CN116328753A - TiO (titanium dioxide) 2 -CeO 2 Composite nano material and preparation method and application thereof - Google Patents
TiO (titanium dioxide) 2 -CeO 2 Composite nano material and preparation method and application thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 184
- 239000002131 composite material Substances 0.000 title claims abstract description 158
- 238000002360 preparation method Methods 0.000 title claims abstract description 71
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 119
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/39—
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- B01J35/40—
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- B01J35/51—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2305/08—Nanoparticles or nanotubes
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a TiO 2 ‑CeO 2 Composite nano material and its preparation process and application, and belongs to the field of nano material technology. TiO of the invention 2 ‑CeO 2 The preparation method of the composite nano material comprises the following steps: to nanometer TiO 2 Adding ammonia water solution into the aqueous dispersion, dispersing uniformly, addingAdding Ce salt, stirring at 95deg.C for 4-4.5 hr to obtain TiO 2 ‑CeO 2 Composite nanomaterial. The invention innovatively adopts a novel green, economical and efficient synthesis method to dope Ce element into TiO 2 To realize TiO 2 Surface modification of (C) to form TiO 2 ‑CeO 2 The composite nano material is spherical, has smaller particle size (smaller than 20 nm), controllable size and morphology and larger specific surface area, and can degrade antibiotics by photocatalysis.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a TiO (titanium dioxide) 2 -CeO 2 Composite nano material and its preparation process and application.
Background
With the continuous progress of social productivity and scientific technology, the continuous improvement of the living standard of people and the acceleration of the industrialization process, the environmental problem is increasingly serious, and the pollution of water resources is particularly prominent. Water, as the most valuable and important natural resource in the world, is threatened by various contaminants, particularly with residual antibiotic contamination. In general, china rivers and lakes contain high concentrations of antibiotics, while sulfonamides and quinolones are the main pollutants in China lake surface water.
At present, the treatment methods for residual antibiotic pollution in water are various and comprise various physical, chemical and biological treatment methods, such as membrane treatment and reverse osmosis; active carbon and chlorination; aerobic and anaerobic methods have been used to treat pharmaceutical wastewater, and the major drawbacks of these treatment methods are membrane blockage, carbon regeneration, size exclusion range limitations, treatment problems (physicochemical treatment), biomass accumulation, slow processes, and long start-up periods (biological treatment) required. Because of the poor degradability of antibiotics, wastewater treatment plants are not suitable for treating these pollutants, and there is a need to develop alternative sustainable treatment methods.
It was found that photocatalysis has the potential to degrade organic contaminants in water and wastewater. The photocatalytic degradation method is widely adopted because the photocatalytic degradation method is carried out at normal temperature and normal pressure, and the photocatalytic degradation method takes dissolved oxygen in air as an oxidant, and has the advantages of low cost and the like. Meanwhile, in a plurality of water pollution treatment schemes, the photocatalytic degradation technology for degrading organic matters is greatly developed and widely explored due to the advantages of high efficiency, long service life, economy, environment friendliness, simplicity in maintenance, low operation cost and the like. However, some semiconductor materials have limited their use in real life due to toxicity or susceptibility to light candles, while titanium dioxide (TiO 2 ) The semiconductor material has wide application prospect in the fields of photocatalytic degradation of organic pollutants, photocatalytic water splitting hydrogen production and the like due to the advantages of high photocatalytic activity, simple photocatalytic technology process, low cost, stable chemical property, no toxicity, good biocompatibility, benefit to ecological natural environment and the like, and is one of the green and environment-friendly photocatalysts with the development prospect. But due to various self factors, the nano TiO is 2 Photocatalytic digestion techniques are greatly limited in practical applications. On the one hand, the higher electron-hole pair recombination rate results in low quantum efficiency, thereby affecting photodegradation efficiency. Under the irradiation of ultraviolet light, semiconductor TiO 2 The photocatalyst is separated after being excited to generate photo-generated electron-hole pairs, wherein most of rapid recombination occurs after migrating to TiO 2 The energy in front of the catalyst surface during the recombination of the absorbed photogenerated carriers will be released as heat and fluorescence. Only 4% of conventional TiO 2 Up to 10%, thereby reducing the reactivity of the catalyst, which limits the applications in production and life to a great extent, making it difficult to compete economically with conventional environmental techniques. On the other hand, tiO 2 The narrow forbidden bandwidth (3.2 eV) limits the photoresponse range, so that the ultraviolet light with the wavelength of 387nm or less can be only utilized, the ultraviolet light in the solar spectrum is only 3-5%, the visible light occupying most of the energy of the solar spectrum can not be effectively utilized, the solar energy utilization rate is low, the catalytic activity is low, and the T is limitediO 2 As a photocatalyst. For this reason, development of a photocatalyst that works under irradiation of visible light accounting for 45% of sunlight is highly desired.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the TiO which has the advantages of spherical shape, small particle size and photocatalysis degradation of antibiotics 2 -CeO 2 Composite nanomaterial.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a TiO 2 -CeO 2 The preparation method of the composite nano material comprises the following steps: to nanometer TiO 2 Adding aqueous ammonia solution into the aqueous dispersion, dispersing uniformly, adding Ce salt, stirring at 95deg.C for 4-4.5 hr to obtain TiO 2 -CeO 2 Composite nanomaterial.
