CN109078645A - A kind of photochemical catalyst and its preparation method and application of novel cladding Z-type structure - Google Patents
A kind of photochemical catalyst and its preparation method and application of novel cladding Z-type structure Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000005253 cladding Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 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 100
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 100
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- 238000007146 photocatalysis Methods 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 51
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- -1 rare-earth ion Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000002738 chelating agent Substances 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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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
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/36—Organic compounds containing halogen
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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
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Abstract
The present invention discloses photochemical catalyst of a kind of novel cladding Z-type structure and preparation method thereof and its photocatalysis while converting the application in Cr in aqueous solution (VI) and rhodamine B degradation (RhB) under simulated solar irradiation irradiation.The photochemical catalyst is CNT/Ni2P/Er3+:Y3Al5O12‑CNT@Bi12GeO20, prepared by hydro-thermal method and sol-gal process.Its light-catalyzed reaction efficiency significantly improves, this is because light induced electron is shifted by CNT, effectively inhibit the compound of electron hole, and CNT is combined with the photochemical catalyst of clad structure and is released more active sites, it is reduced Cr (VI) in CNT surface, rhodamine B (RhB) is in Bi12GeO20It is degraded on surface.Therefore the photocatalytic system has shown brilliant photocatalysis performance, converts have broad prospects in the application of Cr (VI) and rhodamine B degradation (RhB) at the same time.
Description
Technical field
The invention belongs to photocatalysis field more particularly to a kind of photochemical catalyst CNT/Ni of novel cladding Z-type structure2P/Er3 +:Y3Al5O12-CNT@Bi12GeO20Preparation method and its photocatalysis simultaneously convert in Cr (VI) and rhodamine B degradation (RhB)
Application.
Background technique
With the development of the modern industry, environmental pollution is increasingly severe.Reform and hair are had been cited as in China environmental protection
One of the ten great strategy tasks of exhibition, wherein fwaater resources protection is the key subjects of environmental protection.It such as weaves in many industry, make
Heavy metal ion present in industrial wastewater caused by the fields such as paper, process hides and organic pollutant give environmental and human health impacts band
Carry out huge harm.To contain the solution of heavy metal Cr (VI) and organic dyestuff rhodamine B (RhB) simultaneously as mould in this experiment
The sewage system that quasi- heavy metal ion and organic pollutant coexist verifies conversion and the degradation effect of photochemical catalyst.Heavy metal Cr
(VI) with chromate (HCrO4-/CrO4 2-) and bichromate (Cr2O7 2-) form enter environment.Studies have shown that Cr (VI) has height
In 1000 times of carcinogenicity of Cr (III), and usually there is higher dissolubility, toxicity, unstability and bioactivity.Drink
With in water if contain Cr (VI), will increase a possibility that human body suffers from liver cancer, cutaneum carcinoma and bladder cancer.Rhodamine B (RhB) is print
Common a kind of stable cationic basic dye in industry is contaminated, there is stronger carcinogenicity.In face of being difficult to by the dye of fully degraded
How material is always the problem that perplexs scientist by their thorough harmless treatments.Therefore, Cr (VI) is reduced into Cr
(III), it is very necessary for and carrying out thorough harmless treatment simultaneously to dyeing waste water.
In recent years, having been caused more using Heterogeneous Photocatalysis of Semiconductors processing Cr (VI) and rhodamine B (RhB)
More attentions.If allow them in a system while carrying out, reduction reaction is carried out on conduction band respectively, oxygen is carried out in valence band
Change reaction, finally generates Cr (III) in conduction band, and rhodamine B (RhB) is degraded in valence band, then it can be to both substances
It is converted and is degraded simultaneously.But to carry out simultaneously, a problem is photoproduction existing for this Photocatalitic Technique of Semiconductor
Electrons and holes are compound to being easy.Photocatalytic system should carry out oxidation reaction and carry out reduction reaction again, and catalyst is necessary
With enough bandwidth.But it is seldom to meet such semiconductor catalyst, therefore present invention introduces cladding Z-type photocatalysis bodies
System.
In numerous photochemical catalysts, Bi12GeO20And Ni2P is exemplary wideband semiconductor and narrow-band semiconductor photochemical catalyst,
Their bandwidth is 3.2eV and 1.0eV respectively.Bi12GeO20It is opposite broadband semiconductor, it can utilize the height in sunlight
Energy light, Ni2P is opposite narrow-band semiconductor, can utilize the low-energy light in sunlight.It is one relative to nano material CNT
The longer tubular material (0.5-2.0 μm) of kind, and have good conductive property.Electronics is shifted by CNT, can effectively be pressed down
The compound of electron hole is made, and CNT is combined with the photochemical catalyst of clad structure and released more active sites, makes Cr
(VI) it is restored in CNT surface, rhodamine B (RhB) is in Bi12GeO20It degrades on surface.So as to realize simultaneously for Cr
(VI) degradation of conversion and rhodamine B (RhB).Therefore Z-type photochemical catalyst CNT/Ni is coated in the present invention2P/Er3+:
Y3Al5O12-CNT@Bi12GeO20In photocatalytic conversion Cr (VI) and rhodamine B degradation (RhB) reaction with wide before
Scape.
