CN111085185B - CeO 2 :CDs/TiO 2 Nano material and application thereof in photocatalysis - Google Patents
CeO 2 :CDs/TiO 2 Nano material and application thereof in photocatalysis Download PDFInfo
- Publication number
- CN111085185B CN111085185B CN201911267476.0A CN201911267476A CN111085185B CN 111085185 B CN111085185 B CN 111085185B CN 201911267476 A CN201911267476 A CN 201911267476A CN 111085185 B CN111085185 B CN 111085185B
- Authority
- CN
- China
- Prior art keywords
- ceo
- cds
- tio
- solution
- nano material
- 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.)
- Active
Links
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 47
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title abstract description 14
- 238000007146 photocatalysis Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 23
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 15
- 229940043267 rhodamine b Drugs 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 19
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 238000001782 photodegradation Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 230000000593 degrading effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/51—
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/38—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses CeO 2 :CDs/TiO 2 Nano material and its application in photocatalysis. The nano CeO with good crystal form, remarkably improved conductivity and obviously changed degradation performance is synthesized by a simple and convenient method 2 :CDs/TiO 2 A material. The invention takes rare earth oxide as a template and adopts a loading and coating technology to load CDs on the traditional CeO 2 On the nano material, the electron transmission rate in the nano material is accelerated, so that the recombination of photo-generated electrons and holes is reduced, the potential of the material in photodegradation application is stimulated based on the principle, and the degradation time is greatly shortened.
Description
Technical Field
The invention belongs to the field of catalytic chemistry, and particularly relates to a photocatalytic material as well as a preparation method and application thereof.
Background
At present, a common problem faced by human beings is the energy problem, and the problem of solving the energy is more and more important due to the increasing severity of the problems of environmental pollution, exhaustion of fossil fuels and the like. Solar energy is one of the most potential new energy sources for development as an inexhaustible, clean and pollution-free ideal energy source. In recent years, photocatalytic technology, an advanced oxidation method, has been widely used to degrade wastewater due to its ability to generate reducing electrons and oxidizing holes, thereby effectively degrading intractable organic pollutants.
To obtain a good performance photocatalyst, the material constituting the photocatalyst must have a high specific surface area to allow the particles to be sufficiently in contact with organic contaminants, and the photocatalyst should also have good electron transport properties and good solar benefitsAnd (5) the utilization rate. So that the photo-generated electrons can be transmitted to the outside in time, the recombination with the photo-generated electron holes is avoided, and the sunlight is utilized as much as possible. Although some conventional photocatalysts have been used to degrade wastewater in simulated sunlight, such as TiO 2 Unfortunately, the practical use of these conventional catalysts is limited because they respond only to uv light, which is only 5% of sunlight, making the material less efficient for sunlight. On the other hand, the simple nano titanium dioxide small particles are not beneficial to the contact of the photocatalyst and pollutants.
In order to realize high-efficiency degradation performance, the nanoparticles are combined with a proper material, so that the band gap energy of the material can be reduced, the internal resistance of the material can be reduced, the transition of photo-generated electrons is facilitated, the quantity of excited photo-generated electrons is increased, the electronic output characteristic is improved, all the excited photo-generated electrons are rapidly transferred into a reaction liquid as far as possible, the recombination of carriers in the conduction process can be inhibited, and the electron transmission efficiency and the electron collection efficiency can be improved. May also be made of TiO 2 The edge of the light absorption band generates red shift, so that the TiO 2-based photocatalyst responds to the excitation of a visible light source, and the composition of photo-generated electrons and photo-generated holes on the surface of the nanoparticles is reduced, thereby improving the utilization rate of sunlight.
The technology for degrading organic pollutants by using photocatalytic materials also has certain defects: although the degradation effect of the photocatalyst is good, the green photocatalyst is difficult to find, and the semiconductor material applied to the photocatalyst is limited.
Disclosure of Invention
The invention aims to provide CeO capable of effectively reducing the resistance of a photocatalyst and increasing the solar energy utilization rate 2 :CDs/TiO 2 And (3) nano materials.
