CN109499615A - A kind of solid luminescent nano material of polyoxometallic acid salt dopping and its preparation method and application - Google Patents
A kind of solid luminescent nano material of polyoxometallic acid salt dopping and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- 239000002253 acid Substances 0.000 title claims abstract description 15
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- 238000001907 polarising light microscopy Methods 0.000 claims abstract description 46
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 45
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 9
- 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 abstract description 9
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 9
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910020881 PMo12O40 Inorganic materials 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
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- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
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- 239000007788 liquid Substances 0.000 claims description 3
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- 244000111489 Gardenia augusta Species 0.000 claims description 2
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- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 claims description 2
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7719—Halogenides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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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- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
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- Luminescent Compositions (AREA)
Abstract
The invention belongs to solid luminescent technical field of nanometer material preparation, and in particular to a kind of solid luminescent nano material of polyoxometallic acid salt dopping and its preparation method and application.It is inquired into CeF as dopant using different types of POMs in the present invention3The influence of nanocrystal pattern and PL performance, the present invention is using PVP as reaction medium, the higher CeF of low temperature synthetic crystallization degree3And POMs/CeF3Nano material powder, the nano material is as catalyst after 6 h of illumination, catalysis degradation modulus to rhodamine B is up to 98%, originally show that the nano material of preparation has good application prospect as photochemical catalyst in degrading waste water in terms of pollutant, this method has easy to operate, the advantages such as easy to repeat and used raw material is inexpensive, is easy to get, and sintering temperature is low.
Description
Technical field
The invention belongs to solid luminescent technical field of nanometer material preparation, and in particular to a kind of polyoxometallic acid salt dopping
Solid luminescent nano material and its preparation and application.
Background technique
POMs(polyoxometallate) as a kind of important inorganic compound, in catalysis, pharmacology, electronics, magnetic material
The fields such as material and luminescence generated by light are with a wide range of applications.
Nano material (PNMs) based on polyoxometallate is a branch of POMs, due to its form, ingredient or big
It is small to be adjusted by modern synthetic technology, therefore there is practical application value, with other traditional monocrystalline POMs compounds
It compares, PNMs is attracted wide attention with its excellent performance.2002, Zhang et al. used reverse microemulsion process (Zhang
X H, Xie S Y, Jiang Z Y, et al. Starlike nanostructures of polyoxometalates
K3 [PMo12O40]· nH2O synthesized and assembled by an inverse microemulsion
Method [J] Chemical Communications, 2002 (18): 2032-2033.), synthesize K3[PMo12O40]·
nH2O star nanostructure.2003, Liu et al. people to PNMs carried out a large amount of system research (Liu T, Diemann E,
Li H, et al. Self-assembly in aqueous solution of wheel-shaped Mo154 oxide
Clusters into vesicles [J] Nature, 2003,426 (6962): 59.), they have found, have wheel shape
Mo154It can be self-assembled into the vesicle that mean radius is about 45 nm, the metal oxide of this nano-scale in aqueous solution
Aggregation shows hollow ball shape structure, meanwhile, a series of nano vesicles with blackberry, blueberry type structure are obtained, and to its property
It is studied in detail in the solution.Recently, the growth phenomenon of Cronin seminar discovery inorganic matter hollow tubular structures
(Cooper G J T, Boulay A G, Kitson P J, et al. Osmotically driven crystal
morphogenesis: a general approach to the fabrication of micrometer-scale
tubular architectures based on polyoxometalates[J]. Journal of the American
Chemical Society, 2011,133 (15): 5947-5954.), this may send out explaining in bioprocess fossil record
Existing structure is of great significance.The report of different-shape PNMs, it is shown that its diversity in Chemical self-assembly.
A critical nature of luminescence generated by light (PL) property as PNMs, receives more and more attention, but phase in recent years
For other properties of PNMs, the research of photoluminescence performance is relatively fewer.The study found that nano material is in self assembling process
In, POMs may will affect its pattern as dopant, to generate product of different shapes.In addition, POMs is effective electricity
Sub- receptor and carrier, the behavior of this electron transmission intermediary can also make the performance of POM change PL material.
