CN110773145A - Ce-doped TiO based on modified diatomite 2Preparation method and application of floating type photocatalytic composite material - Google Patents
Ce-doped TiO based on modified diatomite 2Preparation method and application of floating type photocatalytic composite material Download PDFInfo
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- 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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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- 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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Abstract
The invention relates to Ce doped TiO based on modified diatomite
2A preparation method and application of a floating type photocatalytic composite material. Mechanically stirring modified diatomite with anhydrous ethanol and glacial acetic acidDripping tetrabutyl titanate and glycol amine to form suspension; then, the mixed solution of cerous nitrate, absolute ethyl alcohol and deionized water is dripped, the pH value is adjusted to 3, and TiO is prepared by a sol-gel method
2A diatomaceous earth powder; mixing modified diatomite with deionized water, adding an organic binder and a fluxing agent, and preparing into wet mud balls by a pelletizer; mixing the wet mud ball with TiO
2Putting 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-doped TiO based on the modified diatomite
2The floating type photocatalysis composite material GCTD. The GCTD provided by the invention is simple to operate when degrading organic dyes and sterilizing, 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-doped TiO based on modified diatomite
2Preparation of the floating type photocatalytic composite material and application of the floating type photocatalytic composite material in degradation of organic dye and sterilization by effectively utilizing visible light.
Background
TiO
2The photocatalytic performance of (a) is mainly influenced by three factors: adsorption performance, photoresponse range and separation efficiency of photo-generated electron-hole pairs. Due to the nanometer TiO
2Has a high band gap energy (3.2eV) and a poor response to visible light, which accounts for 40% of the solar energy radiated to the surface of the earth, so that the nano TiO
2The direct utilization of solar energy for photocatalytic reactions is greatly limited. At present, TiO
2The light source used for photocatalytic oxidation mainly comprises a high-pressure mercury lamp, an ultraviolet germicidal lamp and a black light lamp, and the energy consumption is high, so that the operation cost is high, and the commercialization is difficult to realize. Therefore, to improve TiO
2The utilization rate of sunlight can be directly utilized to carry out photocatalytic reaction, and a technology for optimizing the forbidden bandwidth of the sunlight needs to be developed. Adding TiO into the mixture
2The spectral response range of the TiO is widened to the visible light region, and the TiO with the visible light photocatalytic activity is prepared
2A composite photocatalyst is provided.
In addition, the water environment often contains various microorganisms including various bacteria and fungi, and most of the microorganisms propagate in a large amount under the environmental condition close to normal temperature, so that various problems such as mildew, putrefaction and deterioration of substances such as food and wound infection are caused, and the health of human beings and livestock is seriously affected. Therefore, the research on the environment-friendly material with the sterilization effect has important practical significance.
Disclosure of Invention
To promote TiO
2The invention relates to a visible light utilization rate and separation efficiency of photo-generated electron hole pairs of a diatomite composite sphere
2The diatomite composite sphere is doped and modified by rare earth element Ce. The Ce doped TiO based on modified diatomite provided by the invention
2Floating type photocatalytic composite material (granular Ce doped TiO)
2and/Dt, GCTD) is simple to operate when organic dyes are effectively degraded and sterilized, 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-doped TiO based on modified diatomite
2The preparation method of the floating type photocatalytic composite material comprises the following steps:
1) mixing modified 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 absolute ethyl alcohol, deionized water and cerium nitrate into a mixed solution; 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 TiO
2A diatomaceous earth powder;
2) mixing modified diatomite with deionized water, adding an organic binder and a fluxing agent, uniformly mixing to prepare a mud ball, 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 ball
2Covering with diatomite powder, drying at 80 deg.C, and calcining in muffle furnace for 2 hr to obtain Ce-doped TiO based on modified diatomite
2Floating type photocatalytic composite materialAnd (5) feeding.
Further, the modified diatomite is acid modified diatomite.
Further, the preparation method of the acid modified diatomite comprises the following steps: weighing a proper amount of diatomite raw soil and a diluted 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 modified 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 1g:2.5 mL.