Summary of the invention
In order to provide more active sites and solve the Complex Problem of light induced electron and hole, the present invention designs synthesis one
CNT is efficiently separated the NEW TYPE OF COMPOSITE photochemical catalyst CNT/Ni in light induced electron and hole by kind as conductive channel2P/Er3+:
Y3Al5O12-CNT@Bi12GeO20.Compound involved in the present invention belongs to novel cladding Z-type semiconductor light-catalyst CNT/Ni2P/
Er3+:Y3Al5O12-CNT@Bi12GeO20.It is applied to while converting Cr in aqueous solution (VI) and rhodamine B degradation (RhB)
In reaction, have the advantages that it is easy to operate, pollution-free, be easily isolated no by-product and generate and not will cause environmental pollution.
The technical solution adopted by the present invention is that:
A kind of photochemical catalyst of novel cladding Z-type structure, the photochemical catalyst of the novel cladding Z-type structure is CNT/
Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20。
A kind of preparation method of the photochemical catalyst of the novel cladding Z-type structure, includes the following steps:
1) by GeO2It is dissolved into concentrated ammonia liquor, obtains GeO2Ammonia spirit；By BiCl3It is added in dehydrated alcohol, completely to it
GeO is added after dissolution2In ammonia spirit, stirring 2h generates the colloidal sol of thick white；
2) by etc. quality Er3+:Y3Al5O12And CNT/Ni2P is added in ultrapure water, and fully dispersed using ultrasound
Suspension is heated to boiling point, keeps constant temperature 2min, 80 DEG C of dry 12h after centrifugation by 5min.Powder after drying is ground,
Then 2h is calcined at 400 DEG C, is finally ground, and CNT/Ni is obtained2P/Er3+:Y3Al5O12Nanoparticle powder.
3) CNT/Ni is added into the colloidal sol of thick white2P/Er3+:Y3Al5O1212h is stirred at room temperature, then in nanometer powder
Dry 48h, powder is finely ground, and 600 DEG C of calcining 2h, grind after it is cooled to room temperature, obtain target product in tube furnace
CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20。
The preparation method, CNT/Ni in step 2)2P powder the preparation method comprises the following steps: by NiCl2·6H2O and red phosphorus add
Enter into ultrapure water, 20min is stirred at room temperature, obtains mixed solution；CNT is added in mixed solution, continues to stir 1h, obtain
Aaerosol solution be transferred in reaction kettle 36h at 140 DEG C, collect and with distilled water and washes of absolute alcohol for several times, 60 after centrifugation
DEG C dry 12h, grinds powder after drying, obtains CNT/Ni2P powder.
The preparation method, Er in step 2)3+:Y3Al5O12Powder the preparation method comprises the following steps: by Er2O3、Y2O3Powder is molten
Solution is in concentrated nitric acid and magnetic force heating stirring is until colorless and transparent, obtains rare-earth ion solution；Then by Al (NO3)·9H2O dissolution
In distilled water, is stirred and be slowly added in rare-earth ion solution with glass bar at room temperature, using citric acid as chelating agent
And cosolvent, citric acid is dissolved with distilled water, in 50-60 DEG C of heating stirring, stops when solution is in thick, it is molten to obtain viscose shape
Liquid；Thick solution is put into 80 DEG C of heating 36h of baking oven constant temperature, in the drying process until solvent evaporated does not have sediment raw
At finally obtaining foam sol, then obtained colloidal sol calcines 2h at 1100 DEG C respectively in 500 DEG C of heating 50min respectively.Most
Afterwards, the substance of sintering is taken out from high temperature furnace and is cooled to room temperature to obtain Er in air3+:Y3Al5O12Powder.
The preparation method, in molar ratio, the citric acid: rare earth ion=3:1.
A kind of photochemical catalyst of the novel cladding Z-type structure converts Cr (VI) and rhodamine B degradation in photocatalysis simultaneously
(RhB) application in.
The application, application process are as follows: by CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Nanometer grade powder
It is added in be transformed-degraded solutions, illumination, the to be transformed-degradation is carried out under conditions of pH is the irradiation of 2,500W xenon lamp
Solution is the aqueous solution containing Cr (VI) and rhodamine B (RhB).
The application, the CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Nanometer grade powder is in be transformed-drop
Solving the concentration in solution is 1.0g/L.
The application, Cr (VI) and the concentration ratio of rhodamine B (RhB) are 3:1 in the to be transformed-degraded solutions.
The application, light application time 40min.
The invention has the following advantages:
Cladding Z-type photochemical catalyst CNT/Ni prepared by the present invention2P/Er3+:Y3Al5O12-CNT@Bi12GeO20, be by
Bi12GeO20The light induced electron that conduction band generates is by CNT as conductive channel and Ni2Photohole caused by P valence band combines,
And Ni2Light induced electron caused by P conduction band passes through Bi by CNT12GeO20Surface, by Ni2The produced electronics transfer of P conduction band.To
Improve the separative efficiency in light induced electron and hole.And CNT is also that photocatalytic conversion Cr (VI) provides more active sites,
Bi is also increased simultaneously12GeO20To the hole exposure of rhodamine B (RhB) degradation.It is well known that due to Bi12GeO20Bandwidth
3.20eV, wherein valence band is 2.55eV, and conduction band is -0.25eV.Ni2P bandwidth be 1.00eV, valence band be -0.23eV, conduction band be -
1.23eV.Under the excitation of simulated solar irradiation, electronics transits to conduction band (CB) from valence band (VB), so that being formed has high-energy
Electron-hole pair, these carriers easily compound bury in oblivion and discharge light or heat, the light induced electron and hole that do not bury in oblivion make CNT/
Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Show brilliant photocatalysis performance.Therefore, CNT is used as conduction in the method
Channel makes Bi12GeO20The electronics and Ni that conduction band generates2The hole that P valence band generates combines, and makes Ni2The electronics that P conduction band generates turns
It moves, effectively reduces the compound method in light induced electron and hole.It applies in photocatalysis simultaneously to Cr (VI) conversion and Luo Dan
In the reaction of bright B (RhB) degradation, under the excitation of simulated solar irradiation, electronics caused by photochemical catalyst is by CNT transfer and again
It is stored in CNT surface, so that Cr (VI) is reduced to Cr (III) in CNT surface.Meanwhile in Bi12GeO20Surface it is inevitable
Generation hole.Directly decompose rhodamine B (RhB) dyestuff in generated hole.This method is effectively kept away using conductive channel
The compound of light induced electron and hole is exempted from, and has been Bi12GeO20Surface releases more active sites to make turning for catalyst
Change and degradation efficiency improves very much.
CNT/Ni prepared by the present invention2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Nano-photocatalyst performance efficiency.Its property
Quality high-temperature and acid-alkali-corrosive-resisting.With Ni2P/Er3+:Y3Al5O12@Bi12GeO20And Ni2P@Bi12GeO20It compares, this catalyst exists
Efficiency in the degradation reaction of Cr (VI) and rhodamine B (RhB) is converted under the irradiation of simulated solar irradiation simultaneously have and increases substantially.
Composite photo-catalyst CNT/Ni in the present invention2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Not only there is the excellent of traditional photochemical catalyst
Point, and its most it is worth noting that be directed to Bi12GeO20And Ni2P bandwidth feature and conduction band and valence band location are unique, design
Novel photocatalyst of the CNT as conductive channel.The problem of this method solve light induced electron and hole-recombinations, and urged for light
Change reaction and provides more active sites, photocatalytic conversion Cr (VI) and rhodamine B degradation (RhB) is greatly improved
Efficiency.
Detailed description of the invention
Fig. 1 a is Er3+:YAlO3X-ray powder diffraction (XRD) figure, Fig. 1 b is Bi12GeO20X-ray powder diffraction
(XRD) figure, Fig. 1 c are Ni2X-ray powder diffraction (XRD) figure of P, Fig. 1 d is Ni2P@Bi12GeO20X-ray powder diffraction
(XRD) figure, Fig. 1 e are Ni2P/Er3+:Y3Al5O12@Bi12GeO20X-ray powder diffraction (XRD) figure, Fig. 1 f is CNT/Ni2P/
Er3+:Y3Al5O12-CNT@Bi12GeO20X-ray powder diffraction (XRD) figure of d.
Fig. 2 a is Er3+:YAlO3Scanning electron microscope (SEM) figure, Fig. 2 b is Bi12GeO20Scanning electron microscope
(SEM) figure, Fig. 2 c are Ni2Scanning electron microscope (SEM) figure of P, Fig. 2 d is Ni2P@Bi12GeO20Scanning electron microscope
(SEM) figure, Fig. 2 e are Ni2P/Er3+:Y3Al5O12@Bi12GeO20Scanning electron microscope (SEM) figure, Fig. 2 f is CNT/Ni2P/
Er3+:Y3Al5O12-CNT@Bi12GeO20Scanning electron microscope (SEM) figure.
Fig. 3 is CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Transmission electron microscope (TEM) figure.
Fig. 4 is Ni2P@Bi12GeO20And CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Photoluminescence spectra
(PL) figure.
Fig. 5 is different light application times to photochemical catalyst while converting the effect picture of Cr (VI) and rhodamine B degradation (RhB).
Fig. 6 is different content photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20It is irradiated in simulated solar irradiation
Effect picture that is lower while converting Cr (VI) and rhodamine B degradation (RhB).
Fig. 7 is photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Turn simultaneously under simulated solar irradiation irradiation
Change the Cr (VI) of various concentration and the effect picture of degradation 5.0mg/L rhodamine B (RhB).
Fig. 8 is a kind of novel cladding Z-type structure photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Simultaneously
Convert the mechanism figure of Cr (VI) and rhodamine B degradation (RhB) in aqueous solution.
Specific embodiment
A kind of photochemical catalyst CNT/Ni of novel cladding Z-type structure of embodiment 12P/Er3+:Y3Al5O12-CNT@Bi12GeO20
Preparation method and detection
(1) preparation method includes the following steps:
1)Bi12GeO20The preparation of powder
By 0.031g GeO2It is dissolved into 50mL concentrated ammonia liquor, obtains GeO2Ammonia spirit.By 1.140g BiCl3It is added to nothing
In water-ethanol, GeO is added after it is completely dissolved2In ammonia spirit, stirring 2h generates the colloidal sol of thick white.It is done at 80 DEG C
Dry 12h obtains Bi12GeO20Powder.Powder is finely ground, and then 600 DEG C of calcining 2h in tube furnace, are cooled to room temperature, grinding,
Obtain Bi12GeO20Powder.
2)Er3+:Y3Al5O12The preparation of powder
By 2.7281g Er2O3(99.99%), 0.0464g Y2O3(99.99%) powder is dissolved in concentrated nitric acid
(65.00%) in and magnetic force heating stirring is until colorless and transparent obtain rare-earth ion solution.Then 12.6208g Al is weighed
(NO3)3·9H2O (99.99%) is dissolved in distilled water, is stirred at room temperature with glass bar and to be slowly added to rare earth ion molten
In liquid.Using citric acid as chelating agent and cosolvent, in molar ratio, citric acid: rare earth ion=3:1 is weighed and is used distillation water-soluble
Solution stops in 50-60 DEG C of heating stirring when solution is in thick.It is generated in this process without precipitating, finally obtains hair
Steep glutinous colloidal solution.Thick solution is put into 80 DEG C of heating 36h of baking oven constant temperature.In the drying process until solvent evaporated does not have
Sediment generates, and finally obtains foam sol.Then obtained colloidal sol is forged at 1100 DEG C respectively respectively in 500 DEG C of heating 50min
Burn 2h.Finally, taking out the substance of sintering from high temperature furnace and being cooled to room temperature to obtain Er in air3+:Y3Al5O12Powder.
3)CNT/Ni2The preparation of P powder
By 3.80g NiCl2·6H2The mixing of O and 2.80g red phosphorus is added in 30mL deionized water, is stirred at room temperature
20min obtains mixed solution.It weighs 0.10g CNT to pipette into mixed solution, continues to stir 1h；It is then transferred into 30mL reaction
It is sealed in kettle and keeps 36h at 140 DEG C in air kiln, collected and with distilled water and washes of absolute alcohol 3 times, after centrifugation
60 DEG C of dry 12h, grind powder after drying, finally obtain CNT/Ni2P nanoparticle powder.
4)CNT/Ni2P/Er3+:Y3Al5O12The preparation of powder
By 1.00g Er3+:Y3Al5O12With 1.00g CNT/Ni2P is added in 20mL ultrapure water, and is sufficiently divided using ultrasound
5min is dissipated, suspension is heated to boiling point, keeps constant temperature 2min, 80 DEG C of dry 12h after centrifugation.Powder after drying is ground
Mill, then calcines 2h at 400 DEG C.It finally grinds, obtains CNT/Ni2P/Er3+:Y3Al5O12Nanoparticle powder.
5)CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20The preparation of powder
By 0.031g GeO2It is dissolved into 50mL concentrated ammonia liquor.1.140g BiCl3It is added in 50mL dehydrated alcohol, to it
It is added after being completely dissolved in above-mentioned solution.Stirring at normal temperature 2h is until generate the colloidal sol of thick white.2.030g CNT/ is added
Ni2P/Er3+:Y3Al5O1212h is stirred at room temperature in nanometer powder.Then 48h is dried.Powder is finely ground, it is forged for 600 DEG C in tube furnace
2h is burnt, grinding is cooled to room temperature to it, obtains CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Powder.
(2) it detects
It (1) is Er3+:YAlO3、Bi12GeO20、Ni2P、Ni2P@Bi12GeO20、Ni2P/Er3+:Y3Al5O12@Bi12GeO20、
CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20X-ray powder diffraction (XRD) picture analyzing.
As shown in Figure 1, the structure and composition of the sample prepared is verified by XRD.As the result is shown in Fig. 1.Such as
Fig. 1 a illustrates the absorption peaks of some points in 2 θ=18.10 ° (211), and 27.76 ° (321), 29.78 ° (400), 33.38 °
(420), 35.07 ° (332), 36.68 ° (422), 41.14 ° (521), 46.53 ° (532), 52.74 ° (444), 55.06 °
(640), 57.32 ° (642) and 61.83 ° (800), this and Y3Al5O12Standard card JCPDS card 33-0040 fit like a glove.
It demonstrates Er3+:Y3Al5O12It is successfully prepared, and Er3+Y is come into3Al5O12Lattice instead of Y3+.Such as figure
Shown in 1b, diffraction maximum clearly appears in 24.7 °, and 33.0 °, 35.3 °, 41.7 °, 45.5 °, 49.1 °, 54.1 °, 55.8 °,
61.9 °, correspond to Bi12GeO20(220), (321), (400), (332), (510), (521), (600), (532) and (631)
Diffraction maximum crystal face, this and Bi12GeO20Standard card JCPDS card 14-0117 match.This can prove Bi12GeO20Quilt
It is prepared by success.As illustrated in figure 1 c, sample is in 2 θ=40.8 ° (111), and 44.6 ° (201), at 47.3 ° (210) and 54.2 ° (300)
There is apparent diffraction maximum, this and Ni2The standard card JCPDS card 03-0953 of P is consistent, it was demonstrated that at present can be successfully
Synthesize pure Ni2P crystal.It can be found that Ni2P and Bi12GeO20Characteristic diffraction peak significantly appears in Fig. 1 d.This shows
Ni2P@Bi12GeO20Composite material has been produced.From Fig. 1 e as can be seen that in addition to Ni2P and Bi12GeO20Feature diffraction
Outside peak, Er3+:Y3Al5O12Characteristic diffraction peak also clearly appear in Fig. 1 e, this shows to be successfully prepared Ni2P/
Er3+:Y3Al5O12@Bi12GeO20.It is and unobvious for the diffraction maximum of the CNT in Fig. 1 f, it may be possible to since its content is less.I
Its presence can be further proved by SEM and TEM.
It (2) is Er3+:YAlO3、Bi12GeO20、Ni2P、Ni2P@Bi12GeO20、Ni2P/Er3+:Y3Al5O12@Bi12GeO20、
CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Scanning electron microscope SEM picture analyzing.
Shown in Fig. 2 is the Er prepared3+:Y3Al5O12, Bi12GeO20, Ni2P、Ni2P@Bi12GeO20, Ni2P/Er3+:
Y3Al5O12@Bi12GeO20, CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20The SEM spectrum of powder, for analyzing and researching it
Configuration of surface.The spherical particle of many grapes is observed that from Fig. 2 a, particle size is to receive in 40~60nm, these particles
The up-conversion luminescent material Er of meter ruler cun3+:Y3Al5O12.There are about 800nm to 1 μm of a large amount of irregular flaky crystals in Fig. 2 b
Particle is accredited as Bi12GeO20Particle.There are the spherical particle of 50nm or so, these nanoparticles are recognized for display in Fig. 2 c
To be Ni2P.There are numerous irregular granules in Fig. 2 d and e, particle size is about 400nm to 600nm.Its surface is smooth, table
Sight pattern is different from Fig. 2 b, and particle size is reduced.It is considered that being Bi during cladding12GeO20Particle it is pulverized and
Dispersion.Furthermore we find that observing the presence of CNT in Fig. 2 f, this can prove that we successfully introduce during the experiment
This nano material of CNT.Its length is about 800nm to 1.0 μm.These discoveries demonstrate again that, the CNT/Ni of prediction2P/Er3+:
Y3Al5O12-CNT@Bi12GeO20It has been synthesized.
It (3) is CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Transmission electron microscope (TEM) picture analyzing.
Fig. 3 shows cladding Z-type photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Different magnification ratios
Under TEM image, wherein corresponding unit ratio length is respectively 100nm, 20nm, 10nm and 5nm.Such as Fig. 3 (100nm) institute
Show, some irregular spherical particles are wherein dispersed with nanoparticle not of uniform size, and surface and inside are it is observed that CNT
Presence.It is considered that being that CNT passes through Bi12GeO20Coat Ni2P and Er3+:Y3Al5O12It is formed by clad structure nano particle.
The spheroidal particle of some small sizes should be Ni in Fig. 3 (100nm)2P, around it can be observed that CNT presence, can prove
Ni2P is successfully combined with CNT.We can also be observed that some slightly large-sized spherical black particles should be Er3+:
Y3Al5O12, it is dispersed in Ni2Around P and CNT, therefore it can prove Ni2P-CNT and Er3+:Y3Al5O12Success combines.Amplification
To the scale bar of 20nm and 10nm, as shown in Fig. 3 (20nm) and (10nm), it can be found that the presence of CNT and clad structure are more
Clearly, therefrom clearer to observe Ni2P and Er3+:Y3Al5O12It has been covered by Bi12GeO20The inside.The clad structure its
There are CNT for surface and inside.When 5nm is further amplified in unit scale bar, in Fig. 3 (5nm), it is many clear to present
Lattice fringe.It is compared by counting lattice fringe spacing, and with XRD data, the crystal face of the photochemical catalyst of preparation can
To be determined.They are clearly marked in Fig. 3 (5nm), Er3+:Y3Al5O12(d=0.293nm (221)), Ni2P (d=
0.238nm (111)), Bi12GeO20(d=0.276nm (321)).Therefore, TEM's the result shows that Bi12GeO20Form one with
Ni2P and Er3+:Y3Al5O12Centered on core-shell structure copolymer cladding structure.There is CNT in its surface of the clad structure and inside.
It (4) is Ni2P@Bi12GeO20And CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Photoluminescence spectra
(PL) picture analyzing.
Luminescence generated by light (PL) spectrum is a kind of for confirming that photo-generate electron-hole is to compound important method in semiconductor.
In general, the relatively low intensity signal in PL spectrum shows photo-generate electron-hole to easily compound.On the contrary, higher intensity then shows electricity
Son-hole is relatively high to recombination rate.From Fig. 4 it can be clearly seen that CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20
PL intensity be significantly lower than Ni2P@Bi12GeO20, illustrate CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20With lower
Electron-hole pair recombination rate.Caused by the generation of this phenomenon may be due to the following reasons: CNT-Ni2P, Er3+:
Y3Al5O12And Bi12GeO20It forms cladding Z-type photocatalytic system and is conducive to Bi12GeO20Light induced electron (e on conduction band (CB)–) with
Ni2Hole (h in P valence band (VB)+) compound, and Ni2Light induced electron caused by P conduction band then passes through CNT transference.In short,
The experimental results showed that there are Bi by CNT12GeO20Surface and it is internal can not only serve as active site and receive electronics, can also press down
The recombination rate of electron-hole pair processed.Further, since presence of the CNT as electronics conductive medium, can be further improved electronics
Transfer rate.Therefore, the novel cladding Z-type structure catalyst CNT/Ni of design2P/Er3+:Y3Al5O12-CNT@Bi12GeO20
With excellent photocatalysis performance.
A kind of photochemical catalyst CNT/Ni of novel cladding Z-type structure of embodiment 22P/Er3+:Y3Al5O12-CNT@Bi12GeO20
Convert the application in Cr (VI) and rhodamine B degradation (RhB) simultaneously in photocatalysis
(1) different light application times, different photochemical catalysts for converting the light of Cr (VI) and rhodamine B degradation (RhB) simultaneously
Catalytic affect
Experiment condition:
50mL contains rhodamine B (RhB) aqueous solution of 10.0mg/L Cr (VI) and 5.0mg/L as A group.
50mg photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Powder is added to 50mL and contains 10.0mg/
Rhodamine B (RhB) aqueous solution of L Cr (VI) and 5.0mg/L is as B group.
50mg photochemical catalyst Ni2P/Er3+:Y3Al5O12@Bi12GeO20Powder is added to 50mL and contains 10.0mg/L Cr (VI)
Rhodamine B (RhB) aqueous solution with 5.0mg/L is as C group.
50mg photochemical catalyst Ni2P@Bi12GeO20Powder is added to 50mL and contains 10.0mg/L Cr's (VI) and 5.0mg/L
Rhodamine B (RhB) aqueous solution is as D group.
Under conditions of pH is the irradiation of 2,500W xenon lamp, light application time is respectively -20min, 0min, 20min, 40min.It is real
Result is tested as shown in figure 5, when light application time is 40min, photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20It is dense
When degree is 1.0g/L, 92.0% is reached for the conversion ratio of Cr (VI), the degradation rate for rhodamine B (RhB) is 48.0%.Its
Reason is that CNT as conductive channel, makes Bi12GeO20The light induced electron and Ni that conduction band generates2The photohole knot that P valence band generates
It closes, Ni2The light induced electron transfer that P conduction band generates.The compound of light induced electron and hole is effectively reduced, to significantly improve
The separative efficiencies of electrons and holes.Therefore be not present conductive channel photochemical catalyst Ni2P/Er3+:Y3Al5O12@Bi12GeO20
And Ni2P@Bi12GeO20It compares, the conversion ratio of Cr (VI) and the degradation rate of rhodamine B (RhB) simultaneously is significantly improved, are
35.0%, 57.0% and 42.0%, 46.0%.Hence it is demonstrated that photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20
With efficient photocatalytic activity.
Different light application times change over time for photochemical catalyst while converting Cr (VI) and rhodamine B degradation (RhB)
Photocatalysis influence, optimum illumination time 40min.
(2) different content photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20To Cr (VI) conversion simultaneously
Photocatalysis with rhodamine B degradation (RhB) influences
70mg photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Powder is added to 50mL and contains 10.0mg/
Rhodamine B (RhB) aqueous solution of L Cr (VI) and 5.0mg/L is as A group.
50mg photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Powder is added to 50mL and contains 10.0mg/
Rhodamine B (RhB) aqueous solution of L Cr (VI) and 5.0mg/L is as B group.
30mg photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Powder is added to 50mL and contains 20.0mg/
Rhodamine B (RhB) aqueous solution of L Cr (VI) and 5.0mg/L is as C group.
PH be 2,500W xenon lamp irradiation under conditions of, light application time be respectively -20min, 0min, 20min, 40min,
60min,80min.Experimental result is as shown in Figure 6.Its conversion and removal efficiency when photocatalyst concentrations are 1.4g/L, 1.0g/L
It is close, all have the effect of higher conversion Cr (VI) and rhodamine B degradation (RhB).And when photocatalyst concentrations are 0.6g/L
When, conversion and removal rate are declined.It is 80min, photochemical catalyst CNT/Ni in light application time2P/Er3+:Y3Al5O12-CNT@
Bi12GeO20When concentration is 1.0g/L, 98% is reached for the conversion ratio of Cr (VI), the degradation rate of rhodamine B (RhB) is
59.0%.Therefore 1.0g/L is the optimal use concentration of the photochemical catalyst.And work as photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-
CNT@Bi12GeO20Its conversion and degradation efficiency are fallen to 15.0% and 10.0% when concentration 0.6g/L, it may be possible to due to this
The photochemical catalyst of concentration can not provide enough light induced electrons and hole for light-catalyzed reaction.It is efficient to affect light-catalyzed reaction
It carries out.
(3) photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Various concentration Cr (VI) is converted simultaneously
Photocatalysis with 5ppm rhodamine B (RhB) degradation influences
Experiment condition:
50mg photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Powder, which is added to 50mL and contains concentration, is
Rhodamine B (RhB) aqueous solution of 10.0mg/L Cr (VI) and 5.0mg/L is as A group.
50mg photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Powder, which is added to 50mL and contains concentration, is
Rhodamine B (RhB) aqueous solution of 15.0mg/L Cr (VI) and 5.0mg/L is as B group.
50mg photochemical catalyst CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20Powder, which is added to 50mL and contains concentration, is
Rhodamine B (RhB) aqueous solution of 20.0mg/L Cr (VI) and 5.0mg/L is as C group.
PH be 2,500W xenon lamp irradiation under conditions of, light application time be respectively -20min, 0min, 20min, 40min,
60min,80min.Experimental result is as shown in fig. 7, be 80min, photochemical catalyst CNT/Ni in light application time2P/Er3+:Y3Al5O12-
CNT@Bi12GeO20Concentration is 1.0g/L, and solution C r (VI) concentration is 10.0mg/L, 15.0mg/L, and rhodamine B concentration is
Its conversion is close with degradation efficiency when 5.0mg/L, is 98.0%, 96.0% and 58.0%, 52.0%, all has higher turn
Change and degradation effect.And when solution C r (VI) concentration is 20.0mg/L, and rhodamine B concentration is 5.0mg/L, conversion and degradation
Rate, which has, more significantly falls to 40.0% and 20.0%.It can be seen that rhodamine B concentration is as Cr (VI) concentration 15.0mg/L
When 5.0mg/L, for optium concentration photochemical catalyst conversion and degraded.And its conversion and drop as Cr (VI) concentration 20.0mg/L
Solution efficiency is decreased obviously, it may be possible to due to excessive HCrO4-It is adsorbed on catalyst surface, affects photochemical catalyst for the sound of light
It answers.
A kind of photochemical catalyst CNT/Ni of novel cladding Z-type structure of embodiment 32P/Er3+:Y3Al5O12-CNT@Bi12GeO20
Photocatalysis converts the mechanism of Cr (VI) and rhodamine B degradation (RhB) simultaneously
As seen from Figure 8, Bi12GeO20Bandwidth 3.20eV, wherein valence band be+2.55eV, conduction band be -0.25eV.Ni2P band
Width is 1.00eV, and valence band is -0.23eV, and conduction band is -1.23eV.By Bi12GeO20Conduction band current potential and Ni2The valence band current potential of P is close,
Therefore comparatively ideal Z-type photocatalytic system, which can be formed, can efficiently shift light induced electron and hole pair.But since it is packet
Cover structure, Ni2P is Bi12GeO20It is coated, Ni2Light induced electron caused by P conduction band can not be transferred, in order to by Ni2P conduction band
Generated light induced electron transfer, CNT is added to Bi by us12GeO20With Ni2P, which is formed by clad structure, forms one
It is assumed that redox complex centre.Shift its light induced electron.To form special cladding Z-type photochemical catalyst CNT/
Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20.Convert the reaction of Cr (VI) and rhodamine B degradation (RhB) simultaneously in photocatalysis
In, Ni2Light induced electron caused by P conduction band passes through Bi by CNT12GeO20Interface, and shifted.There is cladding knot in CNT
Structure catalyst it is inside and outside.The CNT being stored in clad structure can be used as conductive channel, and be stored in outside clad structure
CNT then can be used as the active site for photocatalytic conversion Cr (VI).Because there are longer tubular structures by CNT, therefore can be significant
Increase the active site for converting Cr (VI).Bi is also increased simultaneously12GeO20Active site exposure, be Bi12GeO20Drop
Solution rhodamine B (RhB) provides more photoholes.And photohole is in Bi12GeO20Surface can directly decompose it is organic
Pollutant, until completely being decomposed.
Claims (10)
1. a kind of photochemical catalyst of novel cladding Z-type structure, it is characterised in that: the photocatalysis of the novel cladding Z-type structure
Agent is CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20。
2. a kind of preparation method of the photochemical catalyst of novel cladding Z-type structure as described in claim 1, which is characterized in that including
Following steps:
1) by GeO2It is dissolved into concentrated ammonia liquor, obtains GeO2Ammonia spirit；By BiCl3It is added in dehydrated alcohol, is completely dissolved to it
After GeO is added2In ammonia spirit, stirring 2h generates the colloidal sol of thick white；
2) by etc. quality Er3+:Y3Al5O12And CNT/Ni2P is added in ultrapure water, and using the fully dispersed 5min of ultrasound, will
Suspension is heated to boiling point, keeps constant temperature 2min, 80 DEG C of dry 12h after centrifugation.Powder after drying is ground, is then existed
2h is calcined at 400 DEG C, is finally ground, and CNT/Ni is obtained2P/Er3+:Y3Al5O12Nanoparticle powder.
3) CNT/Ni is added into the colloidal sol of thick white2P/Er3+:Y3Al5O12Nanometer powder is stirred at room temperature 12h, then dries
48h, powder is finely ground, and 600 DEG C of calcining 2h, grind after it is cooled to room temperature, obtain target product CNT/ in tube furnace
Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20。
3. preparation method as claimed in claim 2, which is characterized in that CNT/Ni in step 2)2P powder the preparation method comprises the following steps: will
NiCl2·6H2O and red phosphorus are added in ultrapure water, and 20min is stirred at room temperature, and obtain mixed solution；Mixed solution is added in CNT
In, continue to stir 1h, obtained aaerosol solution is transferred in reaction kettle 36h at 140 DEG C, collects and with distilled water and dehydrated alcohol
For several times, 60 DEG C of dry 12h, grind powder after drying, obtain CNT/Ni after centrifugation for cleaning2P powder.
4. preparation method as claimed in claim 2, which is characterized in that Er in step 2)3+:Y3Al5O12The preparation method of powder
Are as follows: by Er2O3、Y2O3Powder is dissolved in concentrated nitric acid and magnetic force heating stirring is until colorless and transparent, obtains rare-earth ion solution；So
Afterwards by Al (NO3)·9H2O is dissolved in distilled water, is stirred at room temperature with glass bar and is slowly added to rare-earth ion solution
In, using citric acid as chelating agent and cosolvent, citric acid is dissolved with distilled water, in 50-60 DEG C of heating stirring, when solution is in viscous
Stop when thick shape, obtains glutinous colloidal solution；Thick solution is put into 80 DEG C of heating 36h of baking oven constant temperature, in the drying process until
Solvent evaporated does not have sediment generation, finally obtains foam sol, then obtained colloidal sol exists respectively in 500 DEG C of heating 50min
1100 DEG C are calcined 2h respectively.Finally, taking out the substance of sintering from high temperature furnace and being cooled to room temperature to obtain Er in air3+:
Y3Al5O12Powder.
5. preparation method as claimed in claim 4, which is characterized in that in molar ratio, the citric acid: rare earth ion=3:1.
6. a kind of photochemical catalyst of novel cladding Z-type structure as described in claim 1 converts Cr (VI) and drop in photocatalysis simultaneously
Solve the application in rhodamine B (RhB).
7. application as claimed in claim 6, which is characterized in that application process is as follows: by CNT/Ni2P/Er3+:Y3Al5O12-
CNT@Bi12GeO20Nanometer grade powder is added in be transformed-degraded solutions, pH be 2,500W xenon lamp irradiation under conditions of into
Row illumination, the to be transformed-degraded solutions are the aqueous solution containing Cr (VI) and rhodamine B (RhB).
8. the use as claimed in claim 7, which is characterized in that the CNT/Ni2P/Er3+:Y3Al5O12-CNT@Bi12GeO20It receives
Concentration of the nanoscale powder in be transformed-degraded solutions is 1.0g/L.
9. the use as claimed in claim 7, which is characterized in that Cr (VI) and rhodamine B in the to be transformed-degraded solutions
(RhB) concentration ratio is 3:1.
10. the use as claimed in claim 7, which is characterized in that light application time 40min.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807261A (en) * | 2006-01-26 | 2006-07-26 | 上海交通大学 | Bismuth germanate nanometer powder preparation method |
| CN103586015A (en) * | 2013-11-22 | 2014-02-19 | 武汉理工大学 | Method for preparing regular-triangular-pyramid-shaped bismuth germinate visible-light catalyst |
| CN104399461A (en) * | 2014-11-25 | 2015-03-11 | 赤峰学院 | Upconversion luminescence nanometer photocatalyst and application of nanometer photocatalyst in hydrogen generation by hydrolysis |
| CN106082330A (en) * | 2016-07-29 | 2016-11-09 | 安徽理工大学 | The Bi that a kind of size is controlled12geO20mesomorphic and synthetic method thereof |
| CN106475121A (en) * | 2016-10-13 | 2017-03-08 | 辽宁大学 | A kind of new catalyst Er: Y3Al5O12/BiPO4And its preparation method and application |
| CN106582722A (en) * | 2016-11-25 | 2017-04-26 | 辽宁大学 | Composite photocatalysis system, and preparation method and application thereof |
| CN106732588A (en) * | 2016-11-15 | 2017-05-31 | 辽宁大学 | Catalyst of Cr (VI) and its preparation method and application in one kind conversion aqueous solution |
| CN108273522A (en) * | 2018-02-02 | 2018-07-13 | 辽宁大学 | A kind of Z-type semiconductor light-catalyst and its preparation method and application with trapezium structure |
-
2018
- 2018-09-04 CN CN201811022220.9A patent/CN109078645B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807261A (en) * | 2006-01-26 | 2006-07-26 | 上海交通大学 | Bismuth germanate nanometer powder preparation method |
| CN103586015A (en) * | 2013-11-22 | 2014-02-19 | 武汉理工大学 | Method for preparing regular-triangular-pyramid-shaped bismuth germinate visible-light catalyst |
| CN104399461A (en) * | 2014-11-25 | 2015-03-11 | 赤峰学院 | Upconversion luminescence nanometer photocatalyst and application of nanometer photocatalyst in hydrogen generation by hydrolysis |
| CN106082330A (en) * | 2016-07-29 | 2016-11-09 | 安徽理工大学 | The Bi that a kind of size is controlled12geO20mesomorphic and synthetic method thereof |
| CN106475121A (en) * | 2016-10-13 | 2017-03-08 | 辽宁大学 | A kind of new catalyst Er: Y3Al5O12/BiPO4And its preparation method and application |
| CN106732588A (en) * | 2016-11-15 | 2017-05-31 | 辽宁大学 | Catalyst of Cr (VI) and its preparation method and application in one kind conversion aqueous solution |
| CN106582722A (en) * | 2016-11-25 | 2017-04-26 | 辽宁大学 | Composite photocatalysis system, and preparation method and application thereof |
| CN108273522A (en) * | 2018-02-02 | 2018-07-13 | 辽宁大学 | A kind of Z-type semiconductor light-catalyst and its preparation method and application with trapezium structure |
Non-Patent Citations (2)
| Title |
|---|
| YIDI WANG ET AL.: ""Photocatalytic conversion of nitrite in aqueous solution over nanocomposite photocatalyst Er3+:Y3Al5O12/BiPO4 using different photosources"", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
| 赵丽敏等: ""纳米二氧化钛复合光催化的制备及其光催化活性的研究"", 《赤峰学院学报（自然科学版）》 * |
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