Photochemical catalyst is commonly called as photocatalyst, refers to the system that the chemical substance of catalytic action can be played under the excitation of photon
Claim.It in human body and the harmful organic substance of environment, and economizes on resources and avoids the mistake of environmental pollution in photocatalysis Decomposition
It is played an important role in journey.With nanoscale composite photo-catalyst POM/CeF3It, can due to the characteristic with high specific area
To provide more active sites for absorption pollutant, facilitate photocatalysis.Therefore, probing into one kind has luminescent properties not similar shape
The POM/CeF of looks3Photo-catalysis function nano material is of great significance.
Summary of the invention
It is a kind of with different-shape the technical problem to be solved by the present invention is to prepare, and the POM/ with luminescent properties
CeF3Photo-catalysis function nano material.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of preparation method of the solid luminescent nano material of polyoxometallic acid salt dopping, comprising the following steps:
1) soluble cerium salt, polyvinylpyrrolidone (PVP), KBF are taken4It is placed in the reaction kettle that volume is 25 ml, adds with POMs
Enter distilled water sample dissolution, stirring at normal temperature 20-40 min obtains mixed solution；
2) reaction kettle is transferred in baking oven, rises to 40-180 DEG C with the heating rate of 0.1-2 DEG C/min, the pressure in reaction kettle
Power rises to 110-170 KPa with the rate of 3-40 KPa/h, and constant temperature and pressure keeps 6-24 h, is cooled to room temperature, is separated by solid-liquid separation,
The mixed liquor (1-5 mL) of solid deionized water and ethyl alcohol washs 2-5 times, the volume ratio of deionized water and ethyl alcohol in mixed liquor
For (1-3): 1, it is then dried overnight at 50-70 DEG C, obtains solid luminescent nano material POM/CeF3。
The solubility cerium salt is cerous nitrate, cerous sulfate or cerium chloride.
Wherein, the POMs is Na3PMo12O40、K4SiW12O40、Na3PW12O40One or more of, for the ease of saying
It is bright, Na3PMo12O40、K4SiW12O40、Na3PW12O40Abbreviation α-PMo respectively12、α-SiW12、α-PW12, synthetic method is with reference to text
It offers: Masteri-Farahani M, Ghorbani M, Ezabadi A, et al. Star-shaped Keggin-type
heteropolytungstate nanostructure as a new catalyst for the preparation of
quinoxaline derivatives[J]. Comptes Rendus Chimie, 2014, 17(11): 1136-1143。
Specifically, soluble cerium salt and KBF in step 1)4Mass ratio be 1:(1-3), specifically, soluble cerium salt with
KBF4Mass ratio be 1:1,1:2 or 1:3, or be expressed as, soluble cerium salt and KBF4Molar ratio be 1:(4-5).
Specifically, soluble cerium salt and POMs mass ratio are (1-9) in step 1): 1, specifically, soluble cerium salt with
POMs mass ratio is (13:1.5), (13:5), (13:10), or is expressed as, and soluble cerium salt and POMs molar ratio are (60-5):
1, specifically, soluble cerium salt and POMs molar ratio are (299:5), (299:8), (299:14), (299:26), (299:53).
Further, in step 1) soluble cerium salt proportion (0.02-0.08) g of every 0.130 g PVP, it is preferred that it is every
The soluble cerium salt of 0.130 g matches the PVP of 0.05 g.
Using the solid luminescent nano material POM/CeF of the polyoxometallic acid salt dopping of above method preparation3。
The solid luminescent nano material POM/CeF of the polyoxometallic acid salt dopping3Pollutant answers in degrading waste water
With specifically, the pollutant is dyestuff or formaldehyde, the dyestuff can be rhodamine B, methylene blue, alizarin red S, cape jasmine
Uranidin G or Congo red, in application, by the nano material POM/CeF of 0.06-0.12 g3Being added to volume is 40-45 mL's
In solution containing pollutant, the concentration of the pollutant is 10-20 mg/L.
Preparation process of the invention is it can be seen that in CeF3In nanocrystal, these crystal accumulations are formed together to be had
The nanometer sheet of disc shape, due to nanometer sheet be it is loose get together, so can have minimum micropore, not POMs's
In the case of, these plate-like nanometer sheets are gradually grown up the hexagonal structure that is positive by neck.