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 methylcellulose and dextrin in a mass ratio of 5: 1.
Further, the fluxing agent is sodium carbonate.
Further, cerium nitrate was added in an amount of 0.02 to 0.20g 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, 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-doped TiO based on modified diatomaceous earth prepared according to the above method
2The floating type photocatalytic composite material is applied to degrading organic dye under visible light.
Further, the organic dye is Rhodamine B (Rhodamine B, RhB for short).
Ce-doped TiO based on modified diatomaceous earth prepared according to the above method
2The floating type photocatalytic composite material is applied to sterilization under visible light.
Further, the bacteria are Escherichia coli, Staphylococcus aureus and Klebsiella pneumoniae.
The invention has the beneficial effects that:
1. to promote TiO
2The 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 adopt cerium nitrate (Ce (NO)
3)
3) Is a Ce source and prepares Ce doped TiO
2The floating type photocatalytic composite material improves TiO
2The 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 GCTD prepared by the invention is simple to operate when degrading organic dye, and the catalyst is pollution-free and convenient to recover.
2. The traditional photocatalyst is in a powder form and forms a suspension system with the polluted water body. Disadvantages of the suspension system are: firstly, the suspension system has a dark color, so that the suspension system has a blocking effect on light transmission, is not beneficial to the surface of the photocatalyst to receive light irradiation, and reduces the photon utilization rate of the photocatalyst. Second, the photocatalyst of deep water level is difficult to achieve high degradation effect. And the floating photocatalyst is positioned on the surface of the water body, so that the defect is not existed. The invention utilizes the combination of the diatomite porous material and the photocatalyst to prepare the floating type photocatalytic material. Due to the porosity of the final composite material, the contact between the air above and catalytic reaction points can be realized, oxygen molecules in the air are used as a natural photoproduction electron capture agent, the recombination of photoproduction electron holes is continuously inhibited, and the photocatalytic degradation effect can be greatly improved. The floating photocatalyst is positioned on the surface of the polluted water body, so that a better recycling purpose can be realized through a simple filtering and recycling process. And the suspension system formed by the powder photocatalytic material and the target polluted water body is difficult to realize effective separation in the later stage of water treatment, and the recycling performance is extremely low.
Drawings
FIG. 1 is a mechanism diagram of the GCTD photocatalytic process.
FIG. 2 is an XRD spectrum of different Ce-doped composite spheres (GCTD) and undoped spheres (TD-G) (A represents anatase phase, R represents rutile phase, and Q represents quartz impurity).
Figure 3 is an adsorption desorption isotherm of different Ce doped composite spheres GCTD and undoped spheres (TD-G).
FIG. 4 is an SEM image of Ce-doped composite spheres (GCTD-2);
wherein, a is 3 μm; b, the proportion is 200 nm.
FIG. 5 is a TEM image of Ce-doped composite spheres (GCTD-2).
FIG. 6a is an XPS spectrum summary of Ce doped spheres (GCTD-2) and undoped spheres (TD-G).
FIG. 6b is an XPS spectrum Ti 2p spectrum of Ce doped spheres (GCTD-2) and undoped spheres (TD-G).
FIG. 6c is an XPS spectrum O1s spectrum of Ce doped spheres (GCTD-2) and undoped spheres (TD-G).
FIG. 6d is an XPS spectrum Ce3d spectrum of Ce doped spheres (GCTD-2).
FIG. 7 is a DRS spectrum of Ce-doped spheres GCTD-2 and undoped spheres (TD-G).
FIG. 8 shows the conversion values of Kubelka-Munk equation for Ce-doped spheres GCTD-2 and undoped spheres (TD-G).
FIG. 9 is a Ce-doped sphere (GCTD), unsphered powder, and unsupported Ce-TiO
2Degradation rate of photodegradation RhB.
FIG. 10 is the recycling performance of Ce-doped composite spheres (GCTD-2) for photodegradation of RhB.
