 is a graph showing the change in absorbance of a methylene blue solution after treatment with the catalytic material of core-shell structure obtained in example 1;
FIG. 3 is a diagram showing the effect of removing Methylene Blue (MB) and recycling the core-shell structure catalytic materials (HCMs) obtained in example 2;
FIG. 4 is a graph showing the change of contaminants in water after treatment at different irradiation times;
FIG. 5 is a liquid chromatography mass spectrometry (LC-MS) analysis chart of the initial solution and the solution after different catalytic treatment times (D-30 adsorption for 30min, L-10 illumination for 10min and L-30 illumination for 30 min).
Detailed Description
Calculating the removal rate D (%) as shown in formula (1):
D＝(c0-ce)/c0(1)，
wherein c is0Initial concentration of dye solution (mg/L); c. CeThe concentration of the dye remaining after the treatment (mg/L) was used.
Example 1
In the embodiment, bamboo fragments are selected as raw materials to prepare the carbon sphere template, and the preparation process of the core-shell structure catalytic material is as follows:
firstly, cutting irregular bamboos into fragments with the size of 1-1.5cm multiplied by 1-2.5cm, cleaning in water, drying, adding 3.2g of bamboo chips and 0.8g of phloroglucinol into a beaker filled with 120ml of distilled water, heating at 80 ℃ for 2h, transferring to a hydrothermal reaction kettle, heating at 220 ℃ for 24h (the heating rate is 1 ℃/min), screening the reaction product through a screen with 240 meshes, filtering out large bamboo residues, centrifugally separating to obtain carbon sphere template sediments, cleaning for three times by using ethanol and distilled water, and drying to obtain the carbon sphere template.
Adding 0.5g of zinc acetate, 2.5g of magnesium chloride and 0.8g of monoethanolamine into 20mL of ethylene glycol monomethyl ether, heating at 60 ℃ for 2h, stirring for dissolving, standing for 48h, and aging to obtain Mg2+/Zn2+And (3) sol.
Respectively and slowly adding 10mL of tetrabutyl titanate, 5mL of triethanolamine and 1mL of distilled water into 50mL of absolute ethyl alcohol, heating at 80 ℃ for 2h, standing for 48h, and aging to obtain the titanium dioxide sol.
Adding 0.5g of carbon sphere template and 8mL of sodium p-styrene sulfonate into 100mL of distilled water for ultrasonic dispersion, stirring for 12h at 60 ℃, and slowly dropwise adding 9mL of Mg2+/Zn2+Stirring the sol at 60 ℃ for 12h, performing centrifugal separation, performing anaerobic calcination at 350 ℃ for 3h (heating rate of 5 ℃/min), adding the sol into the titanium dioxide sol, performing dispersion stirring for 4h, performing centrifugal separation, performing anaerobic calcination at 500 ℃ for 2h, and adding 100mL of 0.1g/L AgNO3In solutionCentrifuging at 80 deg.C for 2h, calcining at 500 deg.C in air for 4h to remove carbon sphere template, and obtaining catalysis-photocatalysis microspheres (HCMs) with core-shell structure, wherein TEM and element mapping are shown in FIG. 1.
The catalytic performance is as follows: the removal effect of 0.04g of HCMs on 100mL of methylene blue (25 mg/L) under 150W xenon lamp irradiation, and the change of the absorbance of the methylene blue solution under different adsorption times (D-10 to D-30) and different illumination times (L-10 to L-240) are shown in FIG. 2.
According to beer's law, the higher the methylene blue concentration, the stronger the absorbance at the maximum absorption wavelength. As can be seen from the absorption spectrum of FIG. 2, after adsorption (30min) and photocatalytic treatment (240min), the absorbance of the solution at the maximum absorption wavelength of methylene blue (640nm) is obviously reduced, the concentration of methylene blue gradually tends to be balanced after adsorption for 30min, and the concentration of methylene blue is rapidly reduced after xenon lamp irradiation for 10min and is gradually reduced along with the increase of irradiation time. The result shows that the core-shell structure catalytic materials (HCMs) have good adsorption and catalytic degradation effects on methylene blue, and the removal rate of 0.04g of HCMs to the methylene blue (100mL,25mg/L) reaches 76.9% after the materials are irradiated for 240 min.
Example 2
In the embodiment, the peel scraps are selected as raw materials to prepare the carbon sphere template, and the preparation process of the core-shell structure catalytic material is as follows:
firstly, cutting pericarp into fragments with the size of 1-1.5cm multiplied by 1-2.5cm, washing dust and impurities in water, adding 6g of the washed pericarp fragments and 1g of phloroglucinol into a beaker filled with 120mL of distilled water, heating at 60 ℃ for 3h, transferring into a hydrothermal reaction kettle, heating at 200 ℃ for 12h (the heating rate is 1.5 ℃/min), sieving a reaction product by a 240-mesh sieve, filtering pericarp residues, carrying out centrifugal separation to obtain carbon sphere template sediments, washing for three times by ethanol and distilled water, and drying to obtain the carbon sphere template.
