CN110665534A - Ce/N codoped TiO2Preparation method and application of acid-leaching diatomite composite sphere - Google Patents
Ce/N codoped TiO2Preparation method and application of acid-leaching diatomite composite sphere Download PDFInfo
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 21
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
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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
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- 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
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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 relates to Ce/N codoped TiO2Preparation method and application of acid-leaching diatomite composite sphere. Mechanically stirring acid-leached diatomite, anhydrous ethanol and glacial acetic acid, and then sequentially dropwise adding tetrabutyl titanate and glycol amine to form a suspension; then, the mixed solution of cerous nitrate, urea, absolute ethyl alcohol and deionized water is dripped, the pH value is adjusted to 3, and TiO is prepared by a sol-gel method2A diatomaceous earth powder; mixing acid-leaching diatomite with deionized water, adding an organic binder and a fluxing agent, and preparing wet mud balls in a pelletizer; mixing the wet mud ball with TiO2Putting the diatomite powder into a high-speed rotating steel barrel together, rotating at high speed, drying the obtained product, and calcining in a muffle furnace to obtain the Ce/N co-doped TiO2/acid-leaching diatomite composite sphere CNTD-G. The CNTD-G prepared by the invention is simple to operate when degrading organic dyes and polycyclic substances, and the photocatalytic material does not introduce secondary pollution and is convenient to recycle.
Description
Technical Field
The invention relates to the field of photocatalysts and application thereof, in particular to Ce/N co-doped TiO2Preparation of acid-leaching diatomite composite spheres and application of the acid-leaching diatomite composite spheres in effectively utilizing visible light to degrade organic dyes and polycyclic substances.
Background
With the intensive research and development and mass production of polycyclic compounds, particularly antibiotic drugs, in the medical field, a tetracycline antibiotic, one of broad-spectrum antibiotics, is widely applied to agricultural production projects such as planting, livestock breeding and the like, and one of the results is that the content of residual antibiotics in natural environment is continuously increased. Meanwhile, the production process of antibiotics is accompanied by the generation of a large amount of wastewater, which often contains antibiotic components, and if the antibiotics are directly discharged into the natural environment without treatment, the antibiotics can cause serious pollution to the environment.
Disclosure of Invention
The invention aims to provide a Ce/N codoped TiO2Acid-leached diatomite composite sphere (Ce/N co-dopedTiO)2CNTD-G) prepared by the invention is simple to operate when organic dyes and polycyclic substances are degraded, and the photocatalytic material does not introduce secondary pollution and is convenient to recycle.
The technical scheme adopted by the invention is as follows: Ce/N codoped TiO2The preparation method of the acid-leaching diatomite composite sphere comprises the following steps:
1) mixing acid-leached diatomite with anhydrous ethanol and glacial acetic acid, mechanically stirring for 30-50min, sequentially dropwise adding tetra-n-butyl titanate and glycol amine, and continuously stirring to form a suspension; preparing mixed solution of cerium nitrate, urea, absolute ethyl alcohol and deionized water; dripping the obtained mixed solution into the suspension under stirring, adjusting pH to 3, continuously stirring for reaction for 5-7 hr, standing for at least 72 hr to obtain gel productDrying the product in an oven at 80 ℃, and grinding to obtain TiO2A diatomaceous earth powder;
2) mixing acid-leaching diatomite with deionized water, adding an organic binder and a fluxing agent, uniformly mixing to prepare a mud mass, and preparing a wet mud ball with the diameter of 1-3mm in a pelletizer;
3) mixing the wet mud ball obtained in the step 2) and the TiO obtained in the step 1)2Putting the diatomite powder into a high-speed rotating steel barrel, rotating at 1440r/min for 20-30min to coat a layer of TiO on the surface of the mud ball2Covering with diatomite powder, drying at 80 deg.C, calcining in muffle furnace for 2 hr to obtain Ce/N codoped TiO2Acid-leached diatomite composite spheres.
Further, the preparation method of the acid-leaching diatomite comprises the following steps: weighing a proper amount of diatomite and dilute sulfuric acid solution, uniformly mixing, keeping a mechanical stirring state at normal temperature for 24 hours, washing the mixture to be neutral by using deionized water, and drying the mixture at 80 ℃ to obtain the acid-leached diatomite.