FIG. 11a shows the results of visible light-induced sterilization and dark-condition sterilization of Escherichia coli by Ce-doped composite spheres (GCTD-2).
FIG. 11b shows the results of visible light-induced sterilization and dark-condition sterilization of Staphylococcus aureus by Ce-doped composite spheres (GCTD-2).
FIG. 11c shows the results of visible light-induced sterilization and dark-condition sterilization of Klebsiella pneumoniae by Ce-doped composite spheres (GCTD-2).
FIG. 12a shows the results of the cyclic sterilization of Escherichia coli by Ce-doped composite spheres (GCTD-2).
FIG. 12b shows the results of the cyclic sterilization of Staphylococcus aureus by Ce-doped composite spheres (GCTD-2).
FIG. 12c shows the results of the cyclic sterilization of Klebsiella pneumoniae by Ce-doped composite spheres (GCTD-2).
Detailed Description
Example 1 Ce-doped TiO based modified diatomaceous Earth
2Floating type photocatalysis composite material (GCTD for short)
(I) preparation of GCTD with different Ce doping amounts
1) The preparation method of the acid modified 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 modified diatomite treated by dilute sulfuric acid.
2) 5.0g of acid-modified diatomaceous earth was mixed with 70.0mL of absolute ethanol and 5.0mL of glacial acetic acid, mechanically stirred for 30min, then sequentially added dropwise with 8.0mL of tetra-n-butyl titanate and 1.0mL of glycol amine, and stirred continuously to form a suspension.
And mixing 24.0mL of anhydrous ethanol and 8.0mL of deionized water, and then adding 0.02g, 0.05g, 0.10g 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 amounts
2Diatomite powder.
3) Another 10.0g of acid-modified diatomaceous earth was mixed with 11.0mL of deionized water, and 0.6g of organic binder (the organic binder is a mixture of hydroxypropyl methylcellulose (HPMC) and dextrin (dextrin) in a mass ratio of 5: 1) was added, along with 0.1g of sodium carbonate as a 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 ball
2Coated with diatomaceous earth powder, the resulting sample was placed in an oven, dried at 80 ℃ and then driedCalcination was carried out in a muffle furnace at 500 ℃ for 2 hours. GCTD with different Ce doping amounts is finally obtained and is respectively marked as GCTD-1 (corresponding to the addition of 0.02g of cerium nitrate), GCTD-2 (corresponding to the addition of 0.05g of cerium nitrate), GCTD-3 (corresponding to the addition of 0.10g of cerium nitrate) and GCTD-4 (corresponding to the addition of 0.20g of cerium nitrate).
(II) comparative example
1. Comparative example 1: the preparation method of the undoped sphere (TD-G for short) comprises the following steps:
1) 5.0g of acid-modified diatomaceous earth was mixed with 70.0mL of absolute ethanol and 5.0mL of glacial acetic acid, mechanically stirred for 30min, then sequentially added dropwise with 8.0mL of tetra-n-butyl titanate and 1.0mL of glycol amine, 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 TiO
2Diatomite powder.
2) Another 10.0g of acid-modified diatomaceous earth was mixed with 11.0mL of deionized water, and 0.6g of organic binder (the organic binder is a mixture of hydroxypropyl methylcellulose (HPMC) and dextrin (dextrin) in a mass ratio of 5: 1) was added, along with 0.1g of sodium carbonate as a 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) Wetting mud balls obtained in the step 2) and 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 ball
2The 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
Grain size of semiconductor photocatalysts and photocatalytic activity thereofClosely related, therefore, to Ce doped TiO based modified diatomaceous earth
2The crystal phase structure of the floating type photocatalytic composite material is subjected to XRD analysis.
