CN103447025A - Dy/BiVO4 photocatalyst as well as preparation method and application thereof - Google Patents
Dy/BiVO4 photocatalyst as well as preparation method and application thereof Download PDFInfo
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- CN103447025A CN103447025A CN2013103570549A CN201310357054A CN103447025A CN 103447025 A CN103447025 A CN 103447025A CN 2013103570549 A CN2013103570549 A CN 2013103570549A CN 201310357054 A CN201310357054 A CN 201310357054A CN 103447025 A CN103447025 A CN 103447025A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000011941 photocatalyst Substances 0.000 title abstract description 6
- 229910002915 BiVO4 Inorganic materials 0.000 title abstract 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000001105 regulatory effect Effects 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 49
- 229910052797 bismuth Inorganic materials 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003760 magnetic stirring Methods 0.000 claims description 30
- 238000009413 insulation Methods 0.000 claims description 24
- 238000010792 warming Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 19
- 238000009938 salting Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- 239000013049 sediment Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 229910052845 zircon Inorganic materials 0.000 claims description 12
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000000356 contaminant Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 4
- 150000001621 bismuth Chemical class 0.000 abstract 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 150000003681 vanadium Chemical class 0.000 abstract 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 abstract 1
- DCKWZDOAGNMKMX-UHFFFAOYSA-N dysprosium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DCKWZDOAGNMKMX-UHFFFAOYSA-N 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 17
- 230000001276 controlling effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 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 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 239000013078 crystal Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention relates to a Dy/BiVO4 photocatalyst as well as a preparation method and an application thereof. The Dy/BiVO4 photocatalyst comprises a principal component of BiVO4, is in a square zircon-shaped structure and contains Dy<3+> in a BiVO4 lattice. The preparation method comprises the following steps: respectively dissolving bismuth nitrate pentahydrate and ammonium metavanadate in water to obtain a bismuth salt solution and a vanadium salt solution; adding the vanadium salt solution to the bismuth salt solution to obtain a mixed solution according to the mole ratio that Bi to V is equal to 1 to1; regulating the pH value of the mixed solution to 8; then adding dysprosium nitrate hexahydrate, wherein the mole ratio of Dy to Bi is (2.04-13.64) to 100; keeping temperature at the power of 300W and the temperature of 180 DEG C for 40 minutes by adopting a microwave hydrothermal method to prepare Dy/BiVO4. The preparation method disclosed by the invention combines the advantages of microwave heating and hydrothermal methods for synthesizing powder, is high in heating speed, uniform in heating, and capable of shortening the reaction time and improving the working efficiency; the synthesized Dy/BiVO4 photocatalyst is relatively high in photocatalysis activity and can be applied to environmental pollutant treatment.
Description
Technical field
The invention belongs to the photocatalyst material field, relate to a kind of Dy/BiVO
4photochemical catalyst and its preparation method and application.
Background technology
In recent years, the application of Photocatalytic Oxidation With Semiconductors method in waste water treatment has been subject to scholars' attention, and it is that the free radical of the strong oxidizing property of utilizing semiconductor light-catalyst to produce under the condition of illumination is thoroughly degraded organic pollution, and finally generates H
2o and CO
2deng inorganic molecules.The consersion unit of this method is simple, secondary pollution is little, operation is easy to control, operating cost is low, can effectively utilize sunshine as the reaction light source.
Yet, BiVO
4be a kind of eco-friendly conductor photocatalysis material, it has three kinds of crystal structures: monocline scheelite type, cubic scheelite type and cubic Zircon cut, wherein, for studying the BiVO of photocatalysis performance
4mainly the BiVO of cubic Zircon cut and monocline scheelite type
4.Monoclinic phase BiVO
4energy gap less (2.40eV), can absorb more visible ray, and in its lattice, distortion has occurred the Bi-O key, and this distortion has improved the separative efficiency in light induced electron and hole, and then has improved to a certain extent photocatalysis performance, so at BiVO
4three kinds of crystal formations in, monoclinic phase BiVO
4visible light catalysis activity the highest, this makes one of its focus that becomes people research, and Tetragonal BiVO
4almost there is no photocatalysis effect under visible ray, seldom studied.But, because the separative efficiency in light induced electron and hole is lower, the monocline scheelite type structure BiVO of pure phase
4photocatalysis effect unsatisfactory.Doping can improve BiVO
4light-catalyzed reaction efficiency and selective, at present to BiVO
4the method of carrying out doping vario-property mostly is infusion process, in traditional solid reaction process, chemical coprecipitation, sol-gel process and hydro-thermal method etc., prepares pure phase BiVO
4after, then select suitable source metal to adopt the method for dipping to be adulterated to it, the method flow process is many, complex process.
