CN110652994A - Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid - Google Patents

Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid Download PDF

Info

Publication number
CN110652994A
CN110652994A CN201910966689.6A CN201910966689A CN110652994A CN 110652994 A CN110652994 A CN 110652994A CN 201910966689 A CN201910966689 A CN 201910966689A CN 110652994 A CN110652994 A CN 110652994A
Authority
CN
China
Prior art keywords
titanium dioxide
nano titanium
modified nano
preparation
waste liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910966689.6A
Other languages
Chinese (zh)
Inventor
于洪霞
张嘉琪
蔡天明
陈立伟
姜灿烂
丁大虎
罗静怡
张天宇
陆玲丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Agricultural University
Original Assignee
Nanjing Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Agricultural University filed Critical Nanjing Agricultural University
Priority to CN201910966689.6A priority Critical patent/CN110652994A/en
Publication of CN110652994A publication Critical patent/CN110652994A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of metal oxide semiconductors, in particular to a preparation method of a modified nano titanium dioxide material for catalyzing and degrading antibiotic waste liquid. The invention provides nitrogen-doped modified TiO2The photocatalytic material of (1) is TiO with tetrabutyl titanate2The precursor is prepared into the nano TiO by adopting a sol-gel method2Then in the presence of nano TiO2Adding a certain proportion of nitrogen source, and preparing modified TiO by dry method2The photocatalytic material of (1); the preparation process can realize continuous production; prepared modified nano TiO2The material has the advantages of large surface activity, high purity, good dispersibility and high efficiency of catalyzing and degrading antibiotics.