Figure 2 is an XRD spectrum of different Ce-doped composite spheres (GCTD) and undoped spheres (a represents anatase phase, R represents rutile phase, and Q represents quartz impurity). And with undoped composite sphere TD-G (TiO)
2Dt-grain) as control. As can be seen from fig. 2, the undoped composite sphere has a mixed crystal phase structure, and the XRD spectrogram thereof has two characteristic peaks of rutile phase and anatase phase at the same time, while the spectrogram of the Ce doped composite sphere has only the characteristic peak of anatase phase. Compared with the undoped composite sphere, the Ce-doped composite sphere has a wider peak shape of anatase phase diffraction peak and weaker strength, which means that introduction of Ce doping inhibits TiO
2The crystal grain growth further raises the crystal phase transition temperature. Further, this suppressing effect is enhanced as the Ce doping amount is increased. This suggests that Ce doping can lead to TiO
2The crystallinity is continuously decreased, i.e., the grain size is reduced. Calculating the TiO on the surface of the sample by a Debye-Scherrer formula
2The results are shown in Table 1. As can be seen from Table 1, TiO of Ce-doped composite spheres is compared to undoped composite spheres
2The grain size decreases with increasing Ce doping. The increasing Ce doping amount causes the reduction of Ti-O-Ti bonding energy and brings the reason into consideration that Ce ions are in TiO
2Ce-O-Ti bonds are formed at the interface, and the effect of stabilizing the crystal phase is achieved. Furthermore, the oxide of Ce is localized in TiO
2Lattice surface and interstitial sites, with Ti
4+The ions form an octahedral structure, and the interaction between Ti tetrahedra and Ti octahedral structure becomes the root cause of the suppression effect. In addition, oxides of Ce whether CeO
2Or Ce
2O
3No diffraction peak was observed in the spectrum of the Ce-doped composite sphere, indicating that the amount of Ce doped was very low and therefore could not be detected by XRD.
TABLE 1 grain sizes of GCTD and TD-G
2. Analysis of specific surface area and pore structure of composite spheres
Because the diatomite has a unique porous structure, the surface conditions, such as specific surface area and pore size distribution, of the corresponding Ce-doped composite sphere are closely related to the adsorption performance of the composite sphere, and therefore the photocatalytic activity of the composite sphere is influenced. Therefore, these two factors were examined by the low-temperature nitrogen adsorption-desorption method.
Figure 3 is the adsorption desorption isotherm of different Ce doped composite spheres GCTD and undoped spheres. The specific surface area values of the different Ce-doped composite spheres GCTD and undoped spheres are indicated in fig. 3. The results show that the introduction of the Ce element can increase the specific surface area of the composite sphere. 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
According to the analysis result of XRD, the crystal size of the Ce-doped composite sphere can be estimated. By applying SEM and TEM test methods to the two composite spheres, the information of the microscopic morphology of the two composite spheres can be obtained, so as to verify the conclusion.
FIG. 4 is an SEM image of Ce-doped composite spheres (GCTD-2). FIG. 5 is a TEM image of Ce-doped composite spheres (GCTD-2). As can be seen from FIGS. 4 and 5, the surface of the Ce-doped composite sphere presents the typical porous disc-shaped micro-morphology of diatomite, and the surface is rough due to the fact that a layer of TiO is loaded
2And (3) nanoparticles. Furthermore, the presence of diatomaceous earth debris, debris from the diatomaceous earth cells, surrounding the diatomaceous earth was observed. From the TEM image, TiO can be further observed
2The particles were well dispersed on the surface of the diatomaceous earth shell and had a crystallite size of about 27nm, which is consistent with the results obtained by XRD described above.
4. Chemical morphological analysis of constituent elements
The chemical forms of the bonding, valence state and the like of the constituent elements of the Ce-doped composite sphere can be measured by an XPS method. Through the detection result, the chemical forms of the main elements and the doping elements in the composite sphere are known, and the doping mechanism of the composite sphere is concluded. XPS spectra of the Ce-doped composite spheres GCTD-2 and the undoped composite spheres TD-G are shown in FIGS. 6a-6 d.