Summary of the invention
The object of the present invention is to provide a kind of Dy/BiVO
4photochemical catalyst and its preparation method and application, the method combines the advantage of heating using microwave and the characteristics of hydro-thermal reaction, and synthetic Dy/BiVO
4photochemical catalyst has higher photocatalytic activity.
For achieving the above object, the technical solution used in the present invention is:
A kind of Dy/BiVO
4photochemical catalyst, its main component is BiVO
4, be cubic Zircon cut structure, and BiVO
4lattice in contain Dy
3+, wherein the mol ratio of Dy element and Bi element is (2.04～13.64): 100.
Its pattern is short cylinder, is of a size of nanoscale.
A kind of Dy/BiVO
4the preparation method of photochemical catalyst comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o is soluble in water, stirs, and obtains the bismuth salting liquid; By NH
4vO
3be dissolved in the water of 100 ℃, heating stirs, and obtains vanadic salts solution;
Step 2: the mol ratio by Bi and V is that 1:1 is added to vanadic salts solution in the bismuth salting liquid, stirs, and obtains mixed liquor;
Step 3: the pH value of regulating mixed liquor is 8, stirs;
Step 4: by Dy (NO
3)
36H
2o joins in the mixed liquor of having regulated after the pH value, stirs, and obtains precursor liquid, and wherein the mol ratio of Dy and Bi is (2.04～13.64): 100;
Step 5: precursor liquid is added in microwave hydrothermal reaction kettle, the microwave hydrothermal reaction kettle sealing is placed in microwave assisted hydrothermal synthesis apparatus, setting pressure is 1.1MPa, under the microwave power of 300W, from room temperature, is warming up to 100 ℃, at 100 ℃ of insulation 8min; Then be warming up to 150 ℃ from 100 ℃, at 150 ℃ of insulation 8min; Be warming up to 180 ℃, end reaction after 180 ℃ of insulation 40min from 150 ℃ again;
Step 6: question response is cooled to room temperature after finishing, and takes out the sediment in microwave hydrothermal reaction kettle, washing, and drying, obtain Dy/BiVO
4photochemical catalyst.
Bi (NO in described bismuth salting liquid
3)
35H
2the concentration of O is 0.4mol/L; NH in vanadic salts solution
4vO
3concentration be 0.4mol/L.
In described step 1 by Bi (NO
3)
35H
2o stirring soluble in water 20min; By NH
4vO
3be dissolved in the water of 100 ℃ and add thermal agitation 20min under 90-100 ℃; Stirring in described step 2 is to stir 15min on magnetic stirring apparatus.
The NaOH solution that is 5mol/L by concentration in described step 3 is regulated the pH value of mixed liquor, and the rate of addition of NaOH solution is less than or equal to 1mL/min.
Stirring in described step 3 is to stir 25min on magnetic stirring apparatus; Stirring in described step 4 is to stir 20min on magnetic stirring apparatus.
In described step 5, the packing ratio of microwave hydrothermal reaction kettle is 55%.
Washing in described step 6 is extremely neutral by deionized water and absolute ethanol washing sediment; Described drying is at 75 ℃ of lower freeze-day with constant temperature 24h.
Dy/BiVO
4the application of photochemical catalyst aspect the environmental contaminants processing.