Description

Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid
Technical Field
The invention relates to the technical field of metal oxide semiconductors, in particular to a preparation method of a modified nano titanium dioxide material for catalyzing and degrading antibiotic waste liquid.
Background
Ciprofloxacin is an artificially synthesized third-generation fluoroquinolone antibiotic and is mainly used for sexually transmitted diseases, urinary tract infection and skin infection. Most fluoroquinolone antibiotics are not completely metabolized in the human body and are discharged out of the body as metabolites, and flow into sewage treatment plants along with sewage. Traditional biological sewage treatment methods do not completely remove such antibiotics and may have long-term destructive effects on ecosystem and human health. Therefore, the pollution caused by the ciprofloxacin in the water is not easy to remove.
At present, most of the sewage treatment methods use traditional physical methods such as chemical adsorption and artificial landfill, and the methods have high cost and may cause secondary pollution to the environment. Semiconductor photocatalysis technology is widely applied to various fields, because of simple operation conditions, no secondary pollution, and the inexhaustible solar energy can be used as energy to degrade organic or inorganic substances, but simultaneously, the semiconductor photocatalysis technology has a very obvious defect that light can cause the rapid recombination of electrons and holes in a photocatalyst material, most of the research is focused on the modification of photocatalysis under visible light, and researchers carry out various modifications of the photocatalyst material, such as the modification by adding metal, so that the rapid combination of the electrons and the holes is effectively prevented. And the material is sensitized by organic dye, so that the material and the dye can absorb light energy to degrade pollutants, and the photocatalytic degradation capability is greatly enhanced. These methods do improve the photocatalytic performance of the material to some extent, but also bring about other problems, such as secondary pollution, and even if the conditions are not well controlled, the absorption activity of the material to visible light is still small.
TiO2The photocatalyst has the advantages of high catalytic activity, stable photochemical property, strong oxidation resistance and the like, is one of the most common semiconductor photocatalysts, and has great application value in the aspects of pollutant treatment, light energy conversion and the like. But pure TiO2The catalytic efficiency is low, and the application of the photocatalyst is limited under visible light, so that how to effectively improve the solar utilization rate of titanium dioxide is a key scientific problem for promoting the large-scale application of the titanium dioxide photocatalyst in the fields of environment and energy.
Disclosure of Invention
The invention aims to provide a preparation method of a modified nano titanium dioxide material for catalyzing and degrading antibiotic waste liquid; the method for preparing the nitrogen-doped modified nano titanium dioxide visible light catalytic material by adopting the sol-gel and dry method has the advantages of capability of realizing continuous production, and large prepared surface activity, high purity and good dispersibility.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid comprises the following steps:
s01, accurately weighing hydroxypropyl cellulose (HPC) with a certain weight, placing the HPC in absolute ethyl alcohol with a certain volume, and fully stirring to prepare 0.004g/mL hydroxypropyl cellulose solution;
s02 distilled water was added to the hydroxypropylcellulose solution obtained in S01, followed by tetra-n-butyl titanate, hydroxypropylcellulose solution: distilled water: the volume ratio of the tetra-n-butyl titanate is as follows: 500:3, (1-15), stirring for 0-4h, centrifuging, removing supernatant, washing with absolute ethyl alcohol for several times, and then putting into an oven at 50-80 ℃ for drying to obtain a dried substance;
s03, taking out the dried substance obtained in S02, mixing the dried substance and the nitrogen source according to the mass ratio of (2:0) - (2:4), grinding, placing the mixture in a muffle furnace for high-temperature calcination at the temperature of 300-800 ℃ for 2-3h, and grinding to obtain the nitrogen-doped modified nano titanium dioxide.
Preferably, the hydroxypropyl cellulose solution in step S02: distilled water: the volume ratio of the tetra-n-butyl titanate is as follows: 500:3:(3-15).
Preferably, the washing with absolute ethanol in step S02 is performed 2 to 4 times.
Preferably, the step S03 is implemented by placing in a muffle furnace for high-temperature calcination, wherein the calcination temperature is 400-600 ℃.
Preferably, the nitrogen source in step S03 is thiourea or urea.
Preferably, the mass ratio of the dried product to the nitrogen source in step S03 is (2:1) - (2: 4).
Preferably, the nitrogen-containing doped modified nano titanium dioxide photocatalytic material is used for catalyzing and degrading antibiotic ciprofloxacin.