The invention is realized by combining TiO 2 Mixing the aqueous dispersion with ammonia water to obtain TiO 2 Forming colloid precipitate, and can better react with Ce salt to prepare TiO in one step 2 -CeO 2 The composite nano material has mild synthesis condition, safe raw materials and environment friendliness.
The stirring time in the preparation method plays a key role in whether the composite nano material can be successfully prepared and the morphology: when the stirring time is less than 4 hours, nano TiO 2 With Ce (NO) 3 ) 3 ·6H 2 Incomplete O reaction and unavailable TiO 2 -CeO 2 A composite nanomaterial; when the stirring time is more than 4.5h, the prepared TiO 2 -CeO 2 The composite nano material has uneven particle size distribution, is unstable and is easy to agglomerate.
The invention innovatively adopts a novel green, economical and efficient synthesis method to dope Ce element into TiO 2 To realize TiO 2 Surface modification of (C) to form TiO 2 -CeO 2 The composite nano material has smaller particle size and larger specific surface area, and can degrade antibiotics by photocatalysis.
As the TiO of the present invention 2 -CeO 2 Preparation of composite nanomaterialIn a preferred embodiment of the method, the concentration of ammonia water in the ammonia water solution is 23-34mM, and the volume of ammonia water is 8-12ml.
In the preferable proportion range, the TiO prepared by the preparation method of the invention 2 -CeO 2 The composite nano material is uniformly distributed and stable and is not easy to agglomerate. When the concentration of the ammonia water solution is more than 34mM and the volume is more than 12ml, the prepared TiO 2 -CeO 2 The particle size distribution of the composite nano material is uneven, and the agglomeration phenomenon is easy to occur; when the concentration of the ammonia water solution is less than 23mM and the volume is less than 8ml, the prepared TiO 2 -CeO 2 The composite nano material has no characteristic absorption peak in UV-Vis, and TiO is not successfully prepared 2 -CeO 2 Composite nanomaterial.
As the TiO of the present invention 2 -CeO 2 In a preferred embodiment of the method for preparing a composite nanomaterial, the concentration of ammonia water in the ammonia water solution is 25-29mM, and the volume of ammonia water is 9-11ml. In the proportion range, the prepared TiO 2 -CeO 2 The composite nano material has more uniform and stable particle size distribution and is not easy to agglomerate.
As the TiO of the present invention 2 -CeO 2 In a preferred embodiment of the method for producing a composite nanomaterial, the concentration of ammonia in the ammonia solution is 27mM, and the volume of ammonia water is 10.1ml. In the proportion range, the prepared TiO 2 -CeO 2 The composite nano material has the most uniform and stable particle size distribution and is not easy to agglomerate.
As the TiO of the present invention 2 -CeO 2 Preferred embodiment of the method for preparing composite nanomaterial, the nano Ti O 2 The molar ratio of the Ti element to the Ce element in the Ce salt is as follows: ce= (3.375-4.125): (0.029-0.036).
The invention optimizes the element proportion of Ti and Ce to obtain TiO 2 -CeO 2 The composite nano material has smaller particle size and larger specific surface area.
As the TiO of the present invention 2 -CeO 2 Preferred embodiment of the method for preparing composite nanomaterial, the nano Ti O 2 Element Ti and element Ce in Ce saltThe molar ratio of (2) is Ti: ce= (3.6-3.9): (0.031-0.033). In the preferred compounding ratio range, the obtained TiO 2 -CeO 2 The composite nano material has smaller particle size and larger specific surface area.
As the TiO of the present invention 2 -CeO 2 Preferred embodiment of the method for preparing composite nanomaterial, the nano Ti O 2 The molar ratio of the Ti element to the Ce element in the Ce salt is as follows: ce=3.75:0.032. In the preferred compounding ratio range, the obtained TiO 2 -CeO 2 The composite nano material has the smallest particle size and the largest specific surface area.