With respect to prior art, beneficial effect of the present invention is:
Dy/BiVO provided by the invention
4the preparation method of photochemical catalyst, with five water bismuth nitrate (Bi (NO
3)
35H
2o) be the bismuth source, ammonium metavanadate (NH
4vO
3) be the vanadium source, preparation BiVO
4, then with six water dysprosium nitrate (Dy (NO
3)
36H
2o) be the dysprosium source, prepare size at nano level high activity Dy/BiVO
4the photochemical catalyst powder.The present invention is by Dy
3+introduce BiVO
4lattice in, improved pure phase BiVO
4efficiency aspect degradable organic pollutant.The present invention adopts microwave-hydrothermal method to synthesize high activity Dy/BiVO
4photochemical catalyst, the method combines the advantage of heating using microwave and hydro-thermal method, can realize the stirring on molecular level, firing rate is fast, and homogeneous heating, without thermograde, without hysteresis effect, overcome the hydro-thermal container and heated inhomogeneous shortcoming, shortened the reaction time, improved operating efficiency, and reaction condition gentleness, technological process is simple, easy to operate, and manufacturing cycle is short.
Dy/BiVO provided by the invention
4photochemical catalyst is cubic Zircon cut structure, and its main component is BiVO
4, and BiVO
4lattice in contain Dy
3+, there is higher photocatalytic activity, can be applied to environmental contaminants processing aspect, improved pure phase BiVO
4photocatalysis performance, reached pure phase BiVO
4carry out the purpose of modification, have a good application prospect.
Further, Dy/BiVO provided by the invention
4the pattern of photochemical catalyst is short cylinder, is of a size of nanoscale.
The accompanying drawing explanation
Fig. 1 is the Dy/BiVO of the embodiment of the present invention 5 preparations
4the FE-SEM figure of photochemical catalyst;
Fig. 2 is the different Dy of the present invention
3+the Dy/BiVO prepared under addition
4the XRD spectra of photochemical catalyst, wherein a is not for adding the pure phase BiVO of Dy
4the XRD collection of illustrative plates, b～g is respectively the Dy/BiVO of embodiment 1～embodiment 6 preparation
4the XRD collection of illustrative plates of photochemical catalyst;
Fig. 3 is the different Dy of the present invention
3+the Dy/BiVO prepared under addition
4degradation rate-the time graph of the rhodamine B degradation of photochemical catalyst, the degradation curve that wherein RhB is rhodamine B self while not adding catalyst; A is not for adding the pure phase BiVO of Dy
4degradation curve, b～g is respectively the Dy/BiVO of embodiment 1～embodiment 6 preparation
4the degradation curve of photochemical catalyst.
The specific embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is described in further detail.
Embodiment 1:
A kind of Dy/BiVO
4photochemical catalyst, its main component is BiVO
4, be cubic Zircon cut structure, and BiVO
4lattice in contain Dy
3+, wherein the mol ratio of Dy element and Bi element is 2.04:100.
A kind of Dy/BiVO
4the preparation method of photochemical catalyst comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o is dissolved in deionized water, stirs 20min on magnetic stirring apparatus, obtains Bi (NO
3)
35H
2the bismuth salting liquid that O concentration is 0.4mol/L; By NH
4vO
3be dissolved in the deionized water of 100 ℃, add thermal agitation 20min under 100 ℃, obtain NH
4vO
3the vanadic salts solution that concentration is 0.4mol/L;
Step 2: the mol ratio by Bi and V is that 1:1 slowly is added drop-wise to vanadic salts solution in the bismuth salting liquid, stirs 15min on magnetic stirring apparatus, obtains mixed liquor;
Step 3: take the rate of addition of 1mL/min to dripping the NaOH solution that concentration is 5mol/L in mixed liquor, the pH that regulates mixed liquor is 8, and stirs 25min on magnetic stirring apparatus;
Step 4: by Dy (NO
3)
36H
2o joins in the mixed liquor of having regulated after the pH value, stirs 20min on magnetic stirring apparatus, is mixed with precursor liquid, and wherein the mol ratio of Dy and Bi is 2.04:100;
Step 5: precursor liquid is added in microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 55%, then the microwave hydrothermal reaction kettle sealing is placed in the microwave hydrothermal synthesizer, select the microwave temperature controlling mode, setting pressure is 1.1MPa, under the microwave power of 300W, be warming up to 100 ℃ from room temperature, at 100 ℃ of insulation 8min; Then be warming up to 150 ℃ from 100 ℃, at 150 ℃ of insulation 8min; Be warming up to 180 ℃, end reaction after 180 ℃ of insulation 40min from 150 ℃ again;
Step 6: question response is cooled to room temperature after finishing, and takes out the sediment in microwave hydrothermal reaction kettle, extremely neutral by deionized water and absolute ethanol washing sediment, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains Dy/BiVO
4photochemical catalyst.