After the technical scheme is adopted, the invention has the following beneficial effects:
(1) the invention creatively adopts a nitrogen source as a doping agent and adopts a dry method to treat TiO2The modification is carried out, the preparation process of the nitrogen-doped modified nano titanium dioxide visible light catalytic material is simple, and continuous production can be realized; the prepared material has the advantages of large surface activity, high purity and good dispersibility.
(2) The invention adopts solution polymerization and dry method to prepare nano TiO2And performing TEM representation and photocatalytic performance test on the material prepared by standing and stirring synthesis, and obtaining the result that the material synthesized in the stirring state has better shape, better dispersibility and better photocatalytic performance.
(3) The invention introduces a nitrogen source in the muffle furnace calcination process to stir the prepared nano TiO2Modifying the material, researching the influence of different calcining temperatures and N/Ti ratios on the photocatalytic performance, adopting a Transmission Electron Microscope (TEM), scanning electron microscope analysis (SEM), X-ray diffraction (XRD), surface chemical element analysis and energy spectrum analysis, and obtaining a characterization result of the modified nano TiO2The photocatalyst sample has more dispersivity and rougher surface, and the modified nitrogen content is obviously increased.
Drawings
FIG. 1 shows that (a) and (b) show nano TiO synthesized under stirring and standing conditions2A material.
FIG. 2 Effect of the state of standing and stirring on the photocatalytic performance of the material produced.
FIG. 3(a) is a diagram showing a TiO solution having a TBOT content of 0.3mL2Material, (b) is TiO with TBOT content of 0.85mL2Material, (c) TiO with TBOT content of 1.5mL2A material.
FIG. 4 modified TiO2And (4) TEM characterization images of samples.
FIG. 5 SEM image of unmodified material and elemental surface distributions of N-K, O-K, Ti-K in corresponding regions.
FIG. 6 is SEM image of modified material and corresponding element surface distribution of N-K, O-K and Ti-K in corresponding area.
FIG. 7a is a synthetic TiO2The materials b and c are unmodified and modified materials prepared by muffle furnace calcination at 500 ℃.
FIG. 8 Effect of unmodified and modified on photocatalytic Properties of materials
EDS map of the material of figure 9.
FIG. 10 effect of materials of different Ti/N ratios on photocatalytic performance.
FIG. 11 shows the nano TiO compound2XRD pattern of (a).
FIG. 12 the effect of different calcination temperatures on the photocatalytic performance of a material.
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
Example 1
1 Experimental materials and instruments
The reagents and materials involved in the experiment are shown in table 1.
TABLE 1 Main chemical reagents
The main instruments and equipment are shown in Table 2
TABLE 2 Main instruments and Equipment
Figure BDA0002230707850000042
Preparation method of 2 nanometer titanium dioxide
A50 mL volume of absolute ethanol was measured and poured into a 250mL Erlenmeyer flask, 0.2g of hydroxypropyl cellulose (HPC) was accurately weighed and slowly poured into the Erlenmeyer flask, and the Erlenmeyer flask was stirred with a magnetic stirrer, 0.3mL of distilled water was added after the HPC was uniformly dispersed, 0.85mL of tetra-n-butyl titanate was then added, and after stirring for 3 hours, the mixture was centrifuged to remove the supernatant. Washing with anhydrous ethanol for three times, drying in 70 deg.C oven, grinding, placing in ceramic small crucible, calcining in muffle furnace at 600 deg.C for 2 hr, and grinding to obtain nanometer TiO2A photocatalyst.
3 Performance and characterization
3.1 Transmission Electron Microscope (TEM)
A Transmission Electron Microscope (TEM) was used for the measurement using a JEM-2100F model instrument manufactured by JEOL, Japan. Mainly uses TEM to observe the modified nano TiO when not fired2Particle morphology and structure of (a).
3.2 surface chemical elemental analysis
In order to observe the distribution of O, N, Ti elements on the surface of the material, the material before and after modification and not yet calcined was tested by an energy spectrometer equipped with a scanning electron microscope, the energy spectrometer being available from edax corporation.
3.3 scanning Electron microscopy analysis (SEM)
The microscopic morphology of the prepared material was visually tested by SEM using a scanning electron microscope model FEI400 FEG.
3.4X-ray diffraction (XRD)
The analysis is carried out by adopting a radiation diffractometer which is produced by Japan and is of a model number of smartlab9, and the test conditions for the radiation diffractometer are as follows: x-rays were provided from a copper target K α source with λ 0.1542nm, a tube current of 150mA, a tube voltage of 40KV, a scanning speed of 0.02 °/s, and a scanning range from 5 ° to 9 °. XRD was used to detect the prepared and modified TiO2Whether the doped titanium dioxide is anatase or not is determined, and the doped ion is analyzed by XRD to probe TiO under different temperatures and Ti/N ratios2Influence of the crystal form.
3.5 photocatalytic Performance test
