CN106975485B - The catalyst and its preparation method and application of Cr (VI) in a kind of Efficient Conversion water - Google Patents
The catalyst and its preparation method and application of Cr (VI) in a kind of Efficient Conversion water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- -1 centrifugation Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 abstract description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 20
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010005003 Bladder cancer Diseases 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 201000009030 Carcinoma Diseases 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 208000007097 Urinary Bladder Neoplasms Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229940035637 spectrum-4 Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 201000005112 urinary bladder cancer Diseases 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
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- 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
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Abstract
The present invention relates to the catalyst and its preparation method and application of Cr (VI) in Efficient Conversion water a kind of.By Er3+:YAlO3It is added Ti (OBu)4、Sr(NO3)2In NaOH mixed liquor, is reacted under the conditions of 180 DEG C for 24 hours, obtain Er3+:YAlO3@SrTiO3；By Er3+:YAlO3@SrTiO3It is dissolved in ethyl alcohol, ultrasonic disperse, while HAuCl is added4·4H2O solution, after heating under boiling point；2h is calcined at 350 DEG C, obtains Er3+:YAlO3@(Au/SrTiO3)-Au；By Er3+:YAlO3@(Au/SrTiO3)-Au and WO3Mixing, ultrasonic disperse will heat 30-40 minutes under suspension boiling point, calcine 2h at 350 DEG C, obtain target product.The method of the present invention is simple and novel, at low cost, and not will cause environmental pollution without by-product generation.
Description
Technical field
The invention belongs to the synthesis of chemical catalysis field more particularly to new catalyst and using catalyst to Cr in water body
(VI) method converted.
Background technique
With the development of the modern industry, the Cr VI (Cr (VI)) in natural water and industrial wastewater has become environment
One big harm.Cr (VI) is mainly derived from the industries such as mining, plating, Treatment of Metal Surface, process hides, printing and dyeing and casting, not
Under the conditions of same concentration or pH, Cr (VI) is with chromate (HCrO4-/CrO4 2-) and bichromate (Cr2O7 2-) form enter ring
Border.Studies have shown that Cr (VI) has a carcinogenicity of 1000 times higher than Cr (III), and usually have higher dissolubility, toxicity,
Unstability and bioactivity.If containing Cr (VI) in drinking water, it will increase human body and suffer from liver cancer, cutaneum carcinoma and bladder cancer
Possibility.On the contrary, suitable Cr (III) is element necessary to human body, therefore, it is very that Cr (VI), which is reduced into Cr (III),
It is necessary.
Photocatalysis technology is because it can be directly using pollutant in the light removal water body absorbed, and easily separated reuse, and by
To extensive concern, such as TiO2Because its catalytic activity is relatively high, physicochemical properties are stablized, and are widely used.For going
Except the Cr (VI) in water body, it would be desirable to the semiconductor having compared with Strong oxdiative ability and reducing power is selected, by Cr (VI)
It is converted into Cr (III), this requires us to select the broadband semiconductor of a relatively high conduction band and relatively low valence band.Through adjusting
It looks into, strontium titanates (SrTiO3) it is a kind of novel metalloid wide-band-gap semiconductor material, photo catalytic reduction performance with higher, however
Because having wider band gap, SrTiO3Ultraviolet light can only be absorbed and carry out light-catalyzed reaction.Ultraviolet light only accounts for solar spectrum
4%, this makes the utilization rate of solar energy become minimum.In order to obtain higher solar energy utilization ratio, it is necessary to which developing being capable of benefit
With the catalyst of visible light.
Summary of the invention
It is an object of the invention to design the new catalyst Er for synthesizing Cr (VI) in a kind of Efficient Conversion water3+:YAlO3@
(Au/SrTiO3)-Au-WO3.Compound involved in the present invention belongs to novel rare metal catalyst, is applied to Cr (VI) and turns
Change, method is simple, pollution-free, catalyst stabilization and is easily isolated.
The technical solution adopted by the invention is as follows: in a kind of Efficient Conversion water Cr (VI) catalyst, the catalyst is
Er3+:YAlO3@(Au/SrTiO3)-Au-WO3。
The preparation method of the catalyst of Cr (VI) in a kind of above-mentioned Efficient Conversion water, the method is as follows:
1) by Ti (OBu)4It is dissolved in ethylene glycol, Sr (NO is added3)2And NaOH solution, magnetic agitation；Er is added3+:
YAlO3, magnetic agitation, and be transferred in hydrothermal reaction kettle, 22-26h is reacted under the conditions of 170-190 DEG C, is filtered, and solids is washed
It washs, it is dry, obtain Er3+:YAlO3@SrTiO3；
2) by Er3+:YAlO3@SrTiO3It dissolves in ethanol, ultrasonic disperse 30-40 minutes, while HAuCl is added4·
4H2O solution；Under magnetic agitation, 30-40min is heated at the boiling point；Filtering, solids washing, after dry, at 300-400 DEG C
1-2h is calcined, grinding obtains Er3+:YAlO3@(Au/SrTiO3)-Au；
3) by Er3+:YAlO3@(Au/SrTiO3)-Au and WO3Mixing, adds deionized water, ultrasonic disperse 30-40 minutes, obtains
Mixed liquor is heated to boiling point, heated 30-40 minutes under boiling point by mixed liquor, centrifugation, sediment washing, after dry, in 300-
1-2h is calcined at 400 DEG C, is ground, is obtained Er3+:YAlO3@(Au/SrTiO3)-Au-WO3。
The preparation method of the catalyst of Cr (VI) in a kind of above-mentioned Efficient Conversion water, in molar ratio, Sr:Ti:Na=1:
1:5；In mass ratio, Er3+:YAlO3:SrTiO3=0.7:1.
The preparation method of the catalyst of Cr (VI), the HAuCl in a kind of above-mentioned Efficient Conversion water4·4H2O's adds
Entering amount is Er3+:YAlO3@SrTiO3The 1-2% of quality.
The preparation method of the catalyst of Cr (VI) in a kind of above-mentioned Efficient Conversion water, in mass ratio, Er3+:YAlO3@
(Au/SrTiO3)-Au:WO3=1:1.
The preparation method of the catalyst of Cr (VI), the Er in a kind of above-mentioned Efficient Conversion water3+:YAlO3Preparation
Method is: by Er2O3And Y2O3It is dissolved in concentrated nitric acid, then sequentially adds Al (NO3)3Aqueous solution and aqueous citric acid solution, in
50-60 DEG C of heating stirring stops when solution is in thick, and must foam glutinous colloidal solution, and the glutinous colloidal solution that will foam is in 75-85
35-40h is heated at DEG C, obtains foam sol, after foam sol is heated 50-60min at 500 DEG C, in 1100 DEG C of calcining 2-3h,
It is cooling, obtain Er3+:YAlO3。
The preparation method of the catalyst of Cr (VI), the WO in a kind of above-mentioned Efficient Conversion water3Preparation method be:
By Na2WO4·2H2After O and citric acid add water and stir uniformly, HCl is added, until pH of mixed=1.00, and 30min is stirred, it will
Mixed liquor is transferred in reaction kettle, is handled 12h at 120 DEG C, is cooled to room temperature, abandon supernatant, sediment deionized water and
Ethanol wash, after 60 DEG C of drying 12, grinding calcines 2h in 500 DEG C of Muffle furnaces, obtains WO3。
The preparation method of the catalyst of Cr (VI) in a kind of above-mentioned Efficient Conversion water, in mass ratio, Na2WO4·2H2O:
Citric acid=5:2.
Application of the above-mentioned catalyst in Efficient Conversion water in Cr (VI).Method is as follows: the solution of Yu Hanyou Cr (VI)
In, above-mentioned catalyst Er is added3+:YAlO3@(Au/SrTiO3)-Au-WO3, irradiated under room temperature, solar irradiation.
The beneficial effects of the present invention are:
1. the present invention, in order to improve SrTiO3Photocatalysis efficiency, and then hexavalent chromium is more effectively converted, by upper turn
Photo etching Er3+:YAlO3It is coated on SrTiO3Inside, in the combination of this photochemical catalyst, Er3+:YAlO3It can be by the visible of absorption
Light is converted into can be by SrTiO3The ultraviolet light directly utilized, to make the SrTiO with wider band gap3It can be more effectively sharp
Light-catalyzed reaction is carried out with sunlight.
2. the present invention adds to achieve the purpose that excite electron-hole pair to improve photocatalysis efficiency using sunlight
A small amount of noble metal Au is in semiconductor surface and narrowband co-catalyst WO3It is compound, illustrate the best light for Cr VI
Catalytic reduction efficiency.
3. the present invention has studied on the basis of a variety of photocatalysis technologies for Cr (VI) with SrTiO3Turn light hair in cladding
Luminescent material simultaneously adds the technology that cocatalyst carries out Cr (VI) conversion.By means of the present invention, the conversion ratio of Cr (VI) reaches
99% or more, without influencing other quality index.Compared with other photocatalysis technologies, process of the present invention is simple, normal temperature and pressure into
Row, mild condition, and using solar energy.
Detailed description of the invention
Fig. 1 a is Er3+:YAlO3XRD diagram.
Fig. 1 b is Er3+:YAlO3SEM figure.
Fig. 2 a is WO3XRD diagram.
Fig. 2 b is WO3SEM figure.
Fig. 3 a is Er3+:YAlO3@SrTiO3XRD diagram.
Fig. 3 b is Er3+:YAlO3@SrTiO3SEM figure.
Fig. 4 a is Er3+:YAlO3@(Au/SrTiO3)-Au-WO3XRD diagram.
Fig. 4 b is Er3+:YAlO3@(Au/SrTiO3)-Au-WO3SEM figure.
Specific embodiment
Embodiment 1
(1) Er3+:YAlO3@(Au/SrTiO3)-Au-WO3Preparation
1.Er3+:YAlO3Preparation: by 0.0232g Er2O3、1.3640g Y2O3It is dissolved in concentrated nitric acid, and magnetic force heats
Stirring obtains rare-earth ion solution until colorless and transparent.Then a beaker is separately taken, 4.5316g Al (NO is weighed3)3·9H2O dissolution
In distilled water, is stirred and be slowly added in above-mentioned rare-earth ion solution with glass bar at room temperature.Weigh 15.2325g lemon
Lemon acid is dissolved as chelating agent and cosolvent and with distilled water, is then added in above-mentioned solution.Then stirred in 50-60 DEG C of heating
It mixes, stops when solution is in thick.It is generated in this process without precipitating, finally obtains the glutinous colloidal solution of foaming.It will hair
It steeps glutinous colloidal solution and is put into baking oven, 80 DEG C of heated at constant temperature 36h.In the drying process until solvent evaporated does not have sediment generation,
Finally obtain foam sol.By obtained foam sol in 500 DEG C of heating 50min, then in 1100 DEG C of calcining 2h.Finally, from
The substance of sintering is taken out in high temperature furnace and is cooled to room temperature to obtain Er in air3+:YAlO3Powder.
2.WO3Preparation: by 1.50g Na2WO4·2H2The citric acid of O and 0.60g is dissolved in 50ml deionized water, magnetic force
Stirring to solution is uniformly mixed, and obtains mixed liquor.Then, the HCl of 6.00mol/L is added dropwise to mixed liquor under continuous stirring
In, until pH of mixed=1.00, solution is presented faint yellow at this time.30min is persistently stirred, mixed liquor is then transferred to 50ml
In reaction kettle, 12h is reacted under the conditions of 120 DEG C.After the reaction was completed, it cools down at room temperature, abandons supernatant, sediment deionization
Water and alcohol are distinguished eccentric cleaning 3 times, after 60 DEG C of one nights of drying, obtain pale yellow powder.Grinding, will be ground faint yellow
Powder is put into 500 DEG C of Muffle furnaces and calcines 2h.The WO that will be obtained3Powder.
3.Er3+:YAlO3@SrTiO3Preparation: by the butyl titanate (Ti (OBu) of 10mmol4) be dissolved in 25ml ethylene glycol,
And magnetic agitation.Then, 2.1163g strontium nitrate (Sr (NO is added3)2) and 10ml 5.00mol/L NaOH solution.Then, by matter
Measure ratio, Er3+:YAlO3:SrTiO3Er is added in=0.7:13+:YAlO3, lasting to stir.1.0h to be mixed is uniformly mixed to solution
Afterwards, mixed liquor is transferred in 50ml hydrothermal reaction kettle, is reacted for 24 hours under the conditions of 180 DEG C.It is completed wait react, reaction kettle is natural
After cooling, supernatant is outwelled, leaves reaction gained white powder.Deionized water and alcohol eccentric cleaning 3 times are used respectively, are outwelled
Products therefrom is placed in baking oven after supernatant, dry 12h, obtains Er under the conditions of 60 DEG C3+:YAlO3@SrTiO3Powder.
4.Er3+:YAlO3@(Au/SrTiO3)-Au preparation: by 1.0g Er3+:YAlO3@SrTiO3It is added to 25ml ethyl alcohol
In, it is placed in ultrasonic machine and carries out ultrasonic disperse.During ultrasonic disperse, appropriate HAuCl is added dropwise4·4H2O solution
(HAuCl4·4H2The quality of O is Er3+:YAlO3@SrTiO3The 1% of quality), ultrasound stirred mixed liquor in magnetic force after 30 minutes
It mixes down and is heated to boiling point, and kept for 30 minutes.Filtering, solids deionized water and alcohol are respectively washed 3 times, then at 60 DEG C
Under the conditions of dry 12h.It after gained powder mull, is placed in 350 DEG C of Muffle furnaces and calcines 1h, after reaction, grinding is collected, and is obtained
To Er3+:YAlO3@(Au/SrTiO3)-Au powder.
5.Er3+:YAlO3@(Au/SrTiO3)-Au-WO3Preparation: by 1g Er3+:YAlO3@(Au/SrTiO3)-Au and 1g
WO3Powder pours into 50ml deionized water, ultrasonic disperse 30 minutes (80kHZ, ultrasonic power output 50W), is dispersed
Uniform mixed liquor.Then, mixed liquor is heated to liquid boiling under the conditions of magnetic agitation, and keeps boiling 30 minutes.Instead
After the completion of answering, filtering, sediment deionized water and alcohol are respectively washed 3 times, then do gained powder under the conditions of 60 DEG C
Dry 12h.1h is calcined finally, gained powder mull is placed in 350 DEG C of Muffle furnaces, to after reaction, obtain Er3+:
YAlO3@(Au/SrTiO3)-Au-WO3。
(2) characterize data
The Er of preparation3+:YAlO3XRD it is as shown in Figure 1a, found out by Fig. 1 a, the diffraction peak of sample and JCPDS standard card
The data of 33-0040 are almost the same, and the sample after being indicated above heat treatment is single body-centered cubic structure, all do not occur
Other miscellaneous phases.This illustrates Er3+The doping of ion does not generate apparent influence on crystal structure.
The Er of preparation3+:YAlO3SEM it is as shown in Figure 1 b, found out by Fig. 1 b, spherical or spherical, grain is presented in gained crystal
Diameter is 40-60nm, and size distribution is relatively uniform, and dispersibility is also preferable.Illustrate sample preparation success.
The WO of preparation3XRD it is as shown in Figure 2 a, found out by Fig. 2 a, can determine WO3Monoclinic crystal structure, as scheme institute
Show, it is all it can be observed that characteristic peaks all with the WO of monoclinic crystal structure3Standard card (JCPDS card No.72-0677)
It is corresponding well.
The WO of preparation3SEM it is as shown in Figure 2 b, found out by Fig. 2 b, nanoscale WO3Sheet, Average Particle Diameters are presented in particle
For 300nm.
The Er of preparation3+:YAlO3@SrTiO3XRD and SEM as best shown in figures 3 a and 3b.It can be seen from Fig. 3 a from figure
It can significantly see upper light conversion agent Er3+:YAlO3Characteristic peak, in addition to this some other characteristic peaks is in 2 θ=22.7 °
(100), 32.28 ° (110), 39.86 ° (111), 46.62 ° (521), 57.6 ° (211) and 67.66 ° (221) are also observed,
This is consistent with standard card JCPDS 35-0734.Found out by Fig. 3 b, the compound features after cladding are that particle size exists
The rod-shaped substance of 270nm.
The Er of preparation3+:YAlO3@(Au/SrTiO3)-Au-WO3XRD and SEM it is as shown in Figs. 4a and 4b.It can be with by Fig. 4 a
Find out, can be found from figure and represent Er3+:YAlO3@SrTiO3Characteristic peak and represent WO3Characteristic peak, illustrate Er3+:
YAlO3@SrTiO3And WO3Form function to be combined with each other.However do not find and significantly represent the characteristic peak of Au, this it is possible because
For the small detection limit or Au particle to lower than XRD spectrum of cocatalyst Au usage amount, dispersion is attached to Er well3+:
YAlO3@SrTiO3-WO3Surface.Found out by Fig. 4 b, in rod-shaped Er3+:YAlO3@SrTiO3Some small are attached on surface
Particulate matter, as Au particle have been compounded in Er as cocatalyst3+:YAlO3@SrTiO3Surface.In addition, in Er3+:YAlO3@
SrTiO3With WO3Between, it was found that finely ground particle substance is that the access that connects as two semiconductors of Au particle has been compounded in two
Between person, the electronics for generating two semiconductors under sunlight irradiation carries out compound, counteracting on access Au, obtains higher
Photocatalytic activity.It can be seen that sunlight catalytic agent Er3+:YAlO3@(Au/SrTiO3)-Au-WO3Compound is successfully made
Standby synthesis,
(3) Cr (VI) method for transformation
In the test tube of light-catalyzed reaction instrument, 50mL Cr (VI) solution (5ppm) and 50mg Er is added3+:YAlO3@(Au/
SrTiO3)-Au-WO3, under room temperature simulated solar illumination, magnetic agitation is opened, reacts 6h, end of reaction, by catalyst and molten
Liquid is separated.
Cr (VI) concentration is measured with diphenyl carbazide spectrophotometry, conversion ratio is obtained and reaches 99% or more.
Claims (10)
1. the catalyst of Cr (VI) in a kind of Efficient Conversion water, which is characterized in that the catalyst is Er3+:YAlO3@(Au/
SrTiO3)-Au-WO3；Upper light conversion agent Er3+:YAlO3It is coated on SrTiO3Inside, Au particle are compounded in Er as cocatalyst3+:
YAlO3@SrTiO3Surface, in Er3+:YAlO3@SrTiO3With WO3Between, access that Au particle is connected as two semiconductors
It is compound therebetween.
2. the preparation method of the catalyst of Cr (VI) in a kind of Efficient Conversion water described in claim 1, which is characterized in that method
It is as follows:
1) by Ti (OBu)4It is dissolved in ethylene glycol, Sr (NO is added3)2And NaOH solution, magnetic agitation；Er is added3+:YAlO3,
Magnetic agitation, and be transferred in hydrothermal reaction kettle, 22-26 h, filtering are reacted under the conditions of 170-190 DEG C, solids washing is done
It is dry, obtain Er3+:YAlO3@SrTiO3；
2) by Er3+:YAlO3@SrTiO3It dissolves in ethanol, ultrasonic disperse 30-40 minutes, while HAuCl is added4·4H2O is molten
Liquid；Under magnetic agitation, 30-40min is heated at the boiling point；Filtering, solids washing calcine 1- at 300-400 DEG C after dry
2 h, grinding, obtain Er3+:YAlO3@(Au/SrTiO3)-Au；
3) by Er3+:YAlO3@(Au/SrTiO3)-Au and WO3Mixing, adds deionized water, ultrasonic disperse 30-40 minutes, must mix
Mixed liquor is heated to boiling point, heated 30-40 minutes under boiling point by liquid, centrifugation, sediment washing, after dry, at 300-400 DEG C
Lower calcining 1-2 h, grinding, obtains Er3+:YAlO3@(Au/SrTiO3)-Au-WO3。
3. the preparation method of the catalyst of Cr (VI) in a kind of Efficient Conversion water according to claim 2, which is characterized in that
In molar ratio, Sr:Ti:Na=1:1:5；In mass ratio, Er3+:YAlO3 : SrTiO3=0.7 : 1。
4. the preparation method of the catalyst of Cr (VI) in a kind of Efficient Conversion water according to claim 2, which is characterized in that
The HAuCl4·4H2The additional amount of O is Er3+:YAlO3@SrTiO3The 1-2% of quality.
5. the preparation method of the catalyst of Cr (VI) in a kind of Efficient Conversion water according to claim 2, which is characterized in that
In mass ratio, Er3+:YAlO3@(Au/SrTiO3)-Au : WO3=1 : 1。
6. the preparation method of the catalyst of Cr (VI) in a kind of Efficient Conversion water according to claim 2, which is characterized in that
The Er3+:YAlO3Preparation method be: by Er2O3And Y2O3It is dissolved in concentrated nitric acid, then sequentially adds Al (NO3)3Water
Solution and aqueous citric acid solution stop in 50-60 °C of heating stirring when solution is in thick, and must foam glutinous colloidal solution, will
The glutinous colloidal solution that foams heats 35-40h under 75-85 °C, obtains foam sol, foam sol is heated 50- under 500 °C
It is cooling in 1100 °C of calcining 2-3h after 60min, obtain Er3+:YAlO3。
7. the preparation method of the catalyst of Cr (VI) in a kind of Efficient Conversion water according to claim 2, which is characterized in that
The WO3Preparation method be: by Na2WO4∙2H2After O and citric acid add water and stir uniformly, HCl is added, until pH of mixed
=1.00, and 30 min are stirred, mixed liquor is transferred in reaction kettle, 12 h are handled at 120 DEG C, are cooled to room temperature, in abandoning
Clear liquid, sediment washing calcine 2 h after dry in 500 DEG C of Muffle furnaces, grind, obtain WO3Powder.
8. the preparation method of the catalyst of Cr (VI) in a kind of Efficient Conversion water according to claim 7, which is characterized in that
In mass ratio, Na2WO4∙2H2O: citric acid=5:2.
9. application of the catalyst described in claim 1 in Efficient Conversion water in Cr (VI).
10. application according to claim 9, which is characterized in that method is as follows: in the solution of Yu Hanyou Cr (VI), being added
Catalyst described in claim 1 irradiates under room temperature, solar irradiation.
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