Embodiment 2:
A kind of Dy/BiVO
4photochemical catalyst, its main component is BiVO
4, be cubic Zircon cut structure, and BiVO
4lattice in contain Dy
3+, wherein the mol ratio of Dy element and Bi element is 4.17:100.
A kind of Dy/BiVO
4the preparation method of photochemical catalyst comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o is dissolved in deionized water, stirs 20min on magnetic stirring apparatus, obtains Bi (NO
3)
35H
2the bismuth salting liquid that O concentration is 0.4mol/L; By NH
4vO
3be dissolved in the deionized water of 100 ℃, add thermal agitation 20min under 90 ℃, obtain NH
4vO
3the vanadic salts solution that concentration is 0.4mol/L;
Step 2: the mol ratio by Bi and V is that 1:1 slowly is added drop-wise to vanadic salts solution in the bismuth salting liquid, stirs 15min on magnetic stirring apparatus, obtains mixed liquor;
Step 3: take the rate of addition of 0.5mL/min to dripping the NaOH solution that concentration is 5mol/L in mixed liquor, the pH that regulates mixed liquor is 8, and stirs 25min on magnetic stirring apparatus;
Step 4: by Dy (NO
3)
36H
2o joins in the mixed liquor of having regulated after the pH value, stirs 20min on magnetic stirring apparatus, is mixed with precursor liquid, and wherein the mol ratio of Dy and Bi is 4.17:100;
Step 5: precursor liquid is added in microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 55%, then the microwave hydrothermal reaction kettle sealing is placed in the microwave hydrothermal synthesizer, select the microwave temperature controlling mode, setting pressure is 1.1MPa, under the microwave power of 300W, be warming up to 100 ℃ from room temperature, at 100 ℃ of insulation 8min; Then be warming up to 150 ℃ from 100 ℃, at 150 ℃ of insulation 8min; Be warming up to 180 ℃, end reaction after 180 ℃ of insulation 40min from 150 ℃ again;
Step 6: question response is cooled to room temperature after finishing, and takes out the sediment in microwave hydrothermal reaction kettle, extremely neutral by deionized water and absolute ethanol washing sediment, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains Dy/BiVO
4photochemical catalyst.
Embodiment 3:
A kind of Dy/BiVO
4photochemical catalyst, its main component is BiVO
4, be cubic Zircon cut structure, and BiVO
4lattice in contain Dy
3+, wherein the mol ratio of Dy element and Bi element is 6.38:100.