The photocatalytic performance test also takes methylene blue (MB, 20mg/L) as a target pollutant, and the photocatalytic degradation performance of the prepared material is evaluated by performing visible light photocatalytic degradation on the target pollutant.
Example 2:
preparation method of 1 nanometer titanium dioxide
50mL of absolute ethanol is weighed and poured into a 250mL conical flask, 0.2g of hydroxypropyl cellulose (HPC) is accurately weighed and slowly poured into the conical flask, 0.3mL of distilled water is added after the hPC is uniformly dispersed, 0.85mL of tetra-n-butyl titanate is added, and after standing for 3h, centrifugation is carried out to remove a supernatant. Washing with anhydrous ethanol for three times, drying in a 70 deg.C oven, grinding, calcining in a muffle furnace at 500 deg.C for 2 hr, and grinding to obtain nanometer TiO2A photocatalyst.
2 TiO 2 in different conditions2TEM characterization of
As shown in FIG. 1, FIG. 1(a) shows the nano TiO prepared in example 1 after continuous stirring for 3h2FIG. 1(b) shows the nano TiO prepared in example 2 after standing and aging for 3h2A material. As is apparent from the figure, the synthesized nano TiO2The sample was spherical but some agglomeration occurred. Counter viewIn FIG. 1(b), after standing for 3 hours, various components in the solution may not be completely reacted, and the prepared materials are different in size, so that the materials are prepared by continuously stirring for 3 hours later.
3 Effect on photocatalytic Performance under different conditions
The polymerization form of the components in the solvent also affects the performance of the photocatalyst, and the photocatalyst is prepared by two different forms of standing (example 2) and stirring (example 1). Methylene blue with the concentration of 20mg/L in a 100mL system is taken as a target pollutant, 40mg of each material is weighed, and the photodegradation experiment is carried out after the materials are adsorbed for 1 hour in the dark. The experimental result is shown in fig. 2, it can be obviously seen that when the two are adsorbed in the dark, there is no obvious degradation, after 60min adsorption equilibrium is reached, the sunlight catalytic degradation is started, and the degradation rate of the two to methylene blue within 3h reaches more than 95%. It is evident that the material produced by stirring degrades significantly faster than the material produced by stirring. The possible reason is that the material produced by stirring reacts better than by standing during the preparation of the material, and HPC is more able to envelop the TiO2So that the material is more uniform and has better dispersibility.
Example 3:
a50 mL volume of absolute ethanol was measured and poured into a 250mL Erlenmeyer flask, 0.2g of hydroxypropyl cellulose (HPC) was accurately weighed and slowly poured into the Erlenmeyer flask, and the Erlenmeyer flask was stirred with a magnetic stirrer, 0.3mL of distilled water was added after the HPC was uniformly dispersed, 0.3mL of tetra-n-butyl titanate was then added, and after stirring for 3 hours, the mixture was centrifuged to remove the supernatant. Washing with anhydrous ethanol for three times, drying in 70 deg.C oven, grinding, placing in ceramic small crucible, calcining in muffle furnace at 500 deg.C for 2 hr, and grinding to obtain nanometer TiO2A photocatalyst.
Example 4:
preparation method of 1 nanometer titanium dioxide
Weighing 50mL absolute ethanol, pouring into 250mL conical flask, accurately weighing 0.2g hydroxypropyl cellulose (HPC), slowly pouring into conical flask, stirring with magnetic stirrer, uniformly dispersing HPC, and adding 0.3mL distilled water, followed by addition of 1.5mL tetra-n-butyl titanate, stirring for 3h, centrifugation, and removal of the supernatant. Washing with anhydrous ethanol for three times, drying in 70 deg.C oven, grinding, placing in ceramic small crucible, calcining in muffle furnace at 500 deg.C for 2 hr, and grinding to obtain nanometer TiO2A photocatalyst.
2 TiO 2 in different conditions2TEM characterization of
FIG. 3(a) is a graph showing that the TBOT content of TiO in example 3 was 0.3mL2Material (b) is TiO 0.85mL TBOT content in EXAMPLE 12Material (c) is TiO with TBOT content of 1.5mL in example 42A material. Nano TiO prepared in example 1 with TBOT content of 0.85mL2The size of the material is the intermediate value of the three formulas, the particle size is more uniform compared with the other two formulas, and the added TBOT content is 0.3mL2The smaller the material particles, and possibly the smaller the proportion of TBOT, the smaller the volume of the spheres formed. Added nano TiO prepared with TBOT content of 1.5mL2The material pellets are significantly larger in diameter but not very uniform in size.
Example 5:
preparation method of 1 nitrogen-containing doped modified nano titanium dioxide
Weighing 50mL of absolute ethyl alcohol, pouring into a 250mL conical flask, accurately weighing 0.2g of hydroxypropyl cellulose (HPC), slowly pouring into the conical flask, placing the conical flask on a magnetic stirrer while pouring, stirring, uniformly dispersing the HPC, adding 0.3mL of distilled water, then adding 0.85mL of tetra-n-butyl titanate, stirring for 3h, centrifuging, removing a supernatant, washing with the absolute ethyl alcohol, repeating for 3 times, drying at 70 ℃, mixing the dry matter and urea in a mass ratio of 1:2, fully mixing and grinding, placing the mixture and the materials into a ceramic small crucible, calcining for 2h at different temperatures in a muffle furnace at 500 ℃, and grinding to obtain the modified photocatalyst.