In POMs/CeF3In sample, when introducing a small amount of POMs, dopant can occupy interstitial hole and micropore, densification aggregation
State cannot be formed, and discoid nanometer sheet is formed.When POMs quantity increases, growth mechanism may change.It can push away
Disconnected, the supersaturation of reaction system has critical impact to crystal growth.With being continuously increased for POMs content, starting material it is total
Concentration increases, and the growth of one side dislocation driving will make nanocrystal be gathered into sphere, on the other hand, fast nucleation and high satiety
The generation that many activated centres in system are promoted with the growth of degree causes nucleus that cannot grow always along certain crystal orientation, institute
To cause dendron to grow, colored form is eventually formed.
In CeF3POMs doping is adulterated in nanocrystal can lead to the variation of crystal morphology, meanwhile, these are received after doping
The PL performance of nano composite material is also different, adulterates different types of POM/CeF3With different emission peaks.By to mixing
The adjustment of miscellaneous amount, can be to POMs/CeF3The shape of nanocrystal is regulated and controled, further, it is also possible to adjust its PL performance.
The invention has the following advantages:
1) inorganic fluorescent fluoride CeF3Crystal has low-down vibrational energy, and the present invention is using with photocatalysis
POMs inquires into it to CeF as dopant3The influence of nanocrystal pattern and PL performance.In turn, to solve simple biology at
Asking for appearance of nano material and FL performance can not be effectively adjusted as present in, wastewater through organic matter degradation and fluorescence chemical sensor
Topic has potential application.
2) by three kinds of α-PMo12, α-SiW12With α-PW12Polyoxometallate (POMs) is doped into CeF respectively3Solid-state
In Illuminant nanometer material, flower-shaped, sheet, spherical has been respectively obtained.Since POMs has the spy for efficiently receiving electronics and carrier
Therefore point is influencing CeF for POMs as a kind of dopant3While self assembly pattern, can also FL property to host generate
It influences.POMs is entrained in CeF by the present invention3In, cause CeF3Lattice defect is generated, while reinforcing material photocatalysis performance,
It is realized again to CeF3The controllability of the photoluminescent property (FL) of nanocrystal adjusts, and blue shift and Red Shift Phenomena occurs, is receiving
In rice material, completes and the dual controllability on its pattern and performance is adjusted.Preparation method of the invention is in material science
Morphological property controlling party mask have broad application prospects, meanwhile, the nano material of preparation is in simple bio-imaging, waste water
It is had potential application in organic matter degradation, fluorescence chemical sensor.
3) present invention is using PVP as reaction medium, the higher POMs/CeF of low temperature synthetic crystallization degree3Nano material powder
End.The preparation method has the advantages such as raw material easy to operate, easy to repeat and used is inexpensive, is easy to get, and sintering temperature is low.
Material catalytic efficiency and recycling rate of waterused in photocatalytic degradation is all higher, and the wasting of resources and additional pollution are few.
Detailed description of the invention
Fig. 1 is PMo prepared by embodiment 112/CeF3, embodiment 2 prepare SiW12/CeF3, embodiment 3 prepare PW12/
CeF3And CeF3Performance test figure；
Fig. 2 is PMo prepared by embodiment 112/CeF3The SEM and EDX of nano flower-like crystal scheme；
Fig. 3 is SiW prepared by embodiment 212/CeF3PW prepared by nanometer sheet and embodiment 312/CeF3The SEM of nanosphere schemes；
Fig. 4 is in embodiment 5 and embodiment 7 using PMo when different dopings12 / CeF3SEM figure；
Fig. 5 be embodiment 6, embodiment 4, in embodiment 1 and embodiment 16 differential responses temperature to PMo12/CeF3The shadow of formation
It rings；
Fig. 6 be embodiment 1, in embodiment 8-15 the differential responses time to PMo12/CeF3The influence of formation；
Fig. 7 is PMo in embodiment 112/CeF3The nanocrystal SEM that stability is probed into water figure；
Fig. 8 is PMo in embodiment 112/CeF3, SiW in embodiment 212/CeF3With PW in embodiment 312/CeF3Nanocrystal
Launching light spectrogram；
Fig. 9 is the PMo of embodiment 1-3 preparation12/CeF3、SiW12/CeF3And PW12/CeF3Rhodamine B is dropped as photochemical catalyst
The relational graph of m- degradation efficiency when solution；
Figure 10 is the PMo of embodiment 1-3 preparation12/CeF3、SiW12/CeF3And PW12/CeF3Photochemical catalyst circular response circulation benefit
With the test result figure of number.