Further, the concentration of the dilute sulfuric acid solution is 15 wt%, and the solid-to-liquid ratio of the diatomite raw soil to the dilute sulfuric acid solution is 1.0g:2.5 mL.
Further, N: Ti ═ (1-4):1 in a molar ratio. Further, N: Ti is 2:1 in terms of molar ratio.
Further, 0.02-0.20g of cerium nitrate was added per 8.0mL of tetra-n-butyl titanate. Further, 0.05g of cerium nitrate was added per 8.0mL of tetra-n-butyl titanate.
Further, the organic binder is one or a combination of more than two of hydroxypropyl methylcellulose, dextrin, sucrose and gelatin. Still further, the organic binder is a combination of hydroxypropyl methylcellulose and dextrin. Further, the organic binder is a combination of hydroxypropyl methyl cellulose and dextrin according to the mass ratio of 1 (0.5-1.5). Further, the organic binder is a combination of hydroxypropyl methylcellulose and dextrin in a mass ratio of 2: 3.
Further, the fluxing agent is sodium carbonate.
Further, in the step 3), the temperature of the calcination in the muffle furnace is 400-600 ℃. Further, in step 3), the temperature of calcination in a muffle furnace was 500 ℃.
Ce/N codoped TiO prepared by the method2The application of the acid-leaching diatomite composite sphere in degrading organic dyes or polycyclic substances under visible light.
Further, the organic dye is Rhodamine B (Rhodamine B, RhB for short).
Further, the polycyclic species is tetracycline hydrochloride.
The invention has the beneficial effects that:
in recent years, the synergistic effect of co-doping rare earth elements and non-metal elements on TiO2The improvement of the photocatalytic activity is concerned by the majority of researchers. Co-doping certain rare earth elements with non-metallic elements can be used to dope TiO2The photoresponse range of (2) is extended to the visible region and the visible activity thereof is improved. TiO 22The photocatalytic performance of (a) is mainly influenced by three factors: adsorption performance, photoresponse range and separation efficiency of photo-generated electron-hole pairs. Adding N-TiO2The nano particles are loaded on the surface of the diatomite, so that the adsorption performance of the composite material can be improved to a certain extent, and the photocatalysis performance of the composite material can be greatly promoted by the target enrichment effect of enriching target pollutants around the photocatalyst through the adsorption effect. To promote TiO2The invention relates to a visible light utilization rate of a diatomite composite sphere and the separation efficiency of a photoproduction electron hole pair, which are modified by doping rare earth element Ce and a non-metal element N, adopts urea as an N source, and adopts cerium nitrate (Ce (NO)3)3) Is a Ce source and prepares Ce/N codoped TiO2Acid-leached diatomite composite sphere (Ce/N co-doped TiO)2/diatomite grain, abbreviated as CNTD-G), improves TiO2The visible light utilization rate and the separation efficiency of the photoproduction electron hole pair of the diatomite composite sphere promote the development and the application of the photocatalysis technology. The CNTD-G prepared by the invention is simple to operate when degrading organic dyes and polycyclic substances, and the photocatalytic material does not introduce secondary pollution and is convenient to recycle.
Drawings
FIG. 1 is a mechanism diagram of a co-doped spherical CNTD-G photocatalysis process.
FIG. 2 is an XRD spectrum of different co-doped composite spheres (CNTD-G) and N-doped, undoped spheres (A represents anatase phase, R represents rutile phase, and Q represents quartz impurity).
FIG. 3 is an adsorption desorption isotherm of co-doped composite spheres (0.05-CNTD-G) and N-doped, undoped spheres (TD-G).
FIG. 4 is an SEM image of a co-doped composite sphere (0.05-CNTD-G).
FIG. 5 is a TEM image of a co-doped composite sphere (0.05-CNTD-G).
FIG. 6a is an XPS spectrum Ti 2p spectrum of co-doped spheres (0.05-CNTD-G) and N-doped spheres.
FIG. 6b is an XPS spectrum O1s spectrum of co-doped spheres (0.05-CNTD-G) and N-doped composite spheres NTD-G.
FIG. 6c is an XPS spectrum Ce 3d spectrum of co-doped spheres (0.05-CNTD-G).
FIG. 6d is an XPS spectrum N1s spectrum of co-doped spheres (0.05-CNTD-G).
FIG. 7 is the DRS spectrum of co-doped spheres 0.05-CNTD-G, NTD-G and TD-G.
FIG. 8 is a conversion of the Kubelka-Munk equation for co-doped spheres 0.05-CNTD-G, NTD-G and TD-G.
Fig. 9 shows the degradation rate of photodegraded RhB of co-doped spheres, single-doped and composite powders.
FIG. 10 is the recycling performance of co-doped composite spheres (0.05-CNTD-G) for photo-degradation of RhB.
FIG. 11 is a PL spectrum of N-doped (NTD-G) and co-doped spheres (CNTD-G).
FIG. 12 shows the results of TOC analysis of visible degradation experiments of TC by co-doped spherical CNTD-G.
FIG. 13 is the effect of the input amount of co-doped composite sphere 0.05-CNTD-G on TC degradation efficiency.
FIG. 14 is the results of a cycle test of co-doped spheres 0.05-CNTD-G against light degradation of TC.
Detailed Description
EXAMPLE 1Ce/N codoped TiO2/acid-dipped diatomite composite sphere (CNTD-G for short)
Preparation of CNTD-G with different Ce doping amounts
1) The preparation method of the acid-leaching diatomite comprises the following steps: weighing diatomite, adding a dilute sulfuric acid solution with the concentration of 15 wt% according to the solid-to-liquid ratio of 1.0g to 2.5mL, uniformly mixing the diatomite and the dilute sulfuric acid, and keeping the mechanical stirring state at normal temperature for 24 hours. And then washing the diatomite to be neutral by using deionized water, and drying the diatomite at 80 ℃ to obtain the acid-leached diatomite treated by dilute sulfuric acid.
2) 5.0g of acid-leached diatomite is mixed with 70.0mL of absolute ethyl alcohol and 5.0mL of glacial acetic acid, mechanically stirred for 30min, then sequentially added with 8.0mL of tetra-n-butyl titanate and 1.0mL of glycol amine dropwise, and stirred continuously to form a suspension.
And mixing 2.8g of urea, 24.0mL of anhydrous ethanol and 8.0mL of deionized water, and then adding 0.02g of cerium nitrate, 0.05g of cerium nitrate, 0.10g of cerium nitrate and 0.20g of cerium nitrate respectively to prepare mixed solutions with different Ce doping amounts.
And dropwise adding the obtained mixed solution with different Ce doping amounts into the obtained suspension under the stirring state, and adjusting the pH value of the obtained reaction system to 3 by using nitric acid. Continuously stirring the reaction system for reaction for at least 5 hours, standing for at least 72 hours to obtain a product in a gel state, putting the product into an oven, drying at 80 ℃, and grinding to obtain TiO with different Ce doping amounts2Diatomite powder.
3) Another 10.0g of acid-leached diatomaceous earth was mixed with 11.0mL of deionized water, and 0.5g of organic binder (the organic binder is a mixture of hydroxypropyl methylcellulose and dextrin in a mass ratio of 2: 3) was added, along with 0.1g of sodium carbonate flux. Evenly mixing to prepare a mud ball, and preparing the mud ball into a wet mud ball with the diameter of about 2mm by a multifunctional pelletizer.
4) Respectively mixing the wet mud ball obtained in the step 3) with the TiO with different Ce doping amounts obtained in the step 2)2Putting the diatomite powder into a high-speed rotating steel barrel (the rotating speed is 1440r/min), rotating for 20min, and coating a layer of TiO on the surface of the mud ball2The samples thus obtained were introduced into an oven, dried at 80 ℃ and then calcined in a muffle furnace at 500 ℃ for 2 hours. Finally obtaining CNTD-G with different Ce doping amounts which are respectively marked as 0.02-CNTD-G and 0.05-CNTD-G, 0.1-CNTD-G and 0.2-CNTD-G.