Wherein, FIG. 6a is the total spectrum of two samples, GCTD-2 and TD-G, from which the characteristic peaks of the following elements can be found: si, Ti, O and foreign C elements (a C pollution source introduced by the XPS sample preparation process). FIG. 6b is a Ti 2p spectrum of Ce-doped composite spheres GCTD-2 and undoped composite spheres TD-G. The spectral peaks are respectively located at 458.1eV and 464.0eV, and are respectively assigned to 2p of Ti
3/2And 2p
1/2A track. It can be seen that the incorporation of Ce element only results in a slight increase in the binding energy of Ti 2 p. That is, Ti
4+The surrounding electron cloud density does not show significant chemical shifts due to Ce doping. Although the electronegativity of Ce atom is 1.1, it is doped with Ti in the lattice gap
4+The Ce-O-Ti bond is formed, but the content is extremely low, and the Si-O-Ti bond does not influence the existing Si-O-Ti bond at the same time, so the change of the Ti 2p orbital binding energy is not caused. FIG. 6c shows the O1s spectra of Ce doped composite spheres GCTD-2 and undoped composite spheres TD-G. The peak at 532.3eV is assigned to the O element in the Si-O-Si chemical bond, and the peak at 529.5eV is assigned to the O element in the Ti-O-Si chemical bond. It can be seen that the introduction of Ce results in a slight decrease in the intensity of the O1s spectrum peak, while its corresponding binding energy increases slightly. FIG. 6d is a Ce3d spectrum of Ce doped composite sphere GCTD-2 and undoped composite sphere TD-G. 3d of Ce
3/2And 3d
1/2The orbitals correspond to two peaks at binding energies of 883.0eV and 903.0eV, respectively, indicating that Ce is not fully oxidized and that there may be a certain number of oxygen vacancies at the lattice surface. Ce
4+And Ce
3+All of which have an ionic radius greater than Ti
4+So that TiO is not easily doped
2The crystal lattice, rather, exists in the form of oxides in the TiO
2Lattice surface and interstitial sites thereof, and with TiO
2Ce-O-Ti bonds are formed between the interfaces.
5. Absorption of visible light by composite spheres
To Ce-TiO
2The/diatomite composite sphere is subjected to ultraviolet-visible Diffuse Reflection (DRS) analysis, and the response range and degree of the/diatomite composite sphere to visible light can be obtained to reflect the visible light catalytic activity of the/diatomite composite sphere.
FIG. 7 is a Ce-doped sphere GCTD-2 and undoped compositeDRS spectrum of sphere TD-G. As can be seen from FIG. 7, pure TiO
2The crystals show strong absorption edges in the uv region below 380nm, similar to which undoped composite spheres have similar light absorption ranges in figure 7. And the DRS spectrogram of the Ce-doped composite sphere GCTD-2 shows that the absorption edge of the DRS spectrum has red shift change and extends to a visible light region. According to the Kubelka-Munk equation, the gap width of the undoped composite sphere was estimated to be about 3.20eV (as shown in FIG. 8), which is consistent with its absorption edge at 387 nm. The forbidden bandwidth value of the Ce-doped composite sphere GCTD-2 is about 2.60eV, which is consistent with a slightly red-shifted absorption edge. The visible light responsiveness of the Ce-doped composite sphere GCTD-2 can be attributed to the introduction of Ce doping, so that the visible light catalytic performance of the composite sphere GCTD-2 is improved.
Example 2 Ce-doped TiO based modified diatomaceous Earth
2Application of floating type photocatalytic composite material in degradation of organic dye
Rhodamine B is used as a target degradation product, the visible light catalytic activity of various Ce-doped composite spheres is investigated, and the photodegradation process is shown in figure 1.
The method comprises the following steps: 1.0g of GCTD with different Ce doping amounts prepared in example 1 is added into 200.0mL of 0.01g/L Rhodamine B (RhB for short) solution respectively, a dark adsorption process is carried out for 30min to ensure that the whole system achieves dynamic adsorption balance, and then the solution is placed under visible light (xenon lamp) with the power of 150W to carry out photocatalytic degradation for 180 min.