Specific embodiment
Following embodiment is implemented under the premise of the technical scheme of the present invention, gives detailed embodiment and tool
The operating process of body, but protection scope of the present invention is not limited to following embodiments.
Use volume for the hydrothermal reaction kettle of 25 ml, material is 316 type stainless steels, 7 mm of wall thickness；Liner is polytetrafluoro
Ethylene, 5 mm of thickness of inner lining.
Embodiment 1
A kind of solid luminescent nano material PMo of polyoxometallic acid salt dopping12 / CeF3Preparation method, comprising the following steps:
1) by the Ce (NO of 0.130 g3)3·6H2O(0.299 mmol), the PVP(polyvinylpyrrolidone of 0.050 g),
The KBF of 0.151 g4(1.199 mmoL) and 0.050 g α-PMo12(0.026 mmoL) is placed in 25 mL reaction kettles, is added
18.5 mL distilled water obtain mixed solution after room temperature is vigorously stirred 30 min；
2) reaction kettle is transferred in baking oven, rises to 140 DEG C with 1.2 DEG C of heating rate per minute, the pressure in reaction kettle
149 KPa are risen to the rate of 26 KPa/h, constant temperature and pressure keeps 12 h, autoclave is slowly cooled to room temperature naturally
Afterwards, yellow mercury oxide is obtained, sediment is centrifugated 10 min with 2500 r/pm rates, later with 2 mL deionized waters and second
Mixed liquor (the V of alcoholH2O:VCH3CH2OH=1:1) it washs three times, it is then dried overnight at 60 DEG C, finally obtains PMo12 / CeF3
Flower-like nanometer particle.
Embodiment 2
A kind of solid luminescent nano material SiW of polyoxometallic acid salt dopping12 / CeF3Preparation method, comprising the following steps:
1) by 0.130 g Ce (NO3)3·6H2O (0.299 mmol), the PVP of 0.050 g, the KBF of 0.151 g4
(1.199 mmoL) and 0.015 g α-SiW12(0.005 mmoL) is placed in 25 mL reaction kettles, 19 mL distilled water is added, often
After temperature is vigorously stirred 35 min, mixed solution is obtained；
2) reaction kettle is transferred in baking oven, rises to 180 DEG C with 1.6 DEG C of heating rate per minute, the pressure in reaction kettle
163 KPa are risen to the rate of 35 KPa/h, constant temperature and pressure keeps 12 h, autoclave is slowly cooled to room temperature naturally
Afterwards, obtain yellow mercury oxide, by sediment with 2500 r/pm rates be centrifugated 5 min obtain sediment, later with 3 mL go from
Mixed liquor (the V of sub- water and ethyl alcoholH2O:VCH3CH2OH=2:1) it washs three times, it is then dried overnight, finally obtains at 70 DEG C
SiW12 / CeF3Nanometer sheet.
Embodiment 3
A kind of solid luminescent nano material PW of polyoxometallic acid salt dopping12 / CeF3Preparation method, comprising the following steps:
1) by 0.130 g Ce (NO3)3·6H2O (0.299 mmol), the PVP of 0.050 g, the KBF of 0.151 g4 (1.199
) and 0.040 g α-PW mmoL12(0.014 mmoL) is placed in 25 mL reaction kettles, and 20 mL distilled water are added, and room temperature acutely stirs
After mixing 25 min, mixed solution is obtained；
2) reaction kettle is transferred in baking oven, rises to 120 DEG C with 1 DEG C of heating rate per minute, the pressure in reaction kettle with
The rate of 21 KPa/h rises to 141 KPa, and constant temperature and pressure keeps 12 h, after autoclave is slowly cooled to room temperature naturally,
Yellow mercury oxide is obtained, sediment is centrifugated 10 min with 2500 r/pm rates and obtains sediment, later with 5 mL deionizations
Mixed liquor (the V of water and ethyl alcoholH2O:VCH3CH2OH=3:1) it washs three times, it is then dried overnight at 50 DEG C, finally obtains PW12
/ CeF3Nanosphere.