(II) comparative example
1. Comparative example 1: the preparation method of the N-doped composite sphere (NTD-G for short) comprises the following steps:
1) 5.0g of acid-leached diatomite is mixed with 70.0mL of absolute ethyl alcohol and 5.0mL of glacial acetic acid, mechanically stirred for 30min, then sequentially added with 8.0mL of tetra-n-butyl titanate and 1.0mL of glycol amine dropwise, and stirred continuously to form a suspension.
And mixing 2.8g of urea, 24.0mL of absolute ethyl alcohol and 8.0mL of deionized water to prepare a mixed solution.
The obtained mixed solution was added dropwise to the above-obtained suspension while stirring, and the pH of the obtained reaction system was adjusted to 3 with nitric acid. Continuously stirring the reaction system for reaction for at least 5 hours, standing for at least 72 hours to obtain a product in a gel state, putting the product into an oven, drying at 80 ℃, and grinding to obtain TiO2Diatomite powder.
2) Another 10.0g of acid-leached diatomaceous earth was mixed with 11.0mL of deionized water, and 0.5g of organic binder (the organic binder is a mixture of hydroxypropyl methylcellulose and dextrin in a mass ratio of 2: 3) was added, along with 0.1g of sodium carbonate flux. Evenly mixing to prepare a mud ball, and preparing the mud ball into a wet mud ball with the diameter of about 2mm by a multifunctional pelletizer.
3) Respectively mixing the wet mud ball obtained in the step 2) and the TiO obtained in the step 1)2Putting the diatomite powder into a high-speed rotating steel barrel (the rotating speed is 1440r/min), rotating for 20min, and coating a layer of TiO on the surface of the mud ball2The samples thus obtained were introduced into an oven, dried at 80 ℃ and then calcined in a muffle furnace at 500 ℃ for 2 hours. Finally obtaining the N-doped composite sphere which is marked as NTD-G.
2. Comparative example 2: the preparation method of the undoped sphere (TD-G for short) comprises the following steps:
1) 5.0g of acid-leached diatomite is mixed with 70.0mL of absolute ethyl alcohol and 5.0mL of glacial acetic acid, mechanically stirred for 30min, then sequentially added with 8.0mL of tetra-n-butyl titanate and 1.0mL of glycol amine dropwise, and stirred continuously to form a suspension.
And preparing a mixed solution by taking 24.0mL of absolute ethyl alcohol and 8.0mL of deionized water.
The obtained mixed solution was added dropwise to the above-obtained suspension while stirring, and the pH of the obtained reaction system was adjusted to 3 with nitric acid. Continuously stirring the reaction system for reaction for at least 5 hours, standing for at least 72 hours to obtain a product in a gel state, putting the product into an oven, drying at 80 ℃, and grinding to obtain TiO2Diatomite powder.
2) Another 10.0g of acid-leached diatomaceous earth was mixed with 11.0mL of deionized water, and 0.5g of organic binder (the organic binder is a mixture of hydroxypropyl methylcellulose and dextrin in a mass ratio of 2: 3) was added, along with 0.1g of sodium carbonate flux. Mixing uniformly to obtain a mud ball, and making into wet mud ball with diameter of 2mm by a multifunctional pelletizer.
3) Respectively mixing the wet mud ball obtained in the step 2) and the TiO obtained in the step 1)2Putting the diatomite powder into a high-speed rotating steel barrel (the rotating speed is 1440r/min), rotating for 20min, and coating a layer of TiO on the surface of the mud ball2The samples thus obtained were introduced into an oven, dried at 80 ℃ and then calcined in a muffle furnace at 500 ℃ for 2 hours. Finally obtaining undoped spheres which are marked as TD-G.
(III) detection
1. Phase analysis of composite spheres
The grain size of the semiconductor photocatalyst is closely related to the photocatalytic activity thereof, and the semiconductor photocatalyst is used for the Ce/N co-doped TiO2XRD analysis of the crystal phase structure of the acid-leached diatomite composite spheres is shown in figure 2.
FIG. 2 is an XRD spectrum of different co-doped composite spheres (CNTD-G) and N-doped, undoped spheres (A represents anatase phase, R represents rutile phase, and Q represents quartz impurity). As can be seen from FIG. 2, compared with the N-doped composite sphere NTD-G and the undoped composite sphere TD-G, the Ce/N-codoped composite sphere prepared by the invention has a wider diffraction peak shape and further weakened peak intensity. The suppression effect is gradually remarkable along with the increasing of the doping amount of Ce. The TiO of the composite sphere is calculated by a Debye-Scherrer formula2Grain size, results are shown in table 1.