As the TiO of the present invention 2 -CeO 2 Preferred embodiment of the preparation method of the composite nanomaterial, wherein the Ce salt is Ce (NO 3 ) 3 ·6H 2 O。
As the TiO of the present invention 2 -CeO 2 In a preferred embodiment of the preparation method of the composite nanomaterial, the uniform dispersion is ultrasonic for 5-10min.
As the TiO of the present invention 2 -CeO 2 Preferred embodiment of the method for preparing composite nanomaterial, the nano TiO 2 The particle size is 5-10nm. Adopts nano TiO with the grain diameter of 5-10nm 2 As a raw material, the obtained TiO 2 -CeO 2 The composite nanomaterial is smaller in particle size.
As the TiO of the present invention 2 -CeO 2 Preferred embodiment of the method for preparing composite nanomaterial, the nano TiO 2 The preparation method of the aqueous dispersion comprises the following steps: uniformly mixing water and isopropyl alcohol solution of isopropyl titanate, and drying to obtain nano TiO 2 An aqueous dispersion, said water being acidic.
The invention innovatively provides the method for preparing the nano TiO with the advantages of environmental protection, economy, reproducibility, easy recovery and stronger photocatalytic performance by using the isopropyl titanate as the raw material and adopting a simple, efficient and environmental protection economical synthesis method 2 And (3) particles.
As the TiO of the present invention 2 -CeO 2 Preferred embodiment of the preparation method of the composite nanomaterial, wherein the acidic water is prepared by adjusting pH value to 5 with concentrated nitric acid, and the isopropyl titanateThe isopropyl titanate concentration in the isopropyl alcohol solution of the ester was 0.84M. Nano TiO prepared under preferable condition 2 The particle size is smaller (5-10 nm), the specific surface area is larger, the stability is better, and the photocatalytic activity is higher.
In a second aspect, the present invention provides a TiO 2 -CeO 2 The composite nano material is prepared by the preparation method.
In a third aspect, the present invention provides the above TiO 2 -CeO 2 The application of the composite nano material in the field of photocatalytic degradation of antibiotics.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention innovatively adopts a novel green, economical and efficient synthesis method to dope Ce element into TiO 2 To realize TiO 2 Surface modification of (C) to form TiO 2 -CeO 2 The composite nano material is spherical, has smaller particle size (15-20 nm), controllable size and morphology and larger specific surface area, and can degrade antibiotics by photocatalysis. In addition, ce element is doped into TiO 2 The surface can also improve TiO 2 The surface acid alkalinity, active site, electron density and the like expand the utilization range of the nano material to the wavelength of solar light, improve the photocatalysis performance, enable the nano material to generate catalytic reaction under the irradiation of visible light accounting for 45 percent of sunlight, and achieve the effect of degrading antibiotics.
2. TiO of the invention 2 -CeO 2 The preparation method of the composite nano material has mild synthesis conditions, safer raw materials, no harmful pollution in the preparation process, low cost in the synthesis process and capability of being expanded to the preparation of other various different nano materials.
3. The invention innovatively provides the method for preparing the nano TiO which is green, economical and renewable, easy to recycle, strong in photocatalytic performance, smaller in particle size (5-10 nm), larger in specific surface area and better in stability by taking isopropyl titanate as a raw material and adopting a simple, efficient and green economical synthesis method 2 。
Drawings
FIG. 1 is a TiO according to example 1 of the present invention 2 -CeO 2 And (5) a composite nanomaterial product graph.
FIG. 2 is a TiO according to example 1 of the present invention 2 -CeO 2 Ultraviolet visible spectrum of the composite nanomaterial.
FIG. 3 is a TiO according to example 1 of the present invention 2 -CeO 2 Particle size distribution of the composite nanomaterial.
FIG. 4 is a TiO according to example 1 of the present invention 2 -CeO 2 Transmission electron microscopy of composite nanomaterial.
FIG. 5 is a TiO according to example 1 of the present invention 2 -CeO 2 Scanning electron microscopy of composite nanomaterial.
FIG. 6 is a TiO according to example 1 of the present invention 2 -CeO 2 Energy spectrum of composite nanomaterial.
FIG. 7 is a TiO according to example 1 of the present invention 2 -CeO 2 X-ray photoelectron spectrum of the composite nanometer material.
FIG. 8 shows TiO of comparative examples 3, 4 of the present invention 2 -CeO 2 Particle size distribution of the composite nanomaterial.
FIG. 9 is a TiO of comparative example 5 of the present invention 2 -CeO 2 Product graph of composite nanomaterial, tiO of comparative example 6 2 -CeO 2 Ultraviolet spectrogram of the composite nano material.