Embodiment 4
A kind of solid luminescent nano material PMo of polyoxometallic acid salt dopping12 / CeF3Preparation method, comprising the following steps:
1) by 0.130 g Ce (NO3)3·6H2O (0.299 mmol), the PVP of 0.050 g, the KBF of 0.151 g4(1.199
) and 0.050 g α-PMo mmoL12(0.026 mmoL) is placed in 50 mL reaction kettles, and 17 mL distilled water are added, and room temperature acutely stirs
After mixing 40 min, mixed solution is obtained；
2) reaction kettle is transferred in baking oven, rises to 80 DEG C with 0.6 DEG C of heating rate per minute, the pressure in reaction kettle with
The rate of 13 KPa/h rises to 127 KPa, and constant temperature and pressure keeps 12 h, after autoclave is slowly cooled to room temperature naturally,
Yellow mercury oxide is obtained, sediment is centrifugated 5 min with 2500 r/pm rates and obtains sediment, later with 2 mL deionizations
Mixed liquor (the V of water and ethyl alcoholH2O:VCH3CH2OH=1:1) it washs three times, it is then dried overnight at 55 DEG C, finally obtains PMo12
/ CeF3Flower-like nanometer particle.
Embodiment 5
A kind of solid luminescent nano material PMo of polyoxometallic acid salt dopping12 / CeF3Preparation method, comprising the following steps:
1) by 0.130 g Ce (NO3)3·6H2O(0.299 mmol), the PVP of 0.050 g, the KBF of 0.151 g4(1.199
) and 0.050 g α-PMo mmoL12(0.026 mmoL) is placed in 50 mL reaction kettles, and 17.5 mL distilled water are added, and room temperature is violent
After stirring 20 min, mixed solution is obtained；
2) reaction kettle is transferred in baking oven, rises to 40 DEG C with 0.15 DEG C of heating rate per minute, the pressure in reaction kettle
113 KPa are risen to the rate of 3.6 KPa/h, constant temperature and pressure keeps 12 h, autoclave is slowly cooled to room temperature naturally
Afterwards, obtain yellow mercury oxide, by sediment with 2500 r/pm rates be centrifugated 5 min obtain sediment, later with 4 mL go from
Mixed liquor (the V of sub- water and ethyl alcoholH2O:VCH3CH2OH=3:1) it washs three times, it is then dried overnight, finally obtains at 65 DEG C
PMo12 / CeF3Flower-like nanometer particle.
Embodiment 6
The present embodiment difference from example 1 is that, 40 DEG C are warming up in step 2.
Embodiment 7
The present embodiment difference from example 1 is that, α-PMo in step 1)12Dosage be 0.016 g(0.008
MmoL)；40 DEG C are warming up in step 2.
Embodiment 8
The present embodiment difference from example 1 is that, in step 2 heating time be 0.5 h.
Embodiment 9
The present embodiment difference from example 1 is that, in step 2 heating time be 1 h.
Embodiment 10
The present embodiment difference from example 1 is that, in step 2 heating time be 2 h.
Embodiment 11
The present embodiment difference from example 1 is that, in step 2 heating time be 4 h.
Embodiment 12
The present embodiment difference from example 1 is that, in step 2 heating time be 6 h.
Embodiment 13
The present embodiment difference from example 1 is that, in step 2 heating time be 8 h.
Embodiment 14
The present embodiment difference from example 1 is that, in step 2 heating time be 14 h.
Embodiment 15
The present embodiment difference from example 1 is that, in step 2 heating time be 24 h.
Embodiment 16
The present embodiment difference from example 1 is that, 180 DEG C are warming up in step 2.
Below to the sample and CeF of embodiment 1-16 preparation3It is detected and analyzed:
(1) composition and Xiang Chundu of sample
Fig. 1 a is CeF3, PMo in embodiment 112/CeF3, SiW in embodiment 212/CeF3, PW in embodiment 312/CeF3XRD diagram
It composes, in the XRD of obtained sample, there's almost no miscellaneous peak, it can be seen from the figure that being CeF3Hexagonal phase (pdf no.
891933), and crystallinity is good, and 2 θ appear in 26 °, 27 °, 30 °, 47 °, 55 ° correspond respectively to (512), (611), (612),
(611) and (550) crystal face.It should be pointed out that POMs can not be detected in this test, reason may be each sample
The content of POMs is lower than CeF in product3, therefore, the diffraction peak intensity of POMs is relatively weak, can be overlapped and be covered.
If Fig. 1 b is PMo in embodiment 112/CeF3, SiW in embodiment 212/CeF3, PW in embodiment 312/CeF3It is infrared
Eigen vibration peak, in PMo12/CeF3In sample, there are 1061 cm‒1(P O), 957 cm‒1(Mo O) and 876 cm‒1
(Mo O Mo) characteristic peak, it was demonstrated that α-PMo12Presence；In addition, in SiW12/CeF3In spectrum, absorption peak appears in 972,
924 and 885 cm‒1Place, is respectively belonging to ν (W Od), ν (Si Oa) and ν (W Ob) characteristic peak, it was demonstrated that α-SiW12It deposits
?.Finally, peak value appears in 1081,980 and 897 cm‒1Place demonstrates α-PW12Also CeF successfully it has been doped into3In.Such as
Fig. 1 c and 1d are PMo in embodiment 112/CeF3The XPS map of nano flower-like crystal, it was confirmed that the valence state of Mo and Ce element is distinguished
It is+6 and+3.
Fig. 2 is PMo in embodiment 112/CeF3The SEM and EDX of nano flower-like crystal scheme.Fig. 2 (a, b, c) is flower-shaped
PMo12/CeF3Nanocrystalline SEM image.Sample is in uniform monodispersed state, and from form, yield is more than or equal to
99.8%.From the point of view of 50 particles of statistics, flower-shaped PMo12/CeF3Nanocrystalline average diameter is about 630 nm, narrow distribution.
Flower-shaped PMo in figure12/CeF3Nanocrystalline size is 645 nm, and under high resolution observations, it be about 22 nm by thickness
Thin slice constitute (such as Fig. 2 c), floriform appearance is common structure in nano material, especially in transition metal oxide
Research field, however, with rare earth fluoride (especially CeF3) based on flower-like structure seldom report so far, especially exist
In the case of POMs compound.Fig. 2 d is the PMo of embodiment 112/CeF3The EDX of flower-like nanometer crystalline substance schemes, including
The mapping of corresponding element schemes.This sample is characterized using silicon wafer as substrate, and analysis result demonstrates P, Mo, O, Ce and F
The presence of component, meanwhile, the element of Mo and Ce are mapped in present in nanocomposite and be uniformly distributed.
Fig. 3 is SiW in embodiment 212/CeF3PW in nanometer sheet (such as Fig. 3 a, 3b) and embodiment 312/CeF3Nanosphere is (such as
Fig. 3 c, 3d) SEM figure.SiW in embodiment 212/CeF3Nanometer sheet and CeF3Nanostructure is similar, except that this knot
Structure is made of discoid particle, the CeF with regular hexagon3There is very big difference in nanostructure.SiW12/CeF3Nanometer
The size of piece is about 446 nm, and thickness is about 177 nm(such as Fig. 3 b).Fig. 3 c and 3d are PW12/CeF3Nanocrystalline SEM figure,
PW12/CeF3It is spherical in shape, about 568 nm(such as Fig. 3 d of size).
Fig. 4 is in embodiment 5 and embodiment 7 using PMo when different dopings12 / CeF3SEM figure.Such as embodiment 7
It is shown, as addition α-PMo12When measuring as 0.016 g(0.008 mmoL) into mixture, the PMo of sheet can be obtained12 /
CeF3 Nanometer sheet (Fig. 4 a, 4b).But with regular hexagon CeF3It compares, edge and corner angle become less obvious, it is known that, α-
PMo12To CeF3Nanocrystalline polymerization has significant impact.Such as embodiment 5, as α-PMo12Dosage reaches 0.100 g (0.053
When mmol), in this reaction system, the separation of crystal is not obtained (shown in such as Fig. 4 c, Fig. 4 d).
Fig. 5 be embodiment 6, embodiment 4, in embodiment 1 and embodiment 16 differential responses temperature to PMo12/CeF3It is formed
It influences, obtained PMo12/CeF3SEM image.As described in Example 6, at 40 DEG C, small amount has been obtained similar to flower-shaped
Particle, and observe unbodied bulk, remaining particle is in irregular shape (Fig. 5 a).80 DEG C are risen to temperature, such as
Embodiment 4, flower-shaped PMo12/CeF3Nanocrystalline size wider distribution, number gradually increase (Fig. 5 b).When temperature further rises to
At 140 DEG C, such as embodiment 1, flower-shaped PMo12/CeF3Nanocrystalline shape becomes uniformly, and most of flower-shaped PMo12/CeF3Nanometer
Brilliant structure is sufficiently complete (Fig. 5 c).When temperature reaches 180 DEG C, such as embodiment 16, there is a large amount of fragment, show height
Temperature can destroy uniform structure (Fig. 5 d).
Fig. 6 be embodiment 1, in embodiment 8-15 the differential responses time to PMo12/CeF3The influence of formation.Using different
Reaction time is to flower-shaped PMo12/CeF3Nanometer crystals growth is studied.0.5 h of reaction time in embodiment 8, in embodiment 9
When 1 h of reaction time, PMo is formed12/CeF3Particle is respectively Fig. 6 a, Fig. 6 b, these particles, but can almost without flower shape
It to be clearly observed this particle is made of nanometer sheet.It can be seen that SEM image shows PMo from Fig. 6 c to Fig. 6 i12/
CeF3Nanocrystal is respectively 2 h, 4 h, 6 h in the reaction time, 8 h, 12 h, 14 h and 24 h(corresponding embodiment 10-
13, embodiment 1, embodiment 14-15).As it can be seen that with the increase in reaction time, PMo12/CeF3Particle shows flower shape.
Sample stability research: PMo prepared by embodiment 112/CeF312 h, 24 h, 36 h and 48 h are placed in water
(respectively corresponding Fig. 7 a, Fig. 7 b, Fig. 7 c, Fig. 7 d) is observed afterwards, as shown in Figure 7.Fig. 7 is to probe into flower-shaped PMo12/CeF3Nanocrystal
The SEM figure that stability is probed into water.It can be seen that, this flower-shaped PMo12/CeF3The stability of nanocrystal in aqueous solution compared with
It is good.It is uniformly monodispersed flower-shaped to be held essentially constant in 48 h.Therefore, which assigns flower-shaped PMo12/CeF3It is nanocrystalline
Practical application value of the body in solution system.
(2) photoluminescence performance
Fig. 8 is PMo in embodiment 112/CeF3, SiW in embodiment 212/CeF3With PW in embodiment 312/CeF3Nanocrystal
Launching light spectrogram.Under 250 nm exciting lights, in 324 positions nm, CeF3Strong emission peak is shown, this and text before
Offer Liu Y, Zhao Y, Luo H, et al. Hydrothermal synthesis of CeF3 nanocrystals
and characterization[J]. Journal of Nanoparticle Research, 2011, 13(5): 2041-
The result of 2047. reports is consistent.At identical conditions, PMo12/CeF3、SiW12/CeF3And PW12/CeF3Nanocrystal difference
Apparent transmitting band is also shown at 305 nm, 333 nm and 338 nm.With CeF3Emission peak is compared, PMo12/CeF3Blue shift
19 nm.On the contrary, SiW12/CeF3And PW12/CeF3Distinguishing red shift is 9 nm and 14 nm.
(3) photocatalysis performance
By PMo in embodiment 112/CeF3, SiW in embodiment 212/CeF3With PW in embodiment 312/CeF3It is urged as photochemical catalyst
Change the test of rhodamine B degradation:
0.12 g photochemical catalyst (PMo is added using ultraviolet 500 W Hg lamp irradiation of invisible light source12/CeF3, SiW12/CeF3Or
PW12/CeF3) into 40 mL rhodamine B solutions (wherein 10 mg/L of rhodamine B concentration), final solution is obtained, and start to count
When, a sample is taken every 1h to light application time, carries out ultraviolet test analysis.Fig. 9 is PMo in embodiment 112/CeF3, embodiment 2
Middle SiW12/CeF3With PW in embodiment 312/CeF3The effect statistical chart of degradation of dye (rhodamine B) respectively.The result shows that
After 6 h of illumination, three kinds of catalyst PMo12/CeF3, SiW12/CeF3And PW12/CeF3Degradation rate be 87% respectively, 98% He
58.5%.This shows that three kinds of photochemical catalyst rhodamine B degradations in Industrial Wastewater Treatment have good application prospect.Figure 10 is to urge
Agent recycles the test result figure of number, using degradation rate as Y-axis in figure, maps by X-axis of catalyst recycling number.