The technical scheme of the invention comprises the following steps:
(1) Adding a sodium citrate solution into the urea solution to obtain a mixed solution of urea and sodium citrate;
(2) Adding cerous chloride into the mixed solution obtained in the step (1), uniformly stirring, slowly adding hydrogen peroxide, and stirring;
(3) Carrying out reaction on the mixed solution obtained in the step (2) by adopting a hydrothermal method, cooling, centrifugally cleaning and drying after the reaction is finished to obtain CeO 2 ；
(4) The CeO obtained in the step (3) 2 Adding the mixture into the carbon point solution, and stirring for 12 hours;
(5) Filtering and drying the solution obtained in the step (4), putting the solution into ethanol, adding tetrabutyl titanate, stirring, centrifugally cleaning and drying to obtain the CeO 2 :CDs/TiO 2 And (3) nano materials.
Preferably, the mass ratio of urea to sodium citrate to cerous chloride is 5.
Preferably, the mass ratio of the cerous chloride to the hydrogen peroxide is 4; the hydrothermal reaction temperature is 180 ℃ and the hydrothermal reaction time is 22 hours.
Preferably, the Carbon Dot (CDs) solution is prepared by (a) dissolving citric acid in ultrapure water, ultrasonically dispersing and then vigorously stirring to homogenize the solution; (b) And carrying out hydrothermal reaction on the obtained dispersion, cooling and centrifuging after the reaction is finished, and reserving a supernatant to obtain a carbon dot solution.
Preferably, ceO 2 The mass ratio of the carbon dot solution to the carbon dot solution is 1.
Preferably, the mass ratio of tetrabutyl titanate to cerous chloride is 10.
The invention also provides CeO 2 :CDs/TiO 2 The application of the nano material in photocatalytic degradation of RhB (rhodamine B).
Compared with the prior art, the invention synthesizes the hollow material loaded with CDs and coated with TiO based on the rare earth oxide which is cheap and has wider application 2 . When CeO is present 2 Hollow nano material loaded with CDs and coated with TiO 2 After the thin layer, the resistance inside the composite material becomes small due to the good conductivity of CDs, while TiO 2 Coating of the thin layer allows TiO to be formed 2 With CeO 2 Forming heterojunction, and under the irradiation of visible light, the generated photogenerated electrons can be rapidly formed by TiO through the loaded CDs 2 Transfer of the conduction band to CeO 2 Layer, secondly, supported on TiO 2 With CeO 2 The intermediate CDs, acting both as electron acceptors and electron donors, facilitate electron transport in the TiO 2 With CeO 2 Meta-transfer, and TiO 2 Or CeO 2 The excess electrons can also be transferred to loaded CDs, which promotes the separation of photogenerated electrons and photogenerated holes, so that the photogenerated electrons have better photocatalytic performance, and the degradation of RhB is finally realized.
Drawings
FIG. 1 shows CeO 2 :CDs/TiO 2 EDS spectra of each element of the nano material.
FIG. 2 is a TEM image of CDs.
FIG. 3 shows CeO 2 :CDs/TiO 2 TEM images of nanomaterials.
FIG. 4 shows CeO 2 :CDs/TiO 2 SEM images of nanomaterials.
FIG. 5 shows CeO 2 :CDs/TiO 2 Ultraviolet-near infrared spectrogram of the nanometer material.
FIG. 6 shows CeO 2 :CDs/TiO 2 Photocurrent response graph of the nanomaterial.
FIG. 7 shows CeO 2 :CDs/TiO 2 The nano material is used for degrading RhB under the photocatalysis of each sample under the irradiation of visible light.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and embodiments.
The invention is in TiO 2 Adding CeO into 2 And the carbon dots are loaded, the electron transport mode of the material is changed through the loading of the carbon dots, and the internal resistance of the material is reduced and the transport speed is accelerated due to the addition of the carbon dots.