2 TEM analysis of the calcined Material after modification
To explore the microstructure and morphology of the composite photocatalyst, we modified the TiO of example 52Sample feedingTEM characterization was performed and it can be observed from fig. 4 that the particle size of the material after firing is uniform.
3 surface chemical elemental analysis
In order to observe the element distribution on the surface of the material, we tested the unmodified material using an energy spectrometer equipped with a projection electron microscope, and it can be seen from the SEM image of fig. 5 that the surface of the material prepared in example 1 is relatively smooth and spherical, and the presence of Ti, O and N in the photocatalyst sample can be compared, and the content of N is minimal compared to the content of Ti and O, which proves that the material before modification also contains a small amount of N.
We also tested the modified material of example 5 to compare the change in the modified elements. As is apparent from fig. 6, the surface of the modified material was relatively rough, and it is apparent that the concentration of N element was increased in comparison with the unmodified material, indicating that the modification was successful.
4 SEM analysis of the Material
FIG. 7a is a synthetic TiO2Materials b, c are unmodified (example 1) and modified (example 5) materials obtained by muffle furnace calcination at 500 ℃. As is apparent from FIG. 7(a), the material produced was spherical before firing, b and c were obtained by calcining in a muffle furnace at the same temperature (500 ℃ C.), and SEM characterization of the material before and after modification was observed2The surface of the material is smooth, and the modified material is calcined to obtain TiO2The spherical shape is obvious, the surface is obviously rough, and the spheres are uniformly dispersed.
Effect of 5-Urea modification on photocatalytic Properties of materials
The material is modified by adding a proper amount of urea in the calcining process, and as is obvious from figure 8, the urea and the urea are only slightly degraded in dark adsorption, and are basically ignored. The modified material (example 5) degraded at a significantly higher rate than the unmodified material (example 1) under visible light for a period of time, and degraded methylene blue to more than 95% within 240min, and both the rate and degree of degradation were better than those of the unmodified material, which indicates that the photocatalytic performance of the modified nano-titania is better than that of the single titania. And the modified nano titanium dioxide material can degrade more than 95% of ciprofloxacin solution of 5mg/L within 2 h.
Example 6:
preparation method of 1 nitrogen-containing doped modified nano titanium dioxide
Weighing 50mL of absolute ethyl alcohol, pouring into a 250mL conical flask, accurately weighing 0.2g of hydroxypropyl cellulose (HPC), slowly pouring into the conical flask, placing the conical flask on a magnetic stirrer while pouring, stirring, uniformly dispersing the HPC, adding 0.3mL of distilled water, then adding 0.85mL of tetra-n-butyl titanate, stirring for 3h, centrifuging, removing a supernatant, washing with the absolute ethyl alcohol, repeating for 3 times, drying at 70 ℃, mixing the dry matter and urea according to a mass ratio of 1:1, fully mixing and grinding, placing the mixture and the materials into a ceramic small crucible, calcining for 2h at different temperatures in a muffle furnace at 500 ℃, and grinding to obtain the modified photocatalyst.
Example 7:
preparation method of 1 nitrogen-containing doped modified nano titanium dioxide
Weighing 50mL of absolute ethyl alcohol, pouring into a 250mL conical flask, accurately weighing 0.2g of hydroxypropyl cellulose (HPC), slowly pouring into the conical flask, placing the conical flask on a magnetic stirrer while pouring, stirring, uniformly dispersing the HPC, adding 0.3mL of distilled water, then adding 0.85mL of tetra-n-butyl titanate, stirring for 3h, centrifuging, removing a supernatant, washing with the absolute ethyl alcohol, repeating for 3 times, drying at 70 ℃, mixing the dry matter and urea in a mass ratio of 2:1, fully mixing and grinding, placing the mixture and the materials into a ceramic small crucible, calcining for 2h at different temperatures in a muffle furnace at 500 ℃, and grinding to obtain the modified photocatalyst.
2 EDS analysis of materials
Fig. 9 is a graph of a nitrogen-doped sample of example 7, wherein N/Ti is 1:2(N means nitrogen source, and Ti means titanium dioxide), and the analysis result shows that: the content of N and Ti is substantially 1:2, and the mass concentration of Ti is the largest, which also contains N, which may indicate that nitrogen has been doped into the material.
3 Effect of materials with different N/Ti ratios on photocatalytic Properties