As seen from the figure, the catalyst (PMo being recycled by four times12/CeF3、SiW12/CeF3And PW12/CeF3) still maintain and urge
Change activity.This shows that the activity of three kinds of composite catalysts of embodiment 1-3 preparation is very high.Meanwhile the high catalytic efficiency of preparation
Catalyst can have the value recycled and reused well in field of industrial waste water treatment.
To sum up, solid luminescence nano material PMo prepared by the present invention12/CeF3、SiW12/CeF3Or PW12/CeF3With hair
Optical property, and morphology controllable, three kinds of nanocrystal PMo12/CeF3、SiW12/CeF3Or PW12/CeF3It is respectively provided with nano flower
Shape, nanometer sheet and nanosphere shape and structure.In addition to this, the PL performance of these nanocomposites is also very different.It mixes
Miscellaneous different types of POM, POM/CeF3Composite material has different emission peaks, by method of the present invention it is found that passing through
While adulterating performance of the different types of POMs to adjust PL, composite nano materials due to very high specific surface area,
Therefore there is very high photocatalysis performance, the degradation rate of rhodamine B can be improved.Therefore, nano material of the present invention is in material
In terms of the morphology and Properties Control of science, in fields such as Pollutants in Wastewater degradation, fluorescence chemical sensor and photoelectric devices
It has broad application prospects.
Above-described embodiment is embodiment of the present invention for example, although to be illustrate and described with specific embodiment
The present invention, however will be appreciated that embodiment of the present invention are not limited by the above embodiments, it is other any without departing from this hair
Made changes, modifications, substitutions, combinations, simplifications under bright spiritual essence and principle, should be equivalent substitute mode, all include
Within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of the solid luminescent nano material of polyoxometallic acid salt dopping, which is characterized in that including following step
It is rapid:
1) soluble cerium salt, polyvinylpyrrolidone, KBF are taken4With POMs uniform dissolution Yu Shuizhong, mixed solution is obtained；
2) by mixed solution in step 1) at a temperature of 40-180 DEG C, under 110-170 KPa pressure, constant temperature and pressure reacts 6-24
H is cooled to room temperature, is separated by solid-liquid separation, and washs, dry, obtains solid luminescent nano material POM/CeF3；
The solubility cerium salt is cerous nitrate, cerous sulfate or cerium chloride；
The POMs is Na3PMo12O40、K4SiW12O40、Na3PW12O40One or more of.
2. preparation method as described in claim 1, which is characterized in that soluble cerium salt and KBF in step 1)4Mass ratio be
1:(1-3).
3. preparation method as described in claim 1, which is characterized in that soluble cerium salt is with POMs mass ratio in step 1)
(1-9): 1.
4. preparation method as described in claim 1, which is characterized in that when being reacted in step 2, the mixed solution is existed
It is warming up to 40-180 DEG C under 0.1-2 DEG C/min rate conditions, boosts to 110-170 under 3-40 KPa/h rate conditions
KPa, constant temperature and pressure react 6-24 h.
5. preparation method as described in claim 1, which is characterized in that when washing in step 2, use deionized water and ethyl alcohol
Mixed liquor wash 2-5 time, mixeding liquid volume is 1-5 mL, and deionized water and the volume ratio of ethyl alcohol are (1-3) in mixed liquor: 1.
6. the solid luminescent nano material of the polyoxometallic acid salt dopping using any the method preparation of claim 1-5.
7. the solid luminescent nano material of polyoxometallic acid salt dopping described in claim 6 pollutant in degrading waste water is answered
With, which is characterized in that the pollutant is dyestuff or formaldehyde.
8. the use as claimed in claim 7, which is characterized in that the dyestuff is rhodamine B, methylene blue, alizarin red S, Cape jasmine
Sub- uranidin G or Congo red.
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