A kind of Dy/BiVO
4the preparation method of photochemical catalyst comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o is dissolved in deionized water, stirs 20min on magnetic stirring apparatus, obtains Bi (NO
3)
35H
2the bismuth salting liquid that O concentration is 0.4mol/L; By NH
4vO
3be dissolved in the deionized water of 100 ℃, add thermal agitation 20min under 95 ℃, obtain NH
4vO
3the vanadic salts solution that concentration is 0.4mol/L;
Step 2: the mol ratio by Bi and V is that 1:1 slowly is added drop-wise to vanadic salts solution in the bismuth salting liquid, stirs 15min on magnetic stirring apparatus, obtains mixed liquor;
Step 3: take the rate of addition of 0.8mL/min to dripping the NaOH solution that concentration is 5mol/L in mixed liquor, the pH that regulates mixed liquor is 8, and stirs 25min on magnetic stirring apparatus;
Step 4: by Dy (NO
3)
36H
2o joins in the mixed liquor of having regulated after the pH value, stirs 20min on magnetic stirring apparatus, is mixed with precursor liquid, and wherein the mol ratio of Dy and Bi is 6.38:100;
Step 5: precursor liquid is added in microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 55%, then the microwave hydrothermal reaction kettle sealing is placed in the microwave hydrothermal synthesizer, select the microwave temperature controlling mode, setting pressure is 1.1MPa, under the microwave power of 300W, be warming up to 100 ℃ from room temperature, at 100 ℃ of insulation 8min; Then be warming up to 150 ℃ from 100 ℃, at 150 ℃ of insulation 8min; Be warming up to 180 ℃, end reaction after 180 ℃ of insulation 40min from 150 ℃ again;
Step 6: question response is cooled to room temperature after finishing, and takes out the sediment in microwave hydrothermal reaction kettle, extremely neutral by deionized water and absolute ethanol washing sediment, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains Dy/BiVO
4photochemical catalyst.
Embodiment 4:
A kind of Dy/BiVO
4photochemical catalyst, its main component is BiVO
4, be cubic Zircon cut structure, and BiVO
4lattice in contain Dy
3+, wherein the mol ratio of Dy element and Bi element is 8.70:100.
A kind of Dy/BiVO
4the preparation method of photochemical catalyst comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o is dissolved in deionized water, stirs 20min on magnetic stirring apparatus, obtains Bi (NO
3)
35H
2the bismuth salting liquid that O concentration is 0.4mol/L; By NH
4vO
3be dissolved in the deionized water of 100 ℃, add thermal agitation 20min under 100 ℃, obtain NH
4vO
3the vanadic salts solution that concentration is 0.4mol/L;
Step 2: the mol ratio by Bi and V is that 1:1 slowly is added drop-wise to vanadic salts solution in the bismuth salting liquid, stirs 15min on magnetic stirring apparatus, obtains mixed liquor;
Step 3: take the rate of addition of 1mL/min to dripping the NaOH solution that concentration is 5mol/L in mixed liquor, the pH that regulates mixed liquor is 8, and stirs 25min on magnetic stirring apparatus;
Step 4: by Dy (NO
3)
36H
2o joins in the mixed liquor of having regulated after the pH value, stirs 20min on magnetic stirring apparatus, is mixed with precursor liquid, and wherein the mol ratio of Dy and Bi is 8.70:100;
Step 5: precursor liquid is added in microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 55%, then the microwave hydrothermal reaction kettle sealing is placed in the microwave hydrothermal synthesizer, select the microwave temperature controlling mode, setting pressure is 1.1MPa, under the microwave power of 300W, be warming up to 100 ℃ from room temperature, at 100 ℃ of insulation 8min; Then be warming up to 150 ℃ from 100 ℃, at 150 ℃ of insulation 8min; Be warming up to 180 ℃, end reaction after 180 ℃ of insulation 40min from 150 ℃ again;
Step 6: question response is cooled to room temperature after finishing, and takes out the sediment in microwave hydrothermal reaction kettle, extremely neutral by deionized water and absolute ethanol washing sediment, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains Dy/BiVO
4photochemical catalyst.
Embodiment 5:
A kind of Dy/BiVO
4photochemical catalyst, its main component is BiVO
4, be cubic Zircon cut structure, and BiVO
4lattice in contain Dy
3+, wherein the mol ratio of Dy element and Bi element is 11.11:100.