It can be seen from FIG. 10 that the modification results are better when the N/Ti ratio is 1:1 (example 6) than when the N/Ti ratio is 1:2 (example 7) and the N/Ti ratio is 2:1 (example 5), and that the TiO can be made to incorporate nitrogen into the crystal lattice2The light absorption range of the photocatalyst is red-shifted, and the absorption of visible light is enhanced, so that the photocatalytic performance is better.
Example 8
Preparation method of 1 nitrogen-containing doped modified nano titanium dioxide
Weighing 50mL of absolute ethyl alcohol, pouring into a 250mL conical flask, accurately weighing 0.2g of hydroxypropyl cellulose (HPC), slowly pouring into the conical flask, placing the conical flask on a magnetic stirrer while pouring, stirring, uniformly dispersing the HPC, adding 0.3mL of distilled water, then adding 0.85mL of tetra-n-butyl titanate, stirring for 3h, centrifuging, removing a supernatant, washing with the absolute ethyl alcohol, repeating for 3 times, drying at 70 ℃, mixing the dry matter and urea according to a mass ratio of 1:1, fully mixing and grinding, placing the mixture and the materials into a ceramic small crucible, calcining for 2h at different temperatures in a muffle furnace at 400 ℃, and grinding to obtain the modified photocatalyst.
Example 9
Preparation method of 1 nitrogen-containing doped modified nano titanium dioxide
Weighing 50mL of absolute ethyl alcohol, pouring into a 250mL conical flask, accurately weighing 0.2g of hydroxypropyl cellulose (HPC), slowly pouring into the conical flask, placing the conical flask on a magnetic stirrer while pouring, stirring, uniformly dispersing the HPC, adding 0.3mL of distilled water, then adding 0.85mL of tetra-n-butyl titanate, stirring for 3h, centrifuging, removing a supernatant, washing with the absolute ethyl alcohol, repeating for 3 times, drying at 70 ℃, mixing the dry matter and urea according to a mass ratio of 1:1, fully mixing and grinding, placing the mixture and the materials into a ceramic small crucible, calcining for 2h at different temperatures in a muffle furnace at 600 ℃, and grinding to obtain the modified photocatalyst.
2 XRD analysis of the Material
XRD is measured on the modified sample to determine its crystal form and components, as shown in fig. 11, the sample which is only dried and not calcined does not have the crystal form, the sample prepared by calcining at 500 ℃ in example 6) has a peak at 2 θ -27.459, according to the PDF standard card, it can be known that at this time, part of anatase is converted into rutile phase, and the rest still follows the feature of anatase peak, and no other peak is added, which indicates that N is doped into the lattice site of titanium dioxide and no other substance is generated. Whereas the sample obtained at 600 c (example 9) was rutile titanium dioxide with a small amount of anatase, the sample obtained at 400 c (example 8) had a crystallization pattern that substantially matched the PDF card of anatase, so that the majority was purer anatase.
3 influence of modified calcined materials at different temperatures on photocatalytic performance
Adopts dry method to calcine and modify nano TiO through a muffle furnace2The material, so different temperatures will certainly have an effect on the photocatalytic properties of the material. As can be seen from FIG. 12, the degradation rate of the sample calcined at three temperatures to methylene blue within 3h after degradation for different time periods reaches more than 98%. When the calcination temperature is 500 deg.C (example 6), the photocatalytic performance of the material is better than that of the material obtained by the steps of 400 deg.C (example 8) and 600 deg.C (example 9).
Example 10
Weighing 50mL of absolute ethyl alcohol, pouring into a 250mL conical flask, accurately weighing 0.2g of hydroxypropyl cellulose (HPC), slowly pouring into the conical flask, placing the conical flask on a magnetic stirrer while pouring, stirring, uniformly dispersing the HPC, adding 0.3mL of distilled water, then adding 1.5mL of tetra-n-butyl titanate, stirring for 4 hours, centrifuging, removing a supernatant, washing with the absolute ethyl alcohol, repeating for 4 times, drying at 50 ℃, mixing the dried product and thiourea in a mass ratio of 1:1, fully mixing and grinding, placing the mixture and the materials into a ceramic small crucible, calcining for 2 hours at different temperatures in a muffle furnace at the calcining temperature of 800 ℃, and grinding to obtain the modified photocatalyst.
Example 11
Weighing 50mL of absolute ethyl alcohol, pouring into a 250mL conical flask, accurately weighing 0.2g of hydroxypropyl cellulose (HPC), slowly pouring into the conical flask, placing the conical flask on a magnetic stirrer while pouring, stirring, uniformly dispersing the HPC, adding 0.3mL of distilled water, then adding 0.1mL of tetra-n-butyl titanate, stirring for 2h, centrifuging, removing a supernatant, washing with the absolute ethyl alcohol, repeating for 2 times, drying at 80 ℃, mixing the dry matter and urea in a mass ratio of 1:1, fully mixing and grinding, placing the mixture and the materials into a ceramic small crucible, calcining for 3h at different temperatures in a muffle furnace at 300 ℃, and grinding to obtain the modified photocatalyst.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.