CeO of the invention 2 :CDs/TiO 2 The preparation method of the nano material comprises the following steps:
(1) Dissolving citric acid in ultrapure water, ultrasonically dispersing, mixing and uniformly stirring to prepare a colorless transparent solution;
(2) Placing the colorless transparent solution in a high-pressure hydrothermal reaction kettle for reaction;
(3) Cooling, centrifuging the light yellow liquid obtained by the reaction, and reserving the supernatant to obtain a carbon dot solution;
(4) Preparing a urea aqueous solution, and adding a sodium citrate solution to obtain a mixed solution of urea and sodium citrate;
(5) Adding cerium chloride into the mixed solution, uniformly stirring, slowly adding hydrogen peroxide, and stirring to obtain a light yellow mixed solution;
(6) Reacting the mixed solution by a hydrothermal method;
(7) After cooling, centrifugally cleaning and drying;
(8) Adding the dried sample into the solution of the carbon dots, and stirring for one night;
(9) Filtering and drying the powder, putting the powder into ethanol, adding tetrabutyl titanate, stirring, centrifugally cleaning, and drying to obtain CeO 2 :CDs/TiO 2 And (3) nano materials.
The application process is as follows: ceO is added 2 :CDs/TiO 2 The nano material is placed in RhB solution according to the feeding ratio of 0.5g/L, after dark reaction for 30min, a light source is turned on, reaction liquid is taken at certain intervals, solid is filtered out, and ultraviolet absorption spectrum data of the liquid is measured. The composite material prepared by the invention has better photocatalytic performance and higher degradation rate than pure CeO 2 The method is greatly improved. Under the dark reaction of 30 minutes, the photocatalyst is dispersed in the RhB solution uniformly under the condition of vigorous stirring, the influence of the dispersion unevenness of materials on the experiment is eliminated, and the measured data are in line with the linear condition. The light source is a 300W xenon lamp provided with a UVCUT420nm type optical filter. The data are recorded as UV absorption Spectroscopy data recording absorbance at wavelength 553 nm.
Examples
1、 CeO 2 :CDs/TiO 2 Preparation of nanomaterials
(1) Dissolving 0.4196g of citric acid in 10mL of ultrapure water, and placing the solution in an ultrasonic cleaning machine for ultrasonic treatment for 20min to completely disperse the solution; after stirring vigorously for 15min, adding the transparent liquid into a polytetrafluoroethylene high-pressure hydrothermal reaction kettle, reacting for 5h at 200 ℃, after the transparent liquid is naturally cooled, centrifuging the solution at 13000 rmp/min for 20min, and removing precipitates to obtain a light yellow solution, namely a carbon dot solution.
(2) 1.0793g of urea is placed in 170mL of ultrapure water for ultrasonic dispersion for 10min, 10mM/L of sodium citrate solution 83mL is added, reaction is carried out for 12min under vigorous stirring, 0.8889g of cerous chloride is added, stirring is carried out for 20min, 1mL of hydrogen peroxide is dripped at a constant speed at a speed of 10mL/min, and stirring is carried out continuously for 30min. Adding the faint yellow mixed solution formed by the reaction into a 50mL polytetrafluoroethylene high-pressure hydrothermal reaction kettle, reacting for 22h at 180 ℃, naturally cooling, centrifugally cleaning, and drying at 60 ℃ to obtain faint yellow CeO 2 And (3) sampling.
(3) 0.1263g of CeO was taken 2 Placing in 2.526g carbon dot solution, ultrasonically dispersing for 30min, stirring for 12h to make the carbon dots fully attached to CeO 2 The above. 20mg of the material with the carbon points attached is taken, 20mL of ethanol and 7mL of acetonitrile are added, 0.25mL of ammonia water is added at the rotating speed of 500r/min, stirring is carried out for 5min, 200 mu L of TBOT is added, and stirring is carried out overnight. The reaction solution is centrifugally cleaned at the rotating speed of 6500rmp/min, and the product is dried at 60 ℃ for later use.
2、CeO 2 :CDs/TiO 2 Characterization of nanomaterials
FIG. 1 shows CeO prepared according to the present invention 2 :CDs/TiO 2 EDS spectrum of the nano material, distribution of Ce element, C element, ti element and O element can be observed from the EDS spectrum to confirm CDs and TiO 2 Is surely supported on CeO 2 Thereon CeO is formed 2 :CDs/TiO 2 And (3) nano materials.