FIG. 10 is a TiO of comparative example 7 according to the invention 2 -CeO 2 Graph of composite nanomaterial product, tiO of comparative example 8 2 -CeO 2 Particle size distribution of the composite nanomaterial.
FIG. 11 is a TiO of comparative example 9 according to the invention 2 -CeO 2 Particle size distribution of composite nanomaterial, ultraviolet spectrum of comparative example 10.
FIG. 12 is a TiO according to example 1 of the present invention 2 -CeO 2 Composite nanomaterial, tiO of comparative example 1 2 Nanomaterial, ceO of comparative example 2 2 The absorbance change curve of the nano material and sulfamethoxazole aqueous solution after being irradiated by an ultraviolet lamp at 365 nm.
FIG. 13 is a diagram showing the TiO of example 1 of the present invention 2 -CeO 2 Composite nanomaterial, tiO of comparative example 1 2 Nanomaterial, pair ofCeO of proportion 2 2 The absorbance change curve of the mixture of the nano material and the sulfamethoxazole water solution after natural lamp irradiation.
FIG. 14 is a TiO according to example 1 of the present invention 2 -CeO 2 Composite nanomaterial, tiO of comparative example 1 2 Nanomaterial, ceO of comparative example 2 2 The absorbance change curve of the mixture of the nanomaterial and ciprofloxacin aqueous solution after irradiation of 365nm ultraviolet lamp.
FIG. 15 is a TiO according to example 1 of the present invention 2 -CeO 2 Composite nanomaterial, tiO of comparative example 1 2 Nanomaterial, ceO of comparative example 2 2 The absorbance change curve of the mixture of the nano material and ciprofloxacin aqueous solution after natural lamp irradiation.
FIG. 16 is a TiO according to example 1 of the present invention 2 -CeO 2 The absorbance change curve of the composite nano material after being irradiated by a 365nm ultraviolet lamp is mixed with ciprofloxacin aqueous solutions with different concentrations.
FIG. 17 is a TiO according to example 1 of the present invention 2 -CeO 2 Absorbance change curves of the composite nano material and ciprofloxacin aqueous solutions with different concentrations after natural lamp irradiation.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the following examples and comparative examples, the materials used are commercially available.
Example 1
TiO of the invention 2 -CeO 2 Composite nanomaterial and one embodiment of a preparation method thereof, the TiO of this embodiment 2 -CeO 2 The preparation method of the composite nano material comprises the following steps:
1. nanometer TiO 2 Is prepared by the following steps.
Adjusting pH to=5 with concentrated nitric acid, adding 20ml isopropyl alcohol solution of 0.84M isopropyl titanate, stirring for 30min, and drying at 60deg.C for 12 hr to obtain nanometer TiO 2 The particle size is 5-10nm.
2、TiO 2 -CeO 2 Composite materialAnd (3) preparing a nano material.
To 100ml of 5mg/ml of nano TiO 2 10.1ml of 27mM aqueous ammonia solution was added to the aqueous dispersion, sonicated for 10min, and 43.4mg of Ce (NO) 3 ) 3 ·6H 2 O, heating to 95 ℃ and stirring for 4.2h.
Example 2
TiO of the invention 2 -CeO 2 Composite nanomaterial and one embodiment of a preparation method thereof, the TiO of this embodiment 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as that of the example 1, and the preparation method of the composite nano material is as follows:
to 100ml of 4.5mg/ml nano TiO 2 8ml of 34mM aqueous ammonia solution was added to the aqueous dispersion, sonicated for 5min, and 29.1mg of Ce (NO) 3 ) 3 ·6H 2 O, heating to 95 ℃ and stirring for 4.5h.
Example 3
TiO of the invention 2 -CeO 2 Composite nanomaterial and one embodiment of a preparation method thereof, the TiO of this embodiment 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as that of the example 1, and the preparation method of the composite nano material is as follows:
to 100ml of 4.8mg/ml nano TiO 2 9.4ml of 29mM aqueous ammonia solution was added to the aqueous dispersion, sonicated for 6min, and 41.1mg of Ce (NO) 3 ) 3 ·6H 2 O, heating to 95 ℃ and stirring for 4 hours.
Example 4
TiO of the invention 2 -CeO 2 Composite nanomaterial and one embodiment of a preparation method thereof, the TiO of this embodiment 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as that of the example 1, and the preparation method of the composite nano material is as follows:
to 100ml of nano TiO 5.2mg/ml 2 Adding 12ml of 23mM ammonia water solution into the water dispersion, ultrasonic treating for 8min, adding 44.4mg of Ce (NO) 3 ) 3 ·6H 2 O, heating to 95 ℃ and stirring for 4.3h.