Adding 0.8g of zinc chloride, 4g of magnesium acetate and 0.2g of triethanolamine into 30mL of ethylene glycol monomethyl ether, heating at 70 ℃, stirring for dissolving for 2.5h, standing for 36h, and aging to obtain Mg2+/Zn2+And (3) sol.
Respectively and slowly adding 10mL of tetrabutyl titanate, 5mL of triethanolamine and 1mL of distilled water into 50mL of absolute ethyl alcohol, heating at 90 ℃ for 1.5h, standing for 24h, and aging to obtain the titanium dioxide sol.
Adding 0.8g of carbon sphere template and 10mL of sodium p-styrene sulfonate into 100mL of distilled water for ultrasonic dispersion, stirring for 12h at 60 ℃, and slowly dropwise adding 10mL of Mg2+/Zn2+Stirring the sol at 80 ℃ for 16h, performing centrifugal separation, performing anaerobic calcination at 300 ℃ for 4h (the heating rate is 3.5 ℃/min), adding the sol into the titanium dioxide sol, performing dispersion stirring for 4h, performing centrifugal separation, performing anaerobic calcination at 550 ℃ for 4h, and adding 100mL of 0.2g/L AgNO3In the solution, centrifuging after 2h at 80 ℃, calcining for 4h in air at 550 ℃ to remove the carbon sphere template, and obtaining the catalysis-photocatalysis microspheres (HCMs) with the core-shell structure.
The effect of 0.01g of HCMs on the removal and recycling of 100mL of methylene blue at 5mg/L under the irradiation of a 150W xenon lamp is shown in FIG. 3.
In fig. 3, it can be seen that the HCMs have a good removal effect on methylene blue, the removal rate of methylene blue reaches more than 98% when the HCMs are used for the first time and are illuminated for 270min, the reduction of the removal effect on methylene blue is small with the increase of the use times of the HCMs, and the removal rate is still more than 80% after the HCMs are used for 5 times in a circulating manner, which indicates that the catalytic material with the core-shell structure has a good removal effect on methylene blue, is stable in chemical properties, and has a good application value.
Example 3
In the embodiment, wheat straws are used as raw materials to prepare the carbon sphere template and the core-shell structure catalytic material, and the preparation process is as follows:
firstly, crushing wheat straws in a crusher for 5min, sieving the crushed wheat straws with a 40-mesh sieve, drying the crushed wheat straws for 24h at 105 ℃, then immersing 6g of wheat straw powder in 100mL of 10% sodium lignosulfonate solution by mass fraction, heating the soaked wheat straw powder in a hydrothermal reaction kettle for 18h at 180 ℃, ultrasonically dispersing and filtering the soaked wheat straw powder with a 240-mesh sieve, and obtaining a carbon ball template after centrifugal separation.
Adding 1g zinc sulfate, 2g magnesium chloride and 0.5g triethanolamine into 40mL propylene glycol ether, heating at 60 deg.C for 1.5 hr, stirring for dissolving, standing for 24 hr, and aging to obtain Mg2+/Zn2+And (3) sol.
15mL of tetrabutyl titanate, 2.8mL of triethanolamine and 5mL of distilled water are respectively and slowly added into 60mL of absolute ethyl alcohol, heated at 70 ℃ for 5h and then kept stand for 48h for aging, thus obtaining the titanium dioxide sol.
Adding 1g of carbon sphere template and 8mL of sodium p-styrene sulfonate into 100mL of distilled water for ultrasonic dispersion, stirring for 6h at 70 ℃, and slowly dropwise adding 15mL of Mg2+/Zn2+Stirring the sol at 70 ℃ for 10h, performing centrifugal separation, performing anaerobic calcination at 400 ℃ for 2h (the heating rate is 1.5 ℃/min), adding the sol into the titanium dioxide sol, performing dispersion stirring for 2h, performing centrifugal separation, performing anaerobic calcination at 450 ℃ for 3h, and adding 100mL of 0.2g/L AgNO3In the solution, centrifuging after 2h at 80 ℃, calcining for 4h in air at 550 ℃ to remove the carbon sphere template, and obtaining the catalysis-photocatalysis microspheres (HCMs) with the core-shell structure.
The effect of 0.04g of HCMs on the removal of 100mL of 25mg/L Methylene Blue (MB) and COD and TOC from water under 150W xenon lamp irradiation is shown in FIG. 4. The removal rate of methylene blue (100mL,25mg/L) by 0.04g of HCMs after 240min of illumination reached 80.9%.
As can be seen from fig. 4, the dye concentration and chemical oxygen demand in the water decreased rapidly with increasing catalytic time, indicating that the organic dye in the water was oxidized and, in addition, there was a slight decrease in the total organic carbon content, indicating that some of the organic matter was even completely decomposed into water and carbon dioxide. To further study the degradation process, the photo-catalyzed methylene blue dye solution was analyzed by liquid chromatography-mass spectrometry (LC-MS), and the analysis results are shown in fig. 5.
As can be seen from FIG. 5, the methylene blue Peak (Peak 1) intensity decreased after 30min of adsorption, while a new Peak (Peak 2) was generated after light irradiation (L-10 and L-30), and Peak 2 represents the Peak according to the mass spectrum results
Figure BDA0002552606580000071
This shows that the methylene blue molecules are decomposed into new small molecules after photocatalysis, which shows that the core-shell structure catalytic materials (HCMs) have good degradation effect on dye molecules.
Example 4
Referring to example 1, the carbon source was replaced with corn stover, orange peel and bagasse, respectively, and the other conditions were unchanged to prepare the corresponding catalytic materials.
Referring to the catalytic performance of the resulting material as measured by the method of example 1, the results of the removal of methylene blue (100mL,25mg/L) by 0.04g of HCMs after 240min of light exposure are shown in Table 1.
TABLE 1 results of catalytic Performance of catalytic materials obtained with different carbon sources
Carbon source Removal rate
Corn stalk 75.2％
Orange peel 82.4％
Bagasse 80.6％
Example 5
Referring to example 1, Mg was prepared by replacing zinc acetate with zinc sulfate and magnesium chloride with magnesium sulfate2+/Zn2+Sol and other conditions are unchanged to prepare the corresponding catalytic material.
Referring to the catalytic performance of the resulting material as measured by the method of example 1, the removal of methylene blue (100mL,25mg/L) from 0.04g of HCMs after 240min of light exposure was 85.4%.
Example 6 exploration for Mg2+/Zn2+Influence of mass ratio of Mg source and Zn source in sol on catalytic performance of obtained composite material
Referring to example 1, Mg prepared2+/Zn2+Replacing the mass ratio of the Mg source to the Zn source in the sol by 1:5, 1:2, 1:1, 2:1 and 1:0 respectively, and preparing the corresponding catalytic material under the same other conditions.
Referring to the catalytic performance of the resulting material measured by the method of example 1, the removal of methylene blue (100mL,25mg/L) by 0.04g of HCMs after 240min of light exposure is shown in Table 2:
TABLE 2 results of catalytic performances of composites obtained with different Mg and Zn source mass ratios
Mg/Zn mass ratio Removal rate
1:5 66.7％
1:2 68.2％
1:1 70.4％
2:1 74.5％
1:0 47.8％
As can be seen, it indicates the mass ratio of Mg source and Zn source to prepare Mg2+/Zn2+The sol system has obvious influence on the dye removing effect of the obtained catalytic material.
Comparative example 1
Firstly, cutting irregular bamboos into fragments with the size of 1-1.5cm multiplied by 1-2.5cm, cleaning in water, drying, adding 3.2g of bamboo chips and 0.8g of phloroglucinol into a beaker filled with 120mL of distilled water, heating at 80 ℃ for 2h, transferring to a hydrothermal reaction kettle, heating at 220 ℃ for 24h (the heating rate is 1 ℃/min), screening the reaction product through a screen with 240 meshes, filtering out large bamboo residues, centrifugally separating to obtain carbon sphere template sediments, cleaning for three times by using ethanol and distilled water, and drying to obtain the carbon sphere template.
Adding 0.5g of zinc acetate, 2.5g of magnesium chloride and 0.8g of monoethanolamine into 20mL of ethylene glycol monomethyl ether, heating at 60 ℃ for 2h, stirring for dissolving, standing for 48h, and aging to obtain Mg2+/Zn2+And (3) sol. Adding 0.5g of carbon sphere template and 8mL of sodium p-styrene sulfonate into 100mL of distilled water for ultrasonic dispersion, stirring for 12h at 60 ℃, and slowly dropwise adding 9mL of Mg2+/Zn2+And (3) continuously stirring the sol at 60 ℃ for 12h, centrifugally separating, and calcining at 500 ℃ in air for 4h to remove the carbon sphere template to obtain the non-photocatalytic material.
Respectively and slowly adding 10mL of tetrabutyl titanate, 5mL of triethanolamine and 1mL of distilled water into 50mL of absolute ethyl alcohol, heating at 80 ℃ for 2h, standing for 48h, and aging to obtain the titanium dioxide sol. Adding 0.5g of carbon sphere template and 8mL of sodium p-styrene sulfonate into 100mL of distilled water for ultrasonic dispersion, then dropwise adding titanium dioxide sol, dispersing and stirring for 4h, then centrifugally separating, carrying out anaerobic calcination at 500 ℃ for 2h, and then adding 100mL of 0.1g/L AgNO3In the solution, after 2 hours at 80 ℃, the solution is centrifugally separated, and the carbon sphere template is removed by calcining the solution in the air at 500 ℃ for 4 hours, thus obtaining the photocatalytic material.
And (3) mixing the obtained non-photocatalytic material with photocatalytic material powder in a mass ratio of 1:1, mixing to obtain the catalytic-photocatalytic mixed microsphere.
Referring to the catalytic performance of the material obtained as measured by the method in example 1, the removal rate of methylene blue (100mL,25mg/L) by 0.04g of mixture after 240min of illumination was 40.7%. Therefore, compared with a simple catalysis-photocatalysis physical composite material, the catalysis-photocatalysis material with the core-shell structure has more excellent effect of catalyzing and degrading organic pollutants.
Comparative example 2 comparison of catalytic degradation of different catalytic materials
With reference to the method for testing the catalytic properties of the material in example 1, HCMs were respectively exchanged for anatase TiO2Rutile TiO2And P25-Ag.
The removal rate of methylene blue (100mL,25mg/L) by 0.04g of catalytic material after 240min of illumination is respectively as follows: 60.3%, 40.5% and 27.6%, indicating that the HCMs prepared in example 1 are superior to the commonly available commercial catalytic materials in dye removal.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A method of preparing a catalytic-photocatalytic composite material for the catalytic degradation of organic pollutants, characterized in that it comprises the steps of:
(1) carbonizing a carbon source to prepare carbon spheres;
(2) mixing the carbon spheres obtained in the step (1) with an anion modifier to carry out anion modification; then Mg is added2+/Zn2+Carrying out reaction on the sol; after the reaction is finished, carrying out solid-liquid separation, collecting precipitate and calcining to prepare a precursor material;
(3) mixing the precursor material obtained in the step (2) with TiO2Mixing sol for reaction, and after the reaction is finished, carrying out solid-liquid separation, collecting precipitate and calcining; adding the calcined product into a silver ion solution for hydrothermal reaction, carrying out solid-liquid separation after the reaction is finished, collecting the precipitate, and drying to obtain the catalytic-photocatalytic composite material.
2. The method of claim 1, wherein Mg in step (2)2+/Zn2+The preparation method of the sol comprises the following steps: dispersing a magnesium source and a zinc source in an organic solvent, then reacting at 50-80 ℃, standing and aging after the reaction is finished to obtain Mg2+/Zn2+And (3) sol.
3. The method of claim 2, wherein the Mg is present2+/Zn2+The mass ratio of the magnesium source to the zinc source in the sol is 1: 1-10: 1.
4. a process according to claim 2 or 3, characterized in that the Mg2+/Zn2+The mass fraction of the magnesium source and the zinc source in the sol is 5 to 30 percent; the mass fraction of the organic solvent is 70-95%.
5. The method according to any one of claims 2 to 4, wherein the magnesium source is one or more of magnesium chloride, magnesium nitrate, magnesium acetate; the zinc source is one or more of zinc nitrate, zinc acetate and zinc chloride; the organic solvent is one or more of ethylene glycol monomethyl ether, triethanolamine, diethanolamine, monoethanolamine and ethanol.
6. The method as claimed in any one of claims 1 to 5, wherein the carbonization in step (1) is carried out at a temperature of 180 ℃ and 260 ℃ for a period of 12h to 36 h.
7. The method of any one of claims 1-6, wherein the negative ion modifier in step (2) is one or more of sodium poly (p-styrene sulfonate), sodium p-styrene sulfonate, sodium dodecyl sulfate, sodium ethylene diamine tetracetate, and alpha-sulfo-monocarboxylic ester.
8. The method according to any one of claims 1 to 7, wherein the mass ratio of the carbon spheres to the negative ion modifier in the step (2) is (1 to 4): (0.5-2).
9. A catalytic-photocatalytic composite material for catalytic degradation of organic pollutants prepared by the method of any one of claims 1 to 8.
10. Use of the catalytic-photocatalytic composite material according to claim 9 for environmental management.
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CN112337456A (en) * 2020-10-12 2021-02-09 重庆三峡学院 Preparation method of ZnO/MgO composite piezoelectric catalyst with core-shell structure
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CN112915989A (en) * 2021-01-27 2021-06-08 中国建筑材料科学研究总院有限公司 SiO (silicon dioxide)2@TiO2Nano composite material and preparation method and application thereof
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