TABLE 1 grain sizes of CNTD-G, NTD-G and TD-G
2. Analysis of specific surface area and pore structure of composite spheres
FIG. 3 is an adsorption desorption isotherm of different co-doped composite spheres (CNTD-G) and N-doped, undoped spheres. As can be seen from FIG. 3, the specific surface area of the Ce/N co-doped composite sphere 0.05-CNTD-G prepared by the invention is 44.9m2The specific surface area of the N-doped composite sphere NTD-G is 42.3m2The specific surface area of the Ce/N co-doped composite sphere prepared by the invention is larger than that of the N-doped composite sphere NTD-G, and thus, the Ce/N co-doped composite sphere is doped with TiO2Grain growth has a dual inhibitory effect (first, grain growth is inhibited, and second, a smaller grain size results in a relatively larger specific surface area). The non-balling doped composite powder has a higher specific surface area than the corresponding composite powder, which indicates that the balling process causes slight loss of the specific surface area.
3. Micro-topography analysis
FIG. 4 is an SEM image of the Ce/N co-doped composite sphere 0.05-CNTD-G prepared by the invention, and FIG. 5 is a TEM image of the Ce/N co-doped composite sphere 0.05-CNTD-G prepared by the invention. As can be seen from FIGS. 4 and 5, similar to the single-doped composite sphere, the surface of the co-doped composite sphere still presents the typical porous disc-shaped micro-morphology of diatomite, and the surface of the sphere is loaded with a layer of TiO2The nanoparticles are relatively coarse. From the TEM image, TiO was further observed2The particles are well dispersed on the surface of the diatomite shell.
4. Chemical morphological analysis of constituent elements
The chemical forms of bonding, valence state and the like of the constituent elements of the Ce/N co-doped composite sphere can be measured by an XPS method.
XPS spectrograms of the Ce/N co-doped composite sphere 0.05-CNTD-G and the N doped composite sphere NTD-G prepared by the invention are shown in figures 6a-6 d. FIG. 6a is a Ti 2p spectrum of two samples, 0.05-CNTD-G and NTD-G, and it can be seen that the introduction of N doping does not have a significant effect on the chemical structure of Ti. FIG. 6b shows both 0.05-CNTD-G and NTD-GThe O1s spectrum of the seed sample. Three peaks were obtained by peak separation software processing. FIG. 6c is the Ce 3d spectrum of co-doped composite sphere 0.05-CNTD-G. Ce is still present in TiO in the form of oxides2Lattice surface and interstitial sites thereof, and with TiO2Ce-O-Ti bonds are formed between the interfaces. FIG. 6d is the spectrum of N1s for co-doped composite sphere 0.05-CNTD-G. The spectrum peak is located at 399.8eV, and belongs to the characteristic peak of gap type N doping.
5. Absorption of visible light by composite spheres
FIG. 7 is a DRS spectrum of co-doped composite sphere 0.05-CNTD-G, N doped composite sphere NTD-G and undoped composite sphere TD-G. As can be seen from FIG. 7, the DRS spectrum of the N-doped composite sphere shows that the absorption edge of the N-doped composite sphere is red-shifted, and the DRS spectrum of the co-doped composite sphere 0.05-CNTD-G shows that the red-shift change of the absorption edge of the N-doped composite sphere is more obvious and the expansion degree of the absorption edge to the visible light region is larger. According to the Kubelka-Munk equation, the forbidden bandwidth of the N-doped composite sphere is estimated to be about 3.14eV (as shown in FIG. 8), which is consistent with the absorption edge at 410-420 nm. The forbidden band width value of the co-doped composite sphere 0.05-CNTD-G is about 2.76eV (as shown in FIG. 8), which is consistent with the absorption edge position at 490-500 nm. Therefore, the Ce/N codoping can effectively promote TiO2The visible light response capability of.