Example 5
TiO of the invention 2 -CeO 2 Composite nanomaterial and one embodiment of a preparation method thereof, the TiO of this embodiment 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as that of the example 1, and the preparation method of the composite nano material is as follows:
to 100ml of nano TiO 5.5mg/ml 2 10.9ml of 25mM aqueous ammonia solution was added to the aqueous dispersion, sonicated for 10min, and 47.7mg of Ce (NO) 3 ) 3 ·6H 2 O, heating to 95 ℃ and stirring for 4.5h.
Comparative example 1
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, the comparative example is TiO 2 Nanomaterial, preparation method is the same as in example 1.
Comparative example 2
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, the comparative example is CeO 2 The preparation method of the nano material comprises the following steps:
217mg Ce (NO) 3 ) 3 ·6H 2 O was stirred with 48.65ml of water for 15min, and 1.35ml of 7.794M aqueous ammonia was added thereto and stirred for 18-24h.
Comparative example 3
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, tiO of comparative example 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as in example 1, and the preparation method of the composite nanomaterial is basically the same as in example 1, except that the concentration of the aqueous ammonia solution used is 40mM and the volume is 6.8ml.
Comparative example 4
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, tiO of comparative example 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as that of example 1, and the preparation method of the composite nano material is basically the same as that of example 1, except that ammonia water is adopted for dissolvingThe concentration of the solution was 20mM and the volume was 13.635ml.
Comparative example 5
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, tiO of comparative example 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as in example 1, and the preparation method of the composite nanomaterial is basically the same as in example 1, except that the heating and stirring time is 5 hours.
Comparative example 6
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, tiO of comparative example 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as in example 1, and the preparation method of the composite nanomaterial is basically the same as in example 1, except that the heating and stirring time is 3 hours.
Comparative example 7
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, tiO of comparative example 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as in example 1, and the preparation method of the composite nanomaterial is basically the same as in example 1, except that nano TiO is used 2 The concentration of the aqueous dispersion was 10mg/ml.
Comparative example 8
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, tiO of comparative example 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as in example 1, and the preparation method of the composite nanomaterial is basically the same as in example 1, except that nano TiO is used 2 The concentration of the aqueous dispersion was 1mg/ml.
Comparative example 9
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, tiO of comparative example 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as that of example 1The preparation method of the composite nanomaterial is basically the same as that of example 1, except that Ce (NO 3 ) 3 ·6H 2 The amount of O was 10mg.
Comparative example 10
TiO of the invention 2 -CeO 2 Composite nanomaterial and comparative example of preparation method thereof, tiO of comparative example 2 -CeO 2 Raw material nano TiO of composite nano material 2 The preparation method is the same as in example 1, and the preparation method of the composite nanomaterial is basically the same as in example 1, except that Ce (NO 3 ) 3 ·6H 2 The amount of O was 70mg.
Effect example 1 characterization data determination
For example 1, tiO was prepared 2 -CeO 2 The composite nanomaterial is characterized, and the measurement items are as follows:
detection of TiO by ultraviolet-visible spectrophotometer 2 -CeO 2 Ultraviolet characteristic absorption peaks of the composite nano material; the ultraviolet-visible spectrophotometer is provided by Shimadzu instruments (Suzhou) limited, and the model is UV-1900;
TiO measurement using nano-particle size and Zeta potential analyzer 2 -CeO 2 Particle size and particle size distribution of the composite nanomaterial; the nanometer granularity and Zeta potential analyzer is provided by Dachang ocean (Shanghai) limited company, and the model is microtrac/nanotrac wave II;
TiO is prepared by a Transmission Electron Microscope (TEM) and a Scanning Electron Microscope (SEM) 2 -CeO 2 Observing the morphology and the particle size of the composite nano material; the transmission electron microscope is provided by Simer Feier technology company and has the model number of FEI Talos F200S; scanning electron microscope was supplied by the zeiss group, germany, model number Sigma 300;
TiO by BrookX-ray spectrometer (EDS) 2 -CeO 2 Analyzing the element composition in the composite nano material; the bruck X-ray spectrometer is provided by bruck, germany, model number quitax;
TiO is prepared by X-ray photoelectron spectroscopy (XPS) 2 -CeO 2 Performing element semi-qualitative analysis on the composite nano material; x-rayThe line photoelectronic energy spectrum technology is provided by the Siemens Feier technology company and is of the model K-Alpha.