1. Study on visible light catalytic activity
Rhodamine B is adopted as a target degradation product, the visible light catalytic activity of various Ce-doped composite spheres is investigated, and meanwhile, non-spherical Ce-TiO is also selected
2Diatomaceous earth powder and TD-G were used for comparison. The results are shown in FIG. 9.
As can be seen from fig. 9, GCTD-2 exhibited the highest photodegradation efficiency among all Ce-doped composite spheres. However, ungelled Ce-TiO
2The diatomaceous earth powder exhibits a higher degradation efficiency than that. This may be because the particulate catalyst can create shadows on adjacent particles, thereby hindering overall light utilization. Can also be usedSo that the photocatalytic activity of the Ce-doped composite sphere GCTD-2 is better than that of the unsupported Ce-TiO
2Mainly due to the targeted enrichment effect caused by the adsorption performance of the fine soil carrier. This synergistic process of adsorption and degradation greatly promotes the overall degradation efficiency of RhB.
It can also be seen from the experimental results that the order of the photodegradation efficiency of the Ce-doped composite spheres is roughly: GCTD-2> GCTD-3> GCTD-1> GCTD-4. This indicates that the optimum doping amount of Ce in the present invention is 0.05-GCTD. Ce doping has the ability to trap electrons in addition to forming a doping level. The photocatalytic activity is enhanced from GCTD-1 to GCTD-4. As the amount of Ce doped further increases, the photocatalytic activity decreases.
2. Study of Recycling Properties
Among many Ce-doped composite spheres, GCTD-2 is the best photocatalytic sphere, and GCTD-2 is taken as an example in the cycling experiment. After the end of the previous set of experiments for photodegradation of RhB, the catalyst samples were separated from the RhB solution by filtration, followed by washing with deionized water. Then, the mixture is placed into an oven to be dried, and sent to the next group of photodegradation RhB experiments (each group of experiments lasts 180 minutes). The cyclic degradation results are shown in FIG. 10. As can be seen from fig. 10, using the Ce-doped composite sphere GCTD-2, after the initial degradation experiment was completed, the degradation rate of RhB was reduced to 81.2% through 5 times of repeated experiments, while the degradation rate of the initial degradation experiment was 85.6%. The reduction in degradation rate may be attributed to the loss of quality during the recovery process. Even so, the Ce-doped composite spheres still maintained stable RhB photodegradation efficiency during repeated use experiments. It is considered that the Ce-doped composite sphere has good photocatalytic stability.
Example 3 Ce-doped TiO based on modified diatomaceous Earth
2Application of floating type photocatalytic composite material in visible light sterilization
Coli (e.coli), staphylococcus aureus (s.aureus) and klebsiella pneumoniae (k.shroud) were used as target bacteria, and the visible light bactericidal activity of the Ce-doped composite spheres was examined.
The method comprises the following steps: centrifuging the cultured colony to obtain sedimentTransferring to 0.85% physiological saline, and adding GCTD with different Ce doping amounts prepared in example 1 to obtain mixed suspension of GCTD and bacteria (ratio of 5.0 g/L). The colony forming units of the suspension were set to 105CFUs mL by dilution
-1. Irradiating the suspension system with visible light. In the photocatalytic sterilization process, sampling operation is performed at an initial state and at time points of every 30min, 1.0mL of suspension is dropwise added to the surface of a culture dish coated with agar gel in advance, and then the culture dish is placed in a colony incubator and incubated at 37 ℃ for 24 h. Corresponding blank tests were also carried out, i.e. without any photocatalytic composite sample during the reaction.
1. The photocatalytic activity of the Ce-doped composite sphere is utilized to perform sterilization experiments on escherichia coli, staphylococcus aureus and klebsiella pneumoniae under the condition of visible light. The experiments all lasted 120min, and the results are shown in FIGS. 11a-11c, respectively. The same experiment was also carried out in a dark environment and was used as a control experiment.