A kind of Dy/BiVO
4the preparation method of photochemical catalyst comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o is dissolved in deionized water, stirs 20min on magnetic stirring apparatus, obtains Bi (NO
3)
35H
2the bismuth salting liquid that O concentration is 0.4mol/L; By NH
4vO
3be dissolved in the deionized water of 100 ℃, add thermal agitation 20min under 98 ℃, obtain NH
4vO
3the vanadic salts solution that concentration is 0.4mol/L;
Step 2: the mol ratio by Bi and V is that 1:1 slowly is added drop-wise to vanadic salts solution in the bismuth salting liquid, stirs 15min on magnetic stirring apparatus, obtains mixed liquor;
Step 3: take the rate of addition of 0.3mL/min to dripping the NaOH solution that concentration is 5mol/L in mixed liquor, the pH that regulates mixed liquor is 8, and stirs 25min on magnetic stirring apparatus;
Step 4: by Dy (NO
3)
36H
2o joins in the mixed liquor of having regulated after the pH value, stirs 20min on magnetic stirring apparatus, is mixed with precursor liquid, and wherein the mol ratio of Dy and Bi is 11.11:100;
Step 5: precursor liquid is added in microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 55%, then the microwave hydrothermal reaction kettle sealing is placed in the microwave hydrothermal synthesizer, select the microwave temperature controlling mode, setting pressure is 1.1MPa, under the microwave power of 300W, be warming up to 100 ℃ from room temperature, at 100 ℃ of insulation 8min; Then be warming up to 150 ℃ from 100 ℃, at 150 ℃ of insulation 8min; Be warming up to 180 ℃, end reaction after 180 ℃ of insulation 40min from 150 ℃ again;
Step 6: question response is cooled to room temperature after finishing, and takes out the sediment in microwave hydrothermal reaction kettle, extremely neutral by deionized water and absolute ethanol washing sediment, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains Dy/BiVO
4photochemical catalyst.
Fig. 1 is the Dy/BiVO of embodiment 5 preparations
4the FE-SEM figure of photochemical catalyst, as can be seen from the figure its crystal morphology is short cylinder, and is of a size of the 50nm left and right in the minor axis direction, the powder size of visible preparation has reached nanoscale.
Embodiment 6:
A kind of Dy/BiVO
4photochemical catalyst, its main component is BiVO
4, be cubic Zircon cut structure, and BiVO
4lattice in contain Dy
3+, wherein the mol ratio of Dy element and Bi element is 13.64:100.
A kind of Dy/BiVO
4the preparation method of photochemical catalyst comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o is dissolved in deionized water, stirs 20min on magnetic stirring apparatus, obtains Bi (NO
3)
35H
2the bismuth salting liquid that O concentration is 0.4mol/L; By NH
4vO
3be dissolved in the deionized water of 100 ℃, add thermal agitation 20min under 96 ℃, obtain NH
4vO
3the vanadic salts solution that concentration is 0.4mol/L;
Step 2: the mol ratio by Bi and V is that 1:1 slowly is added drop-wise to vanadic salts solution in the bismuth salting liquid, stirs 15min on magnetic stirring apparatus, obtains mixed liquor;
Step 3: take the rate of addition of 0.4mL/min to dripping the NaOH solution that concentration is 5mol/L in mixed liquor, the pH that regulates mixed liquor is 8, and stirs 25min on magnetic stirring apparatus;
Step 4: by Dy (NO
3)
36H
2o joins in the mixed liquor of having regulated after the pH value, stirs 20min on magnetic stirring apparatus, is mixed with precursor liquid, and wherein the mol ratio of Dy and Bi is 13.64:100;
Step 5: precursor liquid is added in microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 55%, then the microwave hydrothermal reaction kettle sealing is placed in the microwave hydrothermal synthesizer, select the microwave temperature controlling mode, setting pressure is 1.1MPa, under the microwave power of 300W, be warming up to 100 ℃ from room temperature, at 100 ℃ of insulation 8min; Then be warming up to 150 ℃ from 100 ℃, at 150 ℃ of insulation 8min; Be warming up to 180 ℃, end reaction after 180 ℃ of insulation 40min from 150 ℃ again;
Step 6: question response is cooled to room temperature after finishing, and takes out the sediment in microwave hydrothermal reaction kettle, extremely neutral by deionized water and absolute ethanol washing sediment, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains Dy/BiVO
4photochemical catalyst.