EXAMPLE 2 Ce/N codoped TiO2Application of acid-leached diatomite composite sphere in degradation of organic dye under visible light
Rhodamine B is used as a target degradation product, the visible light catalytic activity of the co-doped composite sphere is examined, and the photodegradation process is shown in figure 1.
The method comprises the following steps: adding 1.0G of CNTD-G with different Ce doping amounts prepared in the embodiment 1 into 200.0mL of 0.01G/L rhodamine B solution respectively, performing a dark adsorption process for 30min to enable the whole system to reach dynamic adsorption balance, and then placing the system under visible light (xenon lamp) with the power of 150W for photocatalytic degradation for 180 min.
1. Study on visible light catalytic activity
Rhodamine B is used as a target degradation product, the visible light catalytic activity of the co-doped composite sphere is examined, and the N-doped composite sphere, the ungelled 0.05-CNTD and TD-G are used as reference samples. The results are shown in FIG. 9.
As can be seen from fig. 9, the order of photodegradation efficiency of the co-doped composite spheres is: 0.05-CNTD-G>0.1-CNTD-G>0.02-CNTD-G>0.2-CNTD-G>NTD-G. This indicates that the effect of Ce/N co-doping exceeds that of a single doping element. Wherein the Ce doping has an optimal doping amount, the invention is preferably that the Ce/N codoped TiO is doped with the Ce2The acid-leaching diatomite composite sphere is 0.05-CNTD-G.
2. Research on recycling performance of photodegraded rhodamine B
Among the co-doped composite spheres, 0.05-CNTD-G is the best photocatalysis sphere, and 0.05-CNTD-G is taken as an example in a cycle experiment. After the previous group of experiments for photodegradation of RhB is finished, the catalyst sample 0.05-CNTD-G is separated from the RhB solution by a filtering method, and then is washed by deionized water. And then, putting the mixture into an oven for drying, and sending the mixture into the next group of photodegradation RhB experiments (each group of experiments lasts for 180 min). The cyclic degradation results are shown in FIG. 10. As can be seen from fig. 10, after the initial degradation experiment was completed, the degradation rate of RhB was reduced to 82.3% through 5 times of repeated experiments, while the degradation rate of the initial degradation experiment was 87.3%. In the repeated use experiment process, the Ce/N codoped composite sphere keeps stable RhB photodegradation efficiency, and the composite sphere has good photocatalytic stability.
3. Discussion of photodegradation mechanism
PL spectra of N-doped composite spheres and co-doped composite spheres of different Ce doping amounts, as shown in fig. 11. The spectrum of the co-doped composite sphere slightly shifts to a low wavelength region relative to the N-doped composite sphere. The PL spectral intensity is: NTD-G >0.2-CNTD-G >0.02-CNTD-G >0.1-CNTD-G > 0.05-CNTD-G. In the co-doped composite sphere, the PL spectrum intensity of 0.05-CNTD-G is relatively lowest, which indicates that the sample has relatively highest visible light catalytic activity.
EXAMPLE 3 Ce/N codoped TiO2Application of acid-leached diatomite composite sphere in degradation of polycyclic substances under visible light
The visible light catalytic activity of the co-doped composite sphere is examined by taking tetracycline hydrochloride (TC) as a target degradation product.
The method comprises the following steps: the CNTD-G prepared in example 1 was added to a TC aqueous solution with an initial concentration of 20.0mg/L and a pH of 6 at an amount of 5.0G/L for 30min to achieve a dynamic adsorption equilibrium, and then placed under visible light (xenon lamp) at a power of 150W for photocatalytic degradation for 240 min.
1. Degradation of TC by codoped composite spherical CNTD-G with different Ce doping amounts
FIG. 12 shows the results of TOC analysis of visible degradation experiments of TC by co-doped spherical CNTD-G. As can be seen from FIG. 12, 0.05-CNTD-G showed the highest photocatalytic degradation efficiency among the various co-doped composite spheres.
2. Influence of different catalyst input amounts on degradation efficiency
The ratio of the input amount of 0.05-CNTD-G to the volume of the TC solution is respectively set as: 2.5g/L, 5.0g/L, 7.5g/L or 10.0 g/L. The initial pH of the aqueous TC solution was 6.