FIG. 11a shows the results of visible light-induced sterilization and dark-condition sterilization of Escherichia coli by Ce-doped composite spheres (GCTD-2). FIG. 11b shows the results of visible light-induced sterilization and dark-condition sterilization of Staphylococcus aureus by Ce-doped composite spheres (GCTD-2). FIG. 11c shows the results of visible light-induced sterilization and dark-condition sterilization of Klebsiella pneumoniae by Ce-doped composite spheres (GCTD-2). As can be seen from the results of visible light sterilization and dark sterilization of the three types of strains of Escherichia coli, Staphylococcus aureus and Klebsiella pneumoniae in FIGS. 11a, 11b and 11c, GCTD-2 belongs to the sample with the highest photocatalytic sterilization activity in the Ce-doped composite sphere. The experimental result of the dark environment shows that the sterilization effect is mainly attributed to the visible light catalytic activity of the Ce-doped composite sphere.
2. Evaluation of the Cyclic usability of Photogermicidal Agents
The samples GCTD-2 with the optimal photocatalytic activity were evaluated for the recycling performance of photo-sterilization, and the results are shown in FIGS. 12a-12 c.
FIG. 12a shows the results of the cyclic sterilization of Escherichia coli by Ce-doped composite spheres (GCTD-2). FIG. 12b shows the results of the cyclic sterilization of Staphylococcus aureus by Ce-doped composite spheres (GCTD-2). FIG. 12c shows the results of the cyclic sterilization of Klebsiella pneumoniae by Ce-doped composite spheres (GCTD-2). As can be seen from FIGS. 12a-12c, after 5 additional cycles of sterilization, the survival rate of the E.coli strains was 17.7%, the survival rate of the S.aureus strains was 18.3%, and the survival rate of the P.leucoderma strains was 20.1%. In the first light sterilization process, the survival rate of the strains of the escherichia coli is 13.6%, the survival rate of the strains of the staphylococcus aureus is 12.1%, and the survival rate of the strains of the klebsiella pneumoniae is 15.3%. The Ce-doped composite sphere has good light sterilization stability and recycling performance no matter escherichia coli, staphylococcus aureus or klebsiella pneumoniae exists.
Claims (10)
1. Ce-doped TiO based on modified diatomite
2The preparation method of the floating type photocatalytic composite material is characterized by comprising the following steps:
1) mixing modified 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 absolute ethyl alcohol, deionized water and cerium nitrate into a mixed solution; 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 TiO
2A diatomaceous earth powder;
2) mixing modified diatomite with deionized water, adding an organic binder and a fluxing agent, uniformly mixing to prepare a mud ball, 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 ball
2Covering with diatomite powder, drying at 80 deg.C, and calcining in muffle furnace for 2 hr to obtain Ce-doped TiO based on modified diatomite
2A floating type photocatalytic composite material.
2. The method according to claim 1, wherein the modified diatomaceous earth is acid-modified diatomaceous earth.
3. The method according to claim 2, wherein the acid-modified diatomaceous earth is prepared by a method comprising the steps of: weighing a proper amount of diatomite raw soil and a diluted 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 modified diatomite.
4. The preparation method according to claim 3, 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.
5. 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.
6. The method of claim 4, wherein the organic binder is a combination of hydroxypropylmethylcellulose and dextrin; the fluxing agent is sodium carbonate.
7. The method according to claim 1, wherein the cerium nitrate is added in an amount of 0.02 to 0.20g per 8.0mL of tetra-n-butyl titanate.
8. The method according to claim 1, wherein the temperature of calcination in the muffle furnace in step 3) is 400-600 ℃.
9. Ce doped TiO based on modified diatomaceous earth prepared according to the process of any one of claims 1 to 8
2The floating type photocatalytic composite material is applied to degrading organic dye under visible light.
10. Ce doped TiO based on modified diatomaceous earth prepared according to the process of any one of claims 1 to 8
2The floating type photocatalytic composite material is applied to sterilization.
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