Claims (7)

1. A preparation method of a modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid is characterized by comprising the following steps: the method comprises the following steps:
s01, accurately weighing hydroxypropyl cellulose (HPC) with a certain weight, placing the HPC in absolute ethyl alcohol with a certain volume, and fully stirring to prepare 0.004g/mL hydroxypropyl cellulose solution;
s02 distilled water was added to the hydroxypropylcellulose solution obtained in S01, followed by tetra-n-butyl titanate, hydroxypropylcellulose solution: distilled water: the volume ratio of the tetra-n-butyl titanate is as follows: 500:3 (1-15), stirring for 0-4h, centrifuging, removing supernatant, washing with anhydrous ethanol for several times, and adding 50-80oC, drying in an oven to obtain a dried substance;
s03 taking out the dried substance obtained in S02, mixing the dried substance and the nitrogen source according to the mass ratio of (2:0) - (2:4), grinding, and placing in a muffle furnace for high-temperature calcination at the calcination temperature of 300-800-oAnd C, grinding the mixture after the calcination time is 2-3h to obtain the nitrogen-doped modified nano titanium dioxide.
2. A preparation method of a modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid is characterized by comprising the following steps: hydroxypropyl cellulose solution in step S02: distilled water: the volume ratio of the tetra-n-butyl titanate is as follows: 500:3:(3-15).
3. A preparation method of a modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid is characterized by comprising the following steps: washing with anhydrous ethanol for 2-4 times in step S02.
4. The preparation method of the modified nano titanium dioxide material for catalyzing and degrading the antibiotic waste liquid according to claim 1, which is characterized in that: step S03, placing the mixture in a muffle furnace for high-temperature calcination at 400-600 deg.CoC。
5. The preparation method of the modified nano titanium dioxide material for catalyzing and degrading the antibiotic waste liquid according to claim 1, which is characterized in that: in step S03, the nitrogen source is thiourea or urea.
6. The preparation method of the modified nano titanium dioxide material for catalyzing and degrading the antibiotic waste liquid according to claim 1, which is characterized in that: the mass ratio of the dried product to the nitrogen source in step S03 was (2:1) - (2: 4).
7. The application of the nano titanium dioxide material for catalytically degrading the antibiotic waste liquid is characterized in that: the nitrogen-containing doped modified nano titanium dioxide photocatalytic material is used for catalyzing and degrading antibiotic ciprofloxacin.
CN201910966689.6A 2019-10-12 2019-10-12 Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid Pending CN110652994A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910966689.6A CN110652994A (en) 2019-10-12 2019-10-12 Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910966689.6A CN110652994A (en) 2019-10-12 2019-10-12 Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid

Publications (1)

Publication Number Publication Date
CN110652994A true CN110652994A (en) 2020-01-07

Family

ID=69040703

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910966689.6A Pending CN110652994A (en) 2019-10-12 2019-10-12 Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid

Country Status (1)

Country Link
CN (1) CN110652994A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112915987A (en) * 2021-01-26 2021-06-08 宿州学院 TiO with formaldehyde degrading effect2@C3N4Photocatalyst and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333002A (en) * 2007-06-27 2008-12-31 中国科学院合肥物质科学研究院 Titanium dioxide nano powder with special morphology and preparation method thereof
CN109647483A (en) * 2019-01-20 2019-04-19 信阳师范学院 A kind of preparation method and applications for the titanium dioxide optical catalyst that boron is nitrogen co-doped

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333002A (en) * 2007-06-27 2008-12-31 中国科学院合肥物质科学研究院 Titanium dioxide nano powder with special morphology and preparation method thereof
CN109647483A (en) * 2019-01-20 2019-04-19 信阳师范学院 A kind of preparation method and applications for the titanium dioxide optical catalyst that boron is nitrogen co-doped

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
L. RIZZO ET AL.: ""Effect of solar simulated N-doped TiO2 photocatalysis on the inactivation and antibiotic resistance of an E. coli strain in biologically treated urban wastewater"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 *
周武艺: ""纳米TiO2的掺杂改性及光催化性能的研究"", 《中国优秀博士学位论文全文数据库工程科技I辑》 *
张晓伟等: ""N掺杂TiO2光催化剂的制备及性能研究"", 《材料导报》 *
邢雪彬: ""UPLC-QTOF MS技术在水中抗生素的光降解治理及药品包装材料安全性研究中的应用"", 《中国优秀硕士学位论文全文数据库工程科技I辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112915987A (en) * 2021-01-26 2021-06-08 宿州学院 TiO with formaldehyde degrading effect2@C3N4Photocatalyst and preparation method thereof

Similar Documents

Publication Publication Date Title
Toloman et al. Photocatalytic activity of SnO2-TiO2 composite nanoparticles modified with PVP
US20220355284A1 (en) Perylene imide and composite photocatalytic material thereof, preparation method therefor and application thereof in removing organic pollutants from water
CN109759110A (en) A kind of N doping porous carbon loaded titanium dioxide photocatalyst and the preparation method and application thereof
Ibrahim Photocatalytic activity of nanostructured ZnO–ZrO2 binary oxide using fluorometric method
CN112007632B (en) Flower-shaped SnO 2 /g-C 3 N 4 Preparation method of heterojunction photocatalyst
CN106732504A (en) The preparation method and application of Graphene optically catalytic TiO 2 composite
Yang et al. Degradation of formaldehyde and methylene blue using wood-templated biomimetic TiO2
CN110586166A (en) Preparation of molybdenum oxide nanosheet and application of molybdenum oxide nanosheet in photocatalytic nitrogen fixation
CN113941357A (en) Si-TiO2/g-C3N4Ternary composite photocatalytic material and preparation method thereof
CN113751048A (en) Molybdenum trioxide in-situ intercalation carbon nitride composite catalyst and preparation method thereof
CN114933709A (en) Preparation method and application of high-yield UiO-66 metal organic framework material
CN108927201B (en) AgBr/g-C3N4Preparation method and application of composite powder
CN110652994A (en) Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid
CN112246264B (en) Molybdenum carbide metal molybdenum silicon carbide ternary composite material, preparation method thereof and effect of molybdenum carbide metal molybdenum silicon carbide ternary composite material on photocatalytic hydrogen production
Drunka et al. Microwave assisted synthesis, modification with platinum and photocatalytical properties of TiO2 nanofibers
Thirugnanam et al. Porous tubular rutile TiO2 nanofibers: synthesis, characterization and photocatalytic properties
Kralchevska et al. The photocatalytic degradation of 17α-ethynylestradiol by pure and carbon nanotubes modified TiO 2 under UVC illumination
CN108940324A (en) A kind of multi-walled carbon nanotube-Ag@AgCl composite nano materials and preparation method thereof with photocatalytic
Haider et al. Property-performance relationship of core-shell structured black TiO2 photocatalyst for environmental remediation
CN105417578B (en) A kind of preparation method of cauliflower-shaped brookite type titanium dioxide
CN111298783A (en) Method for preparing nano microsphere photocatalyst by doping rare earth Ce with ZnO and catalytic degradation method thereof
CN103752301B (en) Receiving bore alkali metal/titanates of alkali-earth metals photochemical catalyst and preparation method thereof
Ye et al. Synthesis and photocatalytic properties of three-dimensional mesoporous titanium dioxide
CN103623800A (en) Method for preparing titanium dioxide ball and obtained product
RU2469954C2 (en) METHOD OF OBTAINING NANOSIZE η-MODIFICATION OF TITANIUM DIOXIDE

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200107