FIGS. 2 and 3 show the carbon dots and CeO prepared by the present invention, respectively 2 :CDs/TiO 2 The TEM image of the field emission transmission electron microscope of the nano material shows that the prepared carbon dots have uniform particle size which is approximately 3nm-5nm in FIG. 2; from FIG. 3, it can be seen that prepared CeO 2 :CDs/TiO 2 The nano material is of a double-layer hollow structure, the particle size is uniform, and the size is about 400 nm.
FIG. 4 shows the preparation of CeO according to the invention 2 :CDs/TiO 2 The SEM image of the field emission scanning electron microscope of the nano material shows that the material is a hollow sphere and is further determined to be a double-layer structure.
FIG. 5 shows the preparation of the inventionThe ultraviolet-near infrared spectrum of the composite material is shown in the specification, wherein a represents a pure carbon point, b represents pure titanium dioxide, c represents pure cerium dioxide, and d represents CeO 2 :CDs/TiO 2 The nano material can absorb light better than three pure substances, and has the best utilization rate of sunlight.
FIG. 6 shows the photocurrent response of the composite material prepared by the present invention under visible light irradiation, and curve a represents pure CeO 2 A photocurrent curve of (a); curve b represents CeO 2 /TiO 2 Curve c represents CeO 2 Photocurrent curve of CDs, curve d represents CeO 2 :CDs/TiO 2 Photocurrent curves for nanomaterials. As can be seen from the figure, ceO prepared by the present invention 2 :CDs/TiO 2 The nano material has the strongest photoresponse current capable of repeatedly responding, and shows that CeO 2 :CDs/TiO 2 The nanomaterial internal resistance is the smallest and the photocurrent the most stable.
3. Nano material photocatalysis performance test
100mL of RhB (C) was taken 0 = 1×10 -5 M), adding 50mg of photocatalyst into the suspension, and continuously stirring the suspension for 30min under dark conditions to ensure that the catalyst and the RhB reach adsorption-desorption equilibrium. At regular intervals, 4mL of the suspension was taken, centrifuged to remove the precipitate and the RhB concentration was further analyzed using a uv spectrophotometer to record absorbance at 553 nm.
FIG. 7 shows the photocatalytic performance curves of different comparative materials, curve a representing pure CeO 2 The performance curve of the photocatalytic degradation of RhB; curve b represents CeO 2 /TiO 2 The curve c represents CeO 2 The performance curve of photocatalytic degradation of CDs to RhB, and the curve d represents CeO 2 :CDs/TiO 2 Performance curve of nano material for photocatalytic degradation of RhB.
It is clearly observed from the figure that 2 Compared with three composite materials, the photocatalytic performance of the composite material is improved to different degrees, wherein CeO 2 :CDs/TiO 2 Photocatalytic activity of composite materialRelatively pure CeO 2 Significantly improved by CeO 2 :CDs/TiO 2 The degradation rate of the composite material to RhB reaches 95.52 percent under the irradiation of a xenon lamp with the wavelength of more than or equal to 420nm for 2 hours.
The results of these experiments show that: ceO prepared by the method of the invention 2 :CDs/TiO 2 The nanometer material effectively changes the internal electron transmission of the material, and improves the electron transmission efficiency and the collection efficiency; the utilization rate of sunlight is enhanced, and the time for degrading RhB by photocatalysis is obviously shortened.