Fig. 2 is different Dy
3+the Dy/BiVO prepared under addition
4the XRD collection of illustrative plates of photochemical catalyst, wherein a is not for adding the pure phase BiVO of Dy
4the XRD collection of illustrative plates, do not add the pure phase BiVO of Dy
4be according to preparation method of the present invention, do not add Dy (NO in step 4
3)
36H
2o obtains; B～g is respectively the Dy/BiVO of embodiment 1～embodiment 6 preparations
4the XRD collection of illustrative plates of photochemical catalyst.In Fig. 2, the intensity of ordinate is relative intensity, and the 2-Theta of abscissa is angle of diffraction.As can be seen from the figure, the pure phase BiVO that does not add Dy
4all diffraction maximums and PDF card (JCPDS NO.75-1866) coincide, and illustrate that its crystalline phase is monocline scheelite phase, add the Dy/BiVO after Dy
4all diffraction maximums of photochemical catalyst are all coincide with PDF card (JCPDS NO.14-0133), illustrate that its crystalline phase is all cubic zircon phase.
Fig. 3 is different Dy
3+the Dy/BiVO prepared under addition
4degradation rate-the time graph of the rhodamine B degradation of photochemical catalyst, the degradation curve that wherein RhB is rhodamine B self while not adding catalyst; A is not for adding the pure phase BiVO of Dy
4degradation curve, do not add the pure phase BiVO of Dy
4be according to preparation method of the present invention, do not add Dy (NO in step 4
3)
36H
2o obtains; B～g is respectively the Dy/BiVO of embodiment 1～embodiment 6 preparations
4the degradation curve of photochemical catalyst.The C/C of ordinate in Fig. 3
0for the concentration after certain rhodamine B degraded constantly and the ratio of its initial concentration.As can be seen from the figure, the Dy/BiVO prepared except embodiment 3
4the degradation effect of photochemical catalyst is lower than pure phase BiVO
4degradation effect, Dy/BiVO prepared by other embodiment
4the degradation effect of photochemical catalyst is all than pure phase BiVO
4good degrading effect, and the Dy/BiVO of embodiment 5 preparation
4photochemical catalyst degradation rate to rhodamine B under the irradiation of 120min reaches 94.40%, and pure phase BiVO
4degradation rate to rhodamine B after the irradiation of 120min is only 37.26%.The Dy/BiVO of visible embodiment 5 preparations
4photochemical catalyst is than pure monoclinic phase BiVO
4degradation rate after the 120min irradiation has improved 57.14%.Therefore the Tetragonal Er/BiVO that prepared by the present invention
4visible-light photocatalyst can be used in degradation of organic substances, and can be applied to environmental contaminants processing aspect.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification of the present invention, be claim of the present invention and contain.
Claims (10)
1. a Dy/BiVO
4photochemical catalyst is characterized in that: its main component is BiVO
4, be cubic Zircon cut structure, and BiVO
4lattice in contain Dy
3+, wherein the mol ratio of Dy element and Bi element is (2.04～13.64): 100.
2. Dy/BiVO according to claim 1
4photochemical catalyst is characterized in that: its pattern is short cylinder, is of a size of nanoscale.
3. a Dy/BiVO
4the preparation method of photochemical catalyst, is characterized in that, comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o is soluble in water, stirs, and obtains the bismuth salting liquid; By NH
4vO
3be dissolved in the water of 100 ℃, heating stirs, and obtains vanadic salts solution;
Step 2: the mol ratio by Bi and V is that 1:1 is added to vanadic salts solution in the bismuth salting liquid, stirs, and obtains mixed liquor;
Step 3: the pH value of regulating mixed liquor is 8, stirs;
Step 4: by Dy (NO
3)
36H
2o joins in the mixed liquor of having regulated after the pH value, stirs, and obtains precursor liquid, and wherein the mol ratio of Dy and Bi is (2.04～13.64): 100;
Step 5: precursor liquid is added in microwave hydrothermal reaction kettle, the microwave hydrothermal reaction kettle sealing is placed in microwave assisted hydrothermal synthesis apparatus, setting pressure is 1.1MPa, under the microwave power of 300W, from room temperature, is warming up to 100 ℃, at 100 ℃ of insulation 8min; Then be warming up to 150 ℃ from 100 ℃, at 150 ℃ of insulation 8min; Be warming up to 180 ℃, end reaction after 180 ℃ of insulation 40min from 150 ℃ again;
Step 6: question response is cooled to room temperature after finishing, and takes out the sediment in microwave hydrothermal reaction kettle, washing, and drying, obtain Dy/BiVO
4photochemical catalyst.
4. Dy/BiVO according to claim 3
4the preparation method of photochemical catalyst is characterized in that: Bi (NO in described bismuth salting liquid
3)
35H
2the concentration of O is 0.4mol/L; NH in vanadic salts solution
4vO
3concentration be 0.4mol/L.
5. according to the described Dy/BiVO of claim 3 or 4
4the preparation method of photochemical catalyst is characterized in that: in described step 1 by Bi (NO
3)
35H
2o stirring soluble in water 20min; By NH
4vO
3be dissolved in the water of 100 ℃ and add thermal agitation 20min under 90-100 ℃; Stirring in described step 2 is to stir 15min on magnetic stirring apparatus.
6. Dy/BiVO according to claim 3
4the preparation method of photochemical catalyst is characterized in that: the NaOH solution that is 5mol/L by concentration in described step 3 is regulated the pH value of mixed liquor, and the rate of addition of NaOH solution is less than or equal to 1mL/min.
7. according to the described Dy/BiVO of claim 3 or 6
4the preparation method of photochemical catalyst is characterized in that: stirring in described step 3 is to stir 25min on magnetic stirring apparatus; Stirring in described step 4 is to stir 20min on magnetic stirring apparatus.
8. Dy/BiVO according to claim 3
4the preparation method of photochemical catalyst is characterized in that: in described step 5, the packing ratio of microwave hydrothermal reaction kettle is 55%.
9. Dy/BiVO according to claim 3
4the preparation method of photochemical catalyst is characterized in that: the washing in described step 6 is extremely neutral by deionized water and absolute ethanol washing sediment; Described drying is at 75 ℃ of lower freeze-day with constant temperature 24h.
10. Dy/BiVO according to claim 1
4the application of photochemical catalyst aspect the environmental contaminants processing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148899A (en) * | 2015-09-29 | 2015-12-16 | 陕西科技大学 | Rare earth co-doped BiVO4 photocatalyst with upconversion characteristic and preparing method and application thereof |
| CN109569650A (en) * | 2018-11-14 | 2019-04-05 | 河北瑞克新能源科技有限公司 | One kind is for CO coupling catalyst for synthesizing oxalic ester and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249305A (en) * | 2011-05-24 | 2011-11-23 | 陕西科技大学 | Method for synthesizing monoclinic phase and tetragonal phase mixed high-catalytic-activity bismuth vanadate powder by microwave hydrothermal process |
| CN102641732A (en) * | 2012-04-17 | 2012-08-22 | 淮阴师范学院 | Multi-morphology rare earth doped BiVO4 composite photocatalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249305A (en) * | 2011-05-24 | 2011-11-23 | 陕西科技大学 | Method for synthesizing monoclinic phase and tetragonal phase mixed high-catalytic-activity bismuth vanadate powder by microwave hydrothermal process |
| CN102641732A (en) * | 2012-04-17 | 2012-08-22 | 淮阴师范学院 | Multi-morphology rare earth doped BiVO4 composite photocatalyst and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148899A (en) * | 2015-09-29 | 2015-12-16 | 陕西科技大学 | Rare earth co-doped BiVO4 photocatalyst with upconversion characteristic and preparing method and application thereof |
| CN105148899B (en) * | 2015-09-29 | 2017-12-22 | 陕西科技大学 | A kind of rare earth codope BiVO with upper transfer characteristic4Photochemical catalyst and its preparation method and application |
| CN109569650A (en) * | 2018-11-14 | 2019-04-05 | 河北瑞克新能源科技有限公司 | One kind is for CO coupling catalyst for synthesizing oxalic ester and preparation method thereof |
| CN109569650B (en) * | 2018-11-14 | 2021-11-23 | 河北瑞克新能源科技有限公司 | Catalyst for synthesizing oxalate through CO coupling and preparation method thereof |
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