CN106975485A - Cr (VI) catalyst and its preparation method and application in a kind of Efficient Conversion water - Google Patents
Cr (VI) catalyst and its preparation method and application in a kind of Efficient Conversion water Download PDFInfo
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- CN106975485A CN106975485A CN201710280782.2A CN201710280782A CN106975485A CN 106975485 A CN106975485 A CN 106975485A CN 201710280782 A CN201710280782 A CN 201710280782A CN 106975485 A CN106975485 A CN 106975485A
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- efficient conversion
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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
- 229910004042 HAuCl4 Inorganic materials 0.000 claims abstract description 5
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 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
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 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
- 238000001914 filtration 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
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005187 foaming 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
- 238000001354 calcination Methods 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
- 239000000126 substance Substances 0.000 abstract description 3
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 abstract description 2
- 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
- 239000002245 particle Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910002367 SrTiO Inorganic materials 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
- 239000003795 chemical substances by application Substances 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- -1 rare-earth ion Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 206010005003 Bladder cancer Diseases 0.000 description 1
- 206010007269 Carcinogenicity Diseases 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
- 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
- 201000001531 bladder carcinoma Diseases 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
- 238000013461 design Methods 0.000 description 1
- 238000011161 development 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
- 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
- 238000009415 formwork 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
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research 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
- 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
- 208000010570 urinary bladder carcinoma Diseases 0.000 description 1
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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- Physics & Mathematics (AREA)
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- Catalysts (AREA)
Abstract
The present invention relates to catalyst of Cr (VI) in a kind of Efficient Conversion water and its preparation method and application.By Er3+:YAlO3Add Ti (OBu)4、Sr(NO3)2In NaOH mixed liquors, 24h is reacted under the conditions of 180 DEG C, Er is obtained3+:YAlO3@SrTiO3；By Er3+:YAlO3@SrTiO3Ethanol, ultrasonic disperse are dissolved in, while adding HAuCl4·4H2After being heated under O solution, boiling point；2h is calcined at 350 DEG C, Er is obtained3+: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 inventive method is simply novel, and cost is low, and the generation of no accessory substance can't cause environmental pollution.
Description
Technical field
The invention belongs to chemical catalysis field, more particularly to the synthesis of new catalyst and utilization catalyst are to Cr in water body
(VI) method converted.
Background technology
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
With concentration or pH under the conditions of, Cr (VI) is with chromate (HCrO4-/CrO4 2-) and bichromate (Cr2O7 2-) form enter ring
Border.Research shows, Cr (VI) has carcinogenicity of 1000 times higher than Cr (III), and generally have higher dissolubility, toxicity,
Unstability and bioactivity.If containing Cr (VI), human body can be increased and suffer from liver cancer, cutaneum carcinoma and carcinoma of urinary bladder in drinking water
Possibility.On the contrary, appropriate Cr (III) is element necessary to human body, therefore, it is very that Cr (VI) is reduced into Cr (III)
It is necessary.
Photocatalysis technology directly can remove pollutant in water body because of it using the light absorbed, and easily separated reuse, and by
To extensive concern, such as TiO2Because its catalytic activity is of a relatively high, physicochemical properties are stable, and are widely used.For going
Except the Cr (VI) in water body, it would be desirable to a semiconductor having compared with Strong oxdiative ability and reducing power is selected, by Cr (VI)
Cr (III) is converted into, this requires us to select an of a relatively high conduction band and the broadband semiconductor of relatively low valence band.Through adjusting
Look into, strontium titanates (SrTiO3) it is a kind of novel metalloid wide-band-gap semiconductor material, with higher photo catalytic reduction performance, but
Because with 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 profit
With the catalyst of visible ray.
The content of the invention
It is an object of the invention to design the new catalyst Er of Cr (VI) in a kind of Efficient Conversion water of synthesis3+:YAlO3@
(Au/SrTiO3)-Au-WO3.Compound involved in the present invention belongs to new rare metal catalyst, is applied to Cr (VI) and turns
Change, method is simple, pollution-free, catalyst stabilization and be easily isolated.
The technical solution adopted by the present invention is as follows：Cr (VI) catalyst in a kind of Efficient Conversion water, the catalyst is
Er3+:YAlO3@(Au/SrTiO3)-Au-WO3。
The preparation method of Cr (VI) catalyst in a kind of above-mentioned Efficient Conversion water, method is as follows：
1) by Ti (OBu)4It is dissolved in ethylene glycol, adds Sr (NO3)2And NaOH solution, magnetic agitation；Add Er3+:
YAlO3, magnetic agitation, and be transferred in hydrothermal reaction kettle, 22-26h is reacted under the conditions of 170-190 DEG C, is filtered, solids is washed
Wash, dry, obtain Er3+:YAlO3@SrTiO3；
2) by Er3+:YAlO3@SrTiO3Dissolve in ethanol, ultrasonic disperse 30-40 minutes, while adding HAuCl4·
4H2O solution；Under magnetic agitation, 30-40min is heated at the boiling point；Filtering, solids washing, after drying, 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, plus deionized water, ultrasonic disperse 30-40 minutes, are obtained
Mixed liquor, mixed liquor is heated to heat 30-40 minutes under boiling point, boiling point, centrifugation, sediment washing, after drying, in 300-
1-2h is calcined at 400 DEG C, grinds, obtains Er3+:YAlO3@(Au/SrTiO3)-Au-WO3。
The preparation method of Cr (VI) catalyst 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 Cr (VI) catalyst, described HAuCl in a kind of above-mentioned Efficient Conversion water4·4H2O's adds
Enter amount for Er3+:YAlO3@SrTiO3The 1-2% of quality.
The preparation method of Cr (VI) catalyst in a kind of above-mentioned Efficient Conversion water, in mass ratio, Er3+:YAlO3@
(Au/SrTiO3)-Au:WO3=1:1.
The preparation method of Cr (VI) catalyst, described 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)3The aqueous 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 foaming is sticked into colloidal solution in 75-85
35-40h is heated at DEG C, foam sol is obtained, foam sol is heated after 50-60min at 500 DEG C, 2-3h is calcined at 1100 DEG C,
Cooling, obtains Er3+:YAlO3。
The preparation method of Cr (VI) catalyst, described WO in a kind of above-mentioned Efficient Conversion water3Preparation method be：
By Na2WO4·2H2O and citric acid add water stir after, add HCl, until pH of mixed=1.00, and stir 30min, will
Mixed liquor is transferred in reactor, is handled 12h at 120 DEG C, is cooled to room temperature, abandons 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 Cr (VI) catalyst 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：In the solution containing Cr (VI)
In, add above-mentioned catalyst Er3+:YAlO3@(Au/SrTiO3)-Au-WO3, irradiated under normal temperature, solar irradiation.
The beneficial effects of the invention are as follows：
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+:YAlO3Can be by the visible of absorption
Light is converted into can be by SrTiO3The ultraviolet light directly utilized, so that the SrTiO with wider band gap3Can be more effectively sharp
Light-catalyzed reaction is carried out with sunshine.
2. the present invention, in order to reach that exciting electron-hole pair using sunshine improves the purpose of photocatalysis efficiency, is added
A small amount of noble metal Au is in semiconductor surface, and arrowband co-catalyst WO3It is compound, illustrate the optimal light for Cr VI
Catalytic reduction efficiency.
3. the present invention have studied with SrTiO on the basis of a variety of photocatalysis technologies for Cr (VI)3Turn light hair in cladding
Luminescent material simultaneously adds the technology that cocatalyst carries out Cr (VI) conversions.By the method for the present invention, Cr (VI) conversion ratio reaches
More than 99%, without influenceing other quality index.Compared with other photocatalysis technologies, process of the present invention is simple, and normal temperature and pressure enters
OK, mild condition, and using solar energy.
Brief description of the drawings
Fig. 1 a are Er3+:YAlO3XRD.
Fig. 1 b are Er3+:YAlO3SEM figure.
Fig. 2 a are WO3XRD.
Fig. 2 b are WO3SEM figure.
Fig. 3 a are Er3+:YAlO3@SrTiO3XRD.
Fig. 3 b are Er3+:YAlO3@SrTiO3SEM figure.
Fig. 4 a are Er3+:YAlO3@(Au/SrTiO3)-Au-WO3XRD.
Fig. 4 b are Er3+:YAlO3@(Au/SrTiO3)-Au-WO3SEM figure.
Embodiment
Embodiment 1
(1) Er3+:YAlO3@(Au/SrTiO3)-Au-WO3Preparation
1.Er3+:YAlO3Prepare：By 0.0232g Er2O3、1.3640g Y2O3It is dissolved in concentrated nitric acid, and magnetic force is heated
Stirring is until water white transparency, obtains rare-earth ion solution.Then a beaker is separately taken, 4.5316g Al (NO are weighed3)3·9H2O dissolves
In distilled water, stirred and be slowly added in above-mentioned rare-earth ion solution with glass bar at room temperature.Weigh 15.2325g lemons
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
Mix, stop when solution is in thick.Generation is not precipitated in this process, finally gives the glutinous colloidal solution of foaming.Will hair
The glutinous colloidal solution of bubble 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 give foam sol.Obtained foam sol is heated into 50min at 500 DEG C, then 2h is calcined at 1100 DEG C.Finally, from
The material of sintering is taken out in high temperature furnace and room temperature is cooled in atmosphere and obtains Er3+:YAlO3Powder.
2.WO3Prepare：By 1.50g Na2WO4·2H2O and 0.60g citric acid is dissolved in 50ml deionized waters, magnetic force
Stirring is well mixed to solution, obtains mixed liquor.Then, 6.00mol/L HCl is added dropwise to mixed liquor under continuous stirring
In, until pH of mixed=1.00, now solution presentation is faint yellow.30min is persistently stirred, mixed liquor is then transferred to 50ml
In reactor, 12h is reacted under the conditions of 120 DEG C.After the completion of reaction, cool down at room temperature, abandon supernatant, sediment deionization
Water and alcohol distinguish eccentric cleaning 3 times, after 60 DEG C dry a night, obtain pale yellow powder.Grinding, will be ground faint yellow
Powder is put into 500 DEG C of Muffle furnaces and calcines 2h.By obtained WO3Powder.
3.Er3+:YAlO3@SrTiO3Prepare：By 10mmol butyl titanate (Ti (OBu)4) be dissolved in 25ml ethylene glycol,
And magnetic agitation.Then, 2.1163g strontium nitrates (Sr (NO are added3)2) and 10ml 5.00mol/L NaOH solutions.Then, by matter
Amount ratio, Er3+:YAlO3:SrTiO3=0.7:1, add Er3+:YAlO3, lasting stirring.1.0h to be mixed is well mixed to solution
Afterwards, mixed liquor is transferred in 50ml hydrothermal reaction kettles, 24h is reacted under the conditions of 180 DEG C.Question response is completed, and reactor is natural
After cooling, supernatant is outwelled, reaction gained white powder is left.Respectively with deionized water and alcohol eccentric cleaning 3 times, outwell
Products therefrom is placed in baking oven after supernatant, 12h is dried under the conditions of 60 DEG C, Er is obtained3+:YAlO3@SrTiO3Powder.
4.Er3+:YAlO3@(Au/SrTiO3)-Au preparations：By 1.0g Er3+:YAlO3@SrTiO3Add to 25ml ethanol
In, it is placed in ultrasonic machine and carries out ultrasonic disperse.During ultrasonic disperse, appropriate HAuCl is added dropwise4·4H2O solution
(HAuCl4·4H2O quality is Er3+:YAlO3@SrTiO3Quality 1%), ultrasound 30 minutes after, mixed liquor is stirred in magnetic force
Mix down and be heated to boiling point, and kept for 30 minutes.Filtering, solids is respectively washed 3 times with deionized water and alcohol, then at 60 DEG C
Under the conditions of dry 12h.After gained powder mull, it is placed in 350 DEG C of Muffle furnaces and calcines 1h, after reaction terminates, grinding is collected, and is obtained
To Er3+:YAlO3@(Au/SrTiO3)-Au powder.
5.Er3+:YAlO3@(Au/SrTiO3)-Au-WO3Prepare：By 1g Er3+:YAlO3@(Au/SrTiO3)-Au and 1g
WO3Powder, is poured into 50ml deionized waters, ultrasonic disperse 30 minutes (80kHZ, ultrasonic power output is 50W), is disperseed
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 is respectively washed 3 times with deionized water and alcohol, then does gained powder under the conditions of 60 DEG C
Dry 12h.Finally, gained powder mull is placed in calcining 1h in 350 DEG C of Muffle furnaces, after question response terminates, obtains Er3+:
YAlO3@(Au/SrTiO3)-Au-WO3。
(2) characterize data
The Er of preparation3+:YAlO3XRD as shown in Figure 1a, found out by Fig. 1 a, the diffraction peak of sample and JCPDS standard cards
33-0040 data are basically identical, and the sample being indicated above after heat treatment is single body-centered cubic structure, is not all occurred
Other dephasigns.This explanation Er3+The doping of ion does not produce obvious influence on crystal structure.
The Er of preparation3+:YAlO3SEM as shown in Figure 1 b, found out by Fig. 1 b, gained crystal present spherical or spherical, grain
Footpath is 40-60nm, and size distribution is dispersed also preferable than more uniform.Illustrate sample preparation success.
The WO of preparation3XRD as shown in Figure 2 a, found out by Fig. 2 a, it may be determined that WO3Monoclinic crystal structure, as figure institute
Show, WO of all characteristic peaks being observed that all with monoclinic crystal structure3Standard card (JCPDS card No.72-0677)
It is corresponding well.
The WO of preparation3SEM as shown in Figure 2 b, found out by Fig. 2 b, nanoscale WO3Sheet, Average Particle Diameters is 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
Upper light conversion agent Er can significantly be seen3+:YAlO3Characteristic peak, in addition 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
270nm shaft-like material.
The Er of preparation3+:YAlO3@(Au/SrTiO3)-Au-WO3XRD and SEM it is as shown in Figs. 4a and 4b.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 work(to be combined with each other.But do not find the obvious characteristic peak for representing Au, this it is possible because
Disperse to be attached to Er well for the small test limit arrived less than XRD spectrum of cocatalyst Au usage amounts, or Au particles3+:
YAlO3@SrTiO3-WO3Surface.Found out by Fig. 4 b, in shaft-like Er3+:YAlO3@SrTiO3Some small are attached on surface
Particulate matter, as Au particles 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 path that is connected as two semiconductors of Au particles has been compounded in two
Between person, the electronics for making two semiconductors be produced under sunshine irradiation is combined on path Au, offset, and is obtained higher
Photocatalytic activity.As 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 are added3+:YAlO3@(Au/
SrTiO3)-Au-WO3, under normal temperature simulated solar illumination, magnetic agitation is opened, 6h is reacted, reaction finishes, by catalyst and molten
Liquid is separated.
Cr (VI) concentration is determined with diphenyl carbazide spectrophotometry, conversion ratio is obtained and reaches more than 99%.
Claims (10)
1. Cr (VI) catalyst in a kind of Efficient Conversion water, it is characterised in that described catalyst is Er3+:YAlO3@(Au/
SrTiO3)-Au-WO3。
2. the preparation method of Cr (VI) catalyst in a kind of Efficient Conversion water described in claim 1, it is characterised in that method
It is as follows：
1) by Ti (OBu)4It is dissolved in ethylene glycol, adds Sr (NO3)2And NaOH solution, magnetic agitation；Add Er3+:YAlO3,
Magnetic agitation, and be transferred in hydrothermal reaction kettle, 22-26h is reacted under the conditions of 170-190 DEG C, is filtered, solids washing is done
It is dry, obtain Er3+:YAlO3@SrTiO3；
2) by Er3+:YAlO3@SrTiO3Dissolve in ethanol, ultrasonic disperse 30-40 minutes, while adding HAuCl4·4H2O is molten
Liquid；Under magnetic agitation, 30-40min is heated at the boiling point；Filtering, solids washing, after drying, 1- is calcined at 300-400 DEG C
2h, grinding, obtains Er3+:YAlO3@(Au/SrTiO3)-Au；
3) by Er3+:YAlO3@(Au/SrTiO3)-Au and WO3Mixing, plus deionized water, ultrasonic disperse 30-40 minutes, must be mixed
Liquid, mixed liquor is heated to heat 30-40 minutes under boiling point, boiling point, centrifugation, sediment washing, after drying, at 300-400 DEG C
Lower calcining 1-2h, grinding, obtains Er3+:YAlO3@(Au/SrTiO3)-Au-WO3。
3. the preparation method of Cr (VI) catalyst in a kind of Efficient Conversion water according to claim 2, it is characterised 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 Cr (VI) catalyst in a kind of Efficient Conversion water according to claim 2, it is characterised in that
Described HAuCl4·4H2O addition is Er3+:YAlO3@SrTiO3The 1-2% of quality.
5. the preparation method of Cr (VI) catalyst in a kind of Efficient Conversion water according to claim 2, it is characterised in that
In mass ratio, Er3+:YAlO3@(Au/SrTiO3)-Au:WO3=1:1.
6. the preparation method of Cr (VI) catalyst in a kind of Efficient Conversion water according to claim 2, it is characterised in that
Described 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, in 50-60 DEG C of heating stirring, stop when solution is in thick, and must foam glutinous colloidal solution, will
The glutinous colloidal solution of foaming obtains foam sol, foam sol is heated into 50- at 500 DEG C in heating 35-40h at 75-85 DEG C
After 60min, 2-3h is calcined at 1100 DEG C, cooling obtains Er3+:YAlO3。
7. the preparation method of Cr (VI) catalyst in a kind of Efficient Conversion water according to claim 2, it is characterised in that
Described WO3Preparation method be：By Na2WO4·2H2O and citric acid add water stir after, HCl is added, until mixed liquor
PH=1.00, and 30min is stirred, mixed liquor is transferred in reactor, 12h is handled at 120 DEG C, is cooled to room temperature, abandon
Clear liquid, sediment washing, after drying, calcines 2h in 500 DEG C of Muffle furnaces, grinds, obtains WO3Powder.
8. the preparation method of Cr (VI) catalyst in a kind of Efficient Conversion water according to claim 7, it is characterised 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, it is characterised in that method is as follows：In the solution containing Cr (VI), add
Catalyst described in claim 1, irradiates under normal temperature, solar irradiation.
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| CN107597142A (en) * | 2017-09-20 | 2018-01-19 | 辽宁大学 | A kind of new Z-type sound catalyst for antibiotic waste water of degrading and its preparation method and application |
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| CN112221481A (en) * | 2020-08-31 | 2021-01-15 | 广东工业大学 | Catalyst for converting Cr (VI) in water by Z-shaped structure and preparation method and application thereof |
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