Claims (3)
1. CeO (CeO) 2 :CDs/TiO 2 The preparation method of the nano material is characterized by comprising the following steps:
(1) Adding a sodium citrate solution into the urea solution to obtain a mixed solution of urea and sodium citrate;
(2) Adding cerous chloride into the mixed solution obtained in the step (1), uniformly stirring, slowly adding hydrogen peroxide, and stirring;
(3) Carrying out reaction on the mixed solution obtained in the step (2) by adopting a hydrothermal method, cooling, centrifugally cleaning and drying after the reaction is finished to obtain CeO 2 ；
(4) The CeO obtained in the step (3) 2 Adding the mixture into a carbon point CDs solution, and stirring for 12 hours;
(5) Filtering and drying the solution obtained in the step (4), putting the solution into ethanol, adding tetrabutyl titanate, stirring, centrifugally cleaning and drying to obtain the CeO 2 :CDs/TiO 2 A nanomaterial;
wherein the mass ratio of urea to sodium citrate to cerous chloride is 5;
CeO 2 the mass ratio of the carbon point solution to the carbon point solution is 1;
the mass ratio of the cerous chloride to the hydrogen peroxide is 4;
the hydrothermal reaction temperature is 180 ℃ and the time is 22 hours;
the mass ratio of tetrabutyl titanate to cerous chloride is 10.
2. Prepared by the process of claim 1CeO 2 :CDs/TiO 2 And (3) nano materials.
3. CeO prepared by the method of claim 1 2 :CDs/TiO 2 The application of the nano material in photocatalytic degradation of rhodamine B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911267476.0A CN111085185B (en) | 2019-12-11 | 2019-12-11 | CeO 2 :CDs/TiO 2 Nano material and application thereof in photocatalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911267476.0A CN111085185B (en) | 2019-12-11 | 2019-12-11 | CeO 2 :CDs/TiO 2 Nano material and application thereof in photocatalysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111085185A CN111085185A (en) | 2020-05-01 |
| CN111085185B true CN111085185B (en) | 2023-02-28 |
Family
ID=70395416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911267476.0A Active CN111085185B (en) | 2019-12-11 | 2019-12-11 | CeO 2 :CDs/TiO 2 Nano material and application thereof in photocatalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111085185B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113457664B (en) * | 2021-05-20 | 2023-11-10 | 扬州大学 | D-CeO 2 :CQDs@WO 3 Nanocomposite hollow material, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212400A (en) * | 2013-03-06 | 2013-07-24 | 山东大学 | Cerium oxide/titanium dioxide nano belt surface heterostructure photocatalyst with capture-catalysis performance and preparation method thereof |
| CN103252201A (en) * | 2012-02-17 | 2013-08-21 | 国家纳米科学中心 | Au@CeO2 nanocomposite material having hollow core-shell structure, and preparation method thereof |
| CN104907060A (en) * | 2015-04-24 | 2015-09-16 | 宿州学院 | CeO2 / TiO2 heterojunction nano flower preparation method |
| CN106179304A (en) * | 2016-07-28 | 2016-12-07 | 南昌航空大学 | A kind of CeO possessing photo catalytic reduction performance2tiO2the preparation method of nano composite material |
| CN106277023A (en) * | 2016-07-29 | 2017-01-04 | 扬州大学 | The preparation method and applications of double-decker CeO2 nano-hollow ball |
| CN107243340A (en) * | 2017-06-22 | 2017-10-13 | 南昌航空大学 | A kind of preparation method of ceric oxide nanorod doping titanium dioxide nano particle photochemical catalyst |
-
2019
- 2019-12-11 CN CN201911267476.0A patent/CN111085185B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103252201A (en) * | 2012-02-17 | 2013-08-21 | 国家纳米科学中心 | Au@CeO2 nanocomposite material having hollow core-shell structure, and preparation method thereof |
| CN103212400A (en) * | 2013-03-06 | 2013-07-24 | 山东大学 | Cerium oxide/titanium dioxide nano belt surface heterostructure photocatalyst with capture-catalysis performance and preparation method thereof |
| CN104907060A (en) * | 2015-04-24 | 2015-09-16 | 宿州学院 | CeO2 / TiO2 heterojunction nano flower preparation method |
| CN106179304A (en) * | 2016-07-28 | 2016-12-07 | 南昌航空大学 | A kind of CeO possessing photo catalytic reduction performance2tiO2the preparation method of nano composite material |