FIG. 13 is the effect of the input amount of co-doped composite sphere 0.05-CNTD-G on TC degradation efficiency. As can be seen from fig. 13, the optimum input amount of the co-doped composite sphere is 5g/L, and the co-doped composite sphere exceeding the input amount adversely affects the photodegradation efficiency thereof.
3. Evaluation of Cyclic degradation Properties of photodegradable Tetracycline
The reusability of 0.05-CNTD-G composite samples with optimal photocatalytic activity during the degradation of TC by light was examined. After the previous set of experiments of photodegradation TC is finished, the composite powder sample is separated from the liquid phase by a method of filtering or applying a magnetic field, and then is washed by deionized water. And then, putting the mixture into an oven for drying, and sending the mixture into the next group of photodegradation TC experiments (each group of experiments lasts for 240 min). The degradation results are shown in FIG. 14. After the initial degradation experiment, the degradation rate of 0.05-CNTD-G is reduced to 96.1 percent through 5 times of repeated experiments, and the degradation rate of the initial degradation experiment is 97.0 percent. In the repeated use experiment process, the co-doped composite sphere still keeps stable TC photodegradation efficiency, and the co-doped composite sphere still has good stability and recycling performance in the aspect of TC photodegradation.
Claims (10)
- Ce/N codoped TiO 12The preparation method of the acid-leaching diatomite composite sphere is characterized by comprising the following steps: the method comprises the following steps:1) mixing acid-leached diatomite with anhydrous ethanol and glacial acetic acid, mechanically stirring for 30-50min, sequentially dropwise adding tetra-n-butyl titanate and glycol amine, and continuously stirring to form a suspension; preparing mixed solution of cerium nitrate, urea, absolute ethyl alcohol and deionized water; dropwise adding the obtained mixed solution into the suspension under stirring, adjusting pH to 3, continuously stirring for reaction for 5-7 hr, standing for at least 72 hr to obtain gel product, oven drying at 80 deg.C, and grinding to obtain TiO2A diatomaceous earth powder;2) mixing acid-leaching diatomite with deionized water, adding an organic binder and a fluxing agent, uniformly mixing to prepare a mud mass, and preparing a wet mud ball with the diameter of 1-3mm in a pelletizer;3) mixing the wet mud ball obtained in the step 2) and the TiO obtained in the step 1)2Putting the diatomite powder into a high-speed rotating steel barrel, rotating at 1440r/min for 20-30min to coat a layer of TiO on the surface of the mud ball2Covering with diatomite powder, drying at 80 deg.C, calcining in muffle furnace for 2 hr to obtain Ce/N codoped TiO2Acid-leached diatomite composite spheres.
- 2. The method of claim 1, wherein the acid-leached diatomaceous earth is prepared by a method comprising the steps of: weighing a proper amount of diatomite and dilute sulfuric acid solution, uniformly mixing, keeping a mechanical stirring state at normal temperature for 24 hours, washing the mixture to be neutral by using deionized water, and drying the mixture at 80 ℃ to obtain the acid-leached diatomite.
- 3. The preparation method according to claim 2, wherein the concentration of the dilute sulfuric acid solution is 15 wt%, and the solid-to-liquid ratio of the diatomite raw soil to the dilute sulfuric acid solution is 1.0g:2.5 mL.
- 4. The process according to claim 1, wherein N is Ti (1-4) to 1 in a molar ratio.
- 5. The process according to claim 1, wherein 0.02 to 0.20g of cerium nitrate is added per 8.0mL of tetra-n-butyl titanate.
- 6. The method according to claim 1, wherein the organic binder is one or a combination of two or more of hydroxypropylmethylcellulose, dextrin, sucrose and gelatin.
- 7. The method of claim 6, wherein the organic binder is a combination of hydroxypropyl methylcellulose and dextrin.
- 8. The method of claim 1, wherein the flux is sodium carbonate.
- 9. The method according to claim 1, wherein the temperature of calcination in the muffle furnace in step 3) is 400-600 ℃.
- 10. The Ce/N-codoped TiO prepared according to the method of any one of claims 1 to 92The application of the acid-leaching diatomite composite sphere in degrading organic dyes or polycyclic substances under visible light.
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