As shown in fig. 1 and 2, tiO 2 -CeO 2 The composite nano material is light yellow/milky white and has an ultraviolet characteristic absorption peak at 265.5 nanometers, which proves that the preparation method can successfully prepare light yellow/milky TiO 2 -CeO 2 Composite nanomaterial. As shown in fig. 3, tiO 2 -CeO 2 The PDI of the composite nano material is 0.264 and less than 0.3, which shows that the TiO prepared by the preparation method of the invention 2 -CeO 2 The composite nano material has uniform particle size distribution and good dispersibility. As shown in fig. 4 and 5, under TEM, tiO 2 -CeO 2 The particle size of the composite nano material is 15-20nm, and TiO is arranged under SEM 2 -CeO 2 The composite nano material is spherical, and the grain diameter is 15-20nm, which shows that the TiO prepared by the invention 2 -CeO 2 The composite nanometer material is spherical, has the grain diameter of 15-20nm and the specific surface area is large. As shown in FIG. 6, tiO is treated by EDS 2 -CeO 2 Analysis of the composite nanomaterial confirmed that the TiO of the present invention 2 -CeO 2 The composite nanomaterial has Ti element, ce element and O element. As shown in fig. 7, according to TiO 2 -CeO 2 The full spectrum scanning spectrum of the composite nano material can obtain the TiO of the invention 2 -CeO 2 The surface of the composite nano material is mainly provided with C, O, ti, ce and other elements, ti can be judged to be positive tetravalent oxide according to the energy position of a spectrum peak (about 458.5 eV), the peak type characteristic and the energy difference of an orbital spin splitting peak, and the spectrum peak is analyzed by adopting a peak-splitting fitting method according to the standard spectrum peak type characteristics of 4-valence cerium oxide and 3-valence cerium oxide (the four-valence cerium oxide has typical 6 characteristic spectrum peaks and the three-valence cerium oxide has 4 characteristic spectrum peaks), and the main trivalent cerium oxide is judged from the peak type characteristics. According to the comprehensive analysis of different patterns and multiple aspects, the TiO can be determined 2 -CeO 2 Successfully preparing composite nano material and preparing the composite nano material and other prepared TiO 2 -CeO 2 Compared with the composite nano material which is spherical in shape, the particle size is smaller, and the specific surface area is larger.
TiO of comparative examples 3 to 10 2 -CeO 2 The composite nanomaterial is analyzed by an ultraviolet visible light instrument and a dynamic light scattering DLS technology.
As shown in FIG. 8, when the concentration of the aqueous ammonia solution is > 34mM and the amount thereof is > 12ml, tiO 2 -CeO 2 The PDI value of the composite nano material is 0.963 and is more than 0.3; tiO when the concentration of the ammonia water solution is less than 23mM and the dosage is less than 8ml 2 -CeO 2 The PDI value of the composite nano material is 0.948 and is more than 0.3, which indicates that the concentration and the dosage of the ammonia water solution are not suitable for preparing the TiO 2 -CeO 2 The composite nano material has uneven particle size distribution, is unstable and is easy to generate agglomeration phenomenon.
As shown in FIG. 9, when the heating and stirring time is > 4.5 hours, tiO 2 -CeO 2 Obvious agglomeration phenomenon occurs in the composite nano material; when the heating and stirring time is less than 4 hours, tiO 2 -CeO 2 The composite nano material has no obvious characteristic peak on an ultraviolet spectrogram, namely TiO is not prepared 2 -CeO 2 Composite nanomaterial.
As shown in fig. 10, when nano TiO 2 When the dosage is more than 550mg, tiO 2 -CeO 2 Obvious precipitation layering phenomenon of the composite nano material occurs; when nano TiO 2 When the dosage is less than 450mg, the nanometer granularity and TiO measured by a Zeta potential analyzer 2 -CeO 2 The composite nano material has larger ruler diameter, the average grain diameter reaches 884nm, the PDI value is 0.76 and is obviously larger than 0.2, which indicates that the size distribution of the composite nano material is also uneven.
As shown in fig. 11, when Ce (NO 3 ) 3 ·6H 2 When the O consumption is more than 47.7mg, the nano granularity and TiO measured by a Zeta potential analyzer 2 -CeO 2 The composite nano material has larger ruler diameter, the average particle diameter reaches 425nm, the PDI value is 0.963 and is obviously larger than 0.2, which indicates that the size distribution of the composite nano material is uneven; when Ce (NO) 3 ) 3 ·6H 2 When the O consumption is less than 39.1mg, tiO 2 -CeO 2 The composite nano material has no characteristic absorption peak on an ultraviolet spectrogram, namely TiO is not successfully prepared 2 -CeO 2 Composite nanomaterial.
Effect example 2 photocatalytic degradation of antibiotics experiments
Sample: tiO of example 1 2 -CeO 2 Composite nanomaterial, tiO of comparative example 1 2 Nanomaterial, ceO of comparative example 2 2 A nanomaterial. The samples were diluted to 18.5mM aqueous dispersion, respectively, before use.
Antibiotics: sulfamethoxazole and ciprofloxacin.
(1) And (3) degrading sulfamethoxazole by ultraviolet light catalysis.
Mixing 5ml of 50 μg/ml sulfamethoxazole water solution with 5ml of sample aqueous dispersion uniformly to obtain mixed solution, placing the mixed solution under a 365nm ultraviolet lamp, stirring and irradiating, respectively taking 1ml of sample mixed solution at 15000rpm and 12 ℃ for 10min when irradiation time is 0min, 5min, 40min, 80min, 120min, 160min, 200min and 240min, respectively, diluting 2 times of 0.9ml of supernatant, uniformly stirring, and characterizing by an ultraviolet spectrophotometer, wherein the result is shown in figure 12. The blank was 5ml of water instead of 5ml of the aqueous sample dispersion mixed with 5ml of 50. Mu.g/ml of aqueous sulfamethoxazole.
As shown in FIG. 12, compared with the blank, the aqueous sulfamethoxazole solution added with different nano materials has a certain degradation effect on sulfamethoxazole under 365nm ultraviolet irradiation, wherein the poor degradation effect is TiO of comparative example 1 2 Nanomaterial, ceO of comparative example 2 2 Nanomaterial, most preferably TiO according to the invention 2 -CeO 2 Composite nanomaterial and degradation degree increases with increasing irradiation time, illustrating the TiO of the present invention upon irradiation with 365nm ultraviolet light 2 -CeO 2 The composite nano material can degrade sulfamethoxazole in water.
(2) And degrading sulfamethoxazole by natural photocatalysis.
The experiment was similar to experiment (1) except that the mixed solution was irradiated under natural light while stirring, and the rest steps were the same, and the result is shown in fig. 13.
As shown in FIG. 13, compared with the blank, the aqueous sulfamethoxazole solution added with different nano materials has a certain degradation effect on sulfamethoxazole under the irradiation of natural light, wherein the degradation effectPoor TiO of comparative example 1 2 Nanomaterial, ceO of comparative example 2 2 Nanomaterial, most preferably TiO according to the invention 2 -CeO 2 Composite nanomaterial and degradation degree increases with irradiation time, illustrating the TiO of the present invention upon natural light irradiation 2 -CeO 2 The composite nano material can degrade sulfamethoxazole in water.
(3) Ultraviolet light catalyzes the degradation of ciprofloxacin.
Mixing 4ml of ciprofloxacin 50 μg/ml with 6ml of sample aqueous dispersion uniformly to obtain mixed solution, placing the mixed solution under a 365nm ultraviolet lamp, stirring and irradiating, respectively taking 1ml of sample mixed solution at 15000rpm and 12 ℃ for 10min when irradiation time is 0min, 5min, 40min, 80min, 120min, 160min, 200min and 240min, respectively, diluting 0.9ml of supernatant for 2 times, uniformly stirring, and characterizing by an ultraviolet spectrophotometer, and the result is shown in figure 14. The blank was 6ml of water instead of 6ml of the aqueous sample dispersion mixed with 4ml of 50. Mu.g/ml ciprofloxacin aqueous solution.
As shown in FIG. 14, the ciprofloxacin aqueous solution added with different nano materials has a certain degradation effect on ciprofloxacin under 365nm ultraviolet irradiation compared with the blank control, wherein the poor degradation effect is TiO of comparative example 1 2 Nanomaterial, ceO of comparative example 2 2 Nanomaterial, most preferably TiO according to the invention 2 -CeO 2 Composite nanomaterial and degradation degree increases with increasing irradiation time, illustrating the TiO of the present invention upon irradiation with 365nm ultraviolet light 2 -CeO 2 The composite nano material can degrade ciprofloxacin in water.
(4) And degrading ciprofloxacin by natural photocatalysis.
The experiment was similar to experiment (3), except that the mixed solution was irradiated while being stirred under natural light, and the rest steps were the same, and the result is shown in fig. 15.
As shown in fig. 15, the ciprofloxacin aqueous solution added with different nano materials has a certain degradation effect on ciprofloxacin under natural light irradiation compared with the blank control, wherein the poor degradation effect is the TiO of comparative example 1 2 Nanomaterial, ce of comparative example 2O 2 Nanomaterial, most preferably TiO according to the invention 2 -CeO 2 Composite nanomaterial and degradation degree increases with irradiation time, illustrating the TiO of the present invention upon natural light irradiation 2 -CeO 2 The composite nano material can degrade ciprofloxacin in water.
(5) Ultraviolet light/natural light catalyzes and degrades ciprofloxacin with different concentrations.
2ml of ciprofloxacin 50 μg/ml was taken and mixed with 8ml of the aqueous dispersion of the sample of example 1 to obtain a mixed solution 1 (final ciprofloxacin concentration is 10 μg/ml); 0.8ml of ciprofloxacin 50. Mu.g/ml was mixed with 9.2ml of the aqueous dispersion of the sample of example 1 to give a mixed solution 2 (final ciprofloxacin concentration: 4. Mu.g/ml). And (3) placing the mixed solution 1 or 2 under a 365nm ultraviolet lamp or natural light, stirring and irradiating, respectively taking 1ml of sample mixed solution at 15000rpm and 12 ℃ for 10min when the irradiation time is 0min, 5min, 40min, 80min, 120min, 160min, 200min and 240min, respectively, diluting 0.9ml of supernatant by 2 times, uniformly stirring, and then characterizing by an ultraviolet spectrophotometer, wherein the ultraviolet photocatalytic degradation result is shown in figure 16, and the natural photocatalytic degradation result is shown in figure 17. The blank was 6ml of water instead of 6ml of the aqueous sample dispersion mixed with 4ml of 50. Mu.g/ml ciprofloxacin aqueous solution.
As shown in FIG. 16, the TiO of example 1 was added as compared with the blank 2 -CeO 2 The ciprofloxacin aqueous solution of the composite nano material has degradation effect on low-concentration ciprofloxacin under 365nm ultraviolet light irradiation, and can degrade 4 mug/ml ciprofloxacin aqueous solution at the minimum, which shows that the TiO of the invention is used under 365nm ultraviolet light irradiation 2 -CeO 2 The composite nano material can completely degrade a small amount of ciprofloxacin in water.
As shown in FIG. 17, the TiO of example 1 was added as compared with the blank 2 -CeO 2 The ciprofloxacin aqueous solution of the composite nano material has degradation effect on low-concentration ciprofloxacin under natural light irradiation, and can degrade 4 mug/ml ciprofloxacin aqueous solution at the minimum, which shows that the TiO of the invention is used when the natural light irradiation is carried out 2 -CeO 2 The composite nano material can completely degrade a small amount of ciprofloxacin in water.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. TiO (titanium dioxide) 2 -CeO 2 The preparation method of the composite nano material is characterized by comprising the following steps: to nanometer TiO 2 Adding aqueous ammonia solution into the aqueous dispersion, dispersing uniformly, adding Ce salt, stirring at 95deg.C for 4-4.5 hr to obtain TiO 2 -CeO 2 Composite nanomaterial.
2. The TiO of claim 1 2 -CeO 2 The preparation method of the composite nano material is characterized in that the concentration of ammonia water in the ammonia water solution is 23-34mM, and the volume of ammonia water is 8-12ml.
3. The TiO of claim 2 2 -CeO 2 The preparation method of the composite nano material is characterized in that the concentration of ammonia water in the ammonia water solution is 25-29mM, and the volume of ammonia water is 9-11ml.
4. The TiO of claim 1 2 -CeO 2 The preparation method of the composite nano material is characterized in that the nano TiO 2 The molar ratio of the Ti element to the Ce element in the Ce salt is as follows: ce= (3.375-4.125): (0.029-0.036).
5. The TiO according to claim 4 2 -CeO 2 The preparation method of the composite nano material is characterized in that the nano TiO 2 The molar ratio of the Ti element to the Ce element in the Ce salt is as follows: ce= (3.6-3.9): (0.031-0.033).
6. The TiO of claim 1 2 -CeO 2 Composite materialThe preparation method of the nano material is characterized in that the nano TiO 2 The particle size is 5-10nm.
7. The TiO according to claim 1 or 6 2 -CeO 2 The preparation method of the composite nano material is characterized in that the nano TiO 2 The preparation method of the aqueous dispersion comprises the following steps: uniformly mixing water and isopropyl alcohol solution of isopropyl titanate, and drying to obtain nano TiO 2 An aqueous dispersion, said water being acidic.
8. The TiO according to claim 7 2 -CeO 2 The preparation method of the composite nano material is characterized in that the pH value of the water is adjusted to 5 by concentrated nitric acid, and the concentration of isopropyl titanate in the isopropyl titanate isopropanol solution is 0.84M.
9. TiO (titanium dioxide) 2 -CeO 2 Composite nanomaterial, characterized in that it is prepared by the preparation method of claims 1 to 8.
10. The TiO according to claim 9 2 -CeO 2 The application of the composite nano material in the field of photocatalytic degradation of antibiotics.
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