| CN106277023A (en) * | 2016-07-29 | 2017-01-04 | 扬州大学 | The preparation method and applications of double-decker CeO2 nano-hollow ball |
| CN107243340A (en) * | 2017-06-22 | 2017-10-13 | 南昌航空大学 | A kind of preparation method of ceric oxide nanorod doping titanium dioxide nano particle photochemical catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Double-shell CeO2@TiO2 hollow spheres composites with enhanced light harvesting and electron transfer in dye-sensitized solar cells;Jingyi Bai，等;《Journal of Alloys and Compounds》;20170610;第864-871页 * |
| Wood powder-derived quantum dots for CeO2 photocatalytic and anticounterfeit applications;Xinchao Gong，等;《Optical Materials》;20190821;第109302页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111085185A (en) | 2020-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Synthesis of hollow TiO2@ g-C3N4/Co3O4 core-shell microspheres for effective photooxidation degradation of tetracycline and MO | |
| CN101653728B (en) | Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst | |
| Jiang et al. | Synthesis of flowerlike g‐C3N4/BiOBr with enhanced visible light photocatalytic activity for dye degradation | |
| Xu et al. | BiOCl decorated NaNbO3 nanocubes: a novel pn heterojunction photocatalyst with improved activity for ofloxacin degradation | |
| CN101537354A (en) | Preparation method of visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst and applications thereof | |
| Zhou et al. | Experimental study on photocatalytic activity of Cu 2 O/Cu nanocomposites under visible light | |
| CN107243340B (en) | Preparation method of cerium dioxide nanorod doped titanium dioxide nanoparticle photocatalyst | |
| CN108654607A (en) | The preparation method of silver nano-grain/carbon/nano titania compound of nucleocapsid | |
| Feng et al. | Two-step construction of WO3@ TiO2/CS-biochar S-scheme heterojunction and its synergic adsorption/photocatalytic removal performance for organic dye and antibiotic | |
| Jinfeng et al. | Preparation, characterization, and activity evaluation of CuO/F-TiO 2 photocatalyst | |
| CN111085227A (en) | CeO2-BiOCl nano material and application thereof in photocatalysis | |
| Zhai et al. | Enhanced photocatalytic degradation of tetracycline over magnetic La0. 7Sr0. 3MnO3/g-C3N4 p–n heterojunction arising from the synergistic effects of oxygen vacancy defects and high-potential photogenerated electrons | |
| CN113769764B (en) | CdS/Cu 7 S 4 /CdMoO 4 Preparation method and application of nano heterostructure | |
| Wang et al. | Enhanced the photocatalytic activity of B–C–N–TiO2 under visible light: Synergistic effect of element doping and Z-scheme interface heterojunction constructed with Ag nanoparticles | |
| Priya et al. | Construction of MoS2 nanoparticles incorporated TiO2 nanosheets heterojunction photocatalyst for enhanced visible light driven hydrogen production | |
| CN111085185B (en) | CeO 2 :CDs/TiO 2 Nano material and application thereof in photocatalysis | |
| Fu et al. | Enhancement of photocatalytic dye degradation and photoconversion capacity of graphene oxide/SnO2 nanocomposites | |
| Guo et al. | Enhanced photocatalytic nitrogen fixation of etched Ag-doped PM-CdS catalyst under visible light irradiation | |
| Luo et al. | Facile synthesis of δ-Bi 2 O 3 particles/rod-like Bi 4 O 7 composite with enhanced visible light-driven photocatalytic performance | |
| Zhang et al. | Fabrication and photocatalytic property of one-dimensional SrTiO 3/nanostructures | |
| CN111437857A (en) | Novel photocatalytic film based on titanium nitride and titanium oxide and preparation method thereof | |
| CN115301225A (en) | Preparation method and application of bismuth/titanium dioxide photocatalytic degradation material with hollow microsphere structure | |
| CN111346627B (en) | Multi-junction TiO2Nano heterostructure photocatalyst and preparation method thereof | |
| CN108855242B (en) | Photocatalyst, preparation method and use method thereof | |
| CN113117661A (en) | Catalyst of graphene quantum dot doped titanium dioxide, preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |