CN103464137A - Multi-morphologic Ho/BiVO4 composite photocatalyst, and preparation method and application thereof - Google Patents

Multi-morphologic Ho/BiVO4 composite photocatalyst, and preparation method and application thereof Download PDF

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CN103464137A
CN103464137A CN2013103558744A CN201310355874A CN103464137A CN 103464137 A CN103464137 A CN 103464137A CN 2013103558744 A CN2013103558744 A CN 2013103558744A CN 201310355874 A CN201310355874 A CN 201310355874A CN 103464137 A CN103464137 A CN 103464137A
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bivo
catalyst
composite photo
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CN103464137B (en
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谈国强
罗洋洋
张丽丽
董国华
任慧君
夏傲
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Yancheng Aerospace Bag Industry Co.,Ltd.
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Shaanxi University of Science and Technology
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Abstract

The invention relates to a multi-morphologic Ho/BiVO4 composite photocatalyst, and a preparation method and an application thereof. The main component of the multi-morphologic Ho/BiVO4 composite photocatalyst is BiVO4, the BiVO4 has a tetragonal zircon phase structure, and the crystal lattice of the BiVO4 contains Ho<3+>. 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 according to a molar ratio of Bi to V of 1:1 to obtain a mixed solution, adjusting the pH value of the mixed solution to 8, adding holmium nitrate hexahydrate according to a molar ratio of Ho to Bi of (2.04-13.64):100, and maintaining the temperature at 180DEG C unchanged for 40min under a power of 300W by using a microwave hydrothermal method to prepare Ho/BiVO4. The preparation method has the advantages of uniform heating, fast heating speed, mild reaction condition, simple process flow, shortened reaction time and increased work efficiency, and the synthesized multi-morphologic Ho/BiVO4 composite photocatalyst has a high photocatalytic activity and can be used for degrading environmental pollutants.

Description

Multiform looks Ho/BiVO 4composite photo-catalyst and its preparation method and application
Technical field
The invention belongs to field of functional materials, be specifically related to a kind of multiform looks Ho/BiVO 4composite photo-catalyst and its preparation method and application.
Background technology
At present, facing mankind the energy and environment two large problems.Along with the exhaustion day by day of fossil energy and increasing the weight of of industrial production environmental pollution, find new clean energy resource and the thing of effectively curbing environmental pollution is the challenge of pendulum in face of the global scientist.Yet the employing photocatalytic method can effectively utilize solar energy and realize the process of photocatalytically degradating organic dye under temperate condition, at this, semiconductor light-catalyst is the core place of realizing this process.
BiVO 4be the more a kind of semiconductor light-catalyst material of Recent study, it has higher responding to visible light catalytic decomposition water and the ability of degradable organic pollutant.But due to BiVO 4the conduction band position lower than the reduction potential of hydrogen, can't reach the purpose that reductive water produces hydrogen, limited its application aspect photolysis water hydrogen; And BiVO 4the electronics and the hole that produced by optical excitation are easily compound, and photocatalysis performance still is subject to certain restrictions, so many scholars take up research to BiVO 4photocatalysis performance carry out modification, in order to improve the effect of its photocatalytic degradation pollutant, finally in real life production, be widely used.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 multiform looks Ho/BiVO 4composite photo-catalyst and its preparation method and application, the method combines the advantage of heating using microwave and the characteristics of hydro-thermal reaction, and the multiform looks Ho/BiVO of preparation 4composite photo-catalyst has higher photocatalytic activity.
For achieving the above object, the technical solution used in the present invention is:
Multiform looks Ho/BiVO 4composite photo-catalyst, its main component is BiVO 4, be cubic zircon phase structure, and BiVO 4lattice in contain Ho 3+, wherein the mol ratio of Ho element and Bi element is (2.04～13.64): 100.
Its pattern is spherical or irregular short cylinder and the little bulk formed by particle agglomeration.
Multiform looks Ho/BiVO 4the preparation method of composite photo-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 Ho (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 Ho 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 1.0MPa, 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 multiform looks Ho/BiVO 4composite photo-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.
Multiform looks Ho/BiVO 4the application of composite photo-catalyst aspect the photocatalytic degradation environmental contaminants.
With respect to prior art, beneficial effect of the present invention is:
Multiform looks Ho/BiVO provided by the invention 4the preparation method of composite photo-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 holmium nitrate (Ho (NO 3) 36H 2o) be the holmium source, prepare multiform looks Ho/BiVO 4the composite photo-catalyst powder.The present invention is by Ho 3+introduce BiVO 4lattice in, improved pure phase BiVO 4the efficiency of photocatalysis to degrade organic matter under visible ray.The present invention adopts microwave-hydrothermal method to synthesize multiform looks Ho/BiVO 4composite photo-catalyst, the method combines the advantage of heating using microwave and hydro-thermal method, can realize the stirring on molecular level, homogeneous heating, overcome the hydro-thermal container and heated inhomogeneous shortcoming, firing rate is fast, has shortened the reaction time, has improved operating efficiency, and reaction condition gentleness, technological process is simple, easy to operate, and manufacturing cycle is short.
Multiform looks Ho/BiVO provided by the invention 4composite photo-catalyst is cubic zircon phase structure, and its main component is BiVO 4, and BiVO 4lattice in contain Ho 3+, there is high photocatalytic activity, be mainly used in photocatalytic degradation environmental contaminants aspect, improved pure phase BiVO 4photocatalysis performance, reached pure phase BiVO 4carry out the purpose of modification, have a good application prospect.
Further, multiform looks Ho/BiVO provided by the invention 4the composite photo-catalyst particle size distribution is even, has different morphologies, and its pattern is spherical or irregular short cylinder and the little bulk formed by particle agglomeration.
The accompanying drawing explanation
Fig. 1 is the multiform looks Ho/BiVO of the embodiment of the present invention 2 preparations 4the FE-SEM figure of composite photo-catalyst;
Fig. 2 is the multiform looks Ho/BiVO of the embodiment of the present invention 3 preparations 4the FE-SEM figure of composite photo-catalyst;
Fig. 3 is the different Ho of the present invention 3+the multiform looks Ho/BiVO prepared under addition 4the XRD spectra of composite photo-catalyst, wherein a is not for adding the pure phase BiVO of Ho 4the XRD collection of illustrative plates, b～g is respectively the multiform looks Ho/BiVO of embodiment 1～embodiment 6 preparation 4the XRD spectra of composite photo-catalyst;
Fig. 4 is the different Ho of the present invention 3+the multiform looks Ho/BiVO prepared under addition 4degradation rate-the time graph of the rhodamine B degradation of composite photo-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 Ho 4degradation curve, b～g is respectively the multiform looks Ho/BiVO of embodiment 1～embodiment 6 preparation 4the degradation curve of composite photo-catalyst.
The specific embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is described in further detail.
Embodiment 1:
Multiform looks Ho/BiVO 4composite photo-catalyst, its main component is BiVO 4, be cubic zircon phase structure, and BiVO 4lattice in contain Ho 3+, wherein the mol ratio of Ho element and Bi element is 2.04:100.
Multiform looks Ho/BiVO 4the preparation method of composite photo-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 Ho (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 Ho 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 1.0MPa, 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, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains multiform looks Ho/BiVO 4composite photo-catalyst.
Embodiment 2:
Multiform looks Ho/BiVO 4composite photo-catalyst, its main component is BiVO 4, be cubic zircon phase structure, and BiVO 4lattice in contain Ho 3+, wherein the mol ratio of Ho element and Bi element is 4.17:100.
Multiform looks Ho/BiVO 4the preparation method of composite photo-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 Ho (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 Ho 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 1.0MPa, 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, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains multiform looks Ho/BiVO 4composite photo-catalyst.
Fig. 1 is the multiform looks Ho/BiVO of the embodiment of the present invention 2 preparations 4the FE-SEM figure of composite photo-catalyst.From figure, can find out, its pattern is that a large amount of granule reunions has formed large ball together, and specific area reduces greatly, and this is the multiform looks Ho/BiVO that causes embodiment 2 preparations 4one of major reason of composite photocatalyst for degrading weak effect.
Embodiment 3:
Multiform looks Ho/BiVO 4composite photo-catalyst, its main component is BiVO 4, be cubic zircon phase structure, and BiVO 4lattice in contain Ho 3+, wherein the mol ratio of Ho element and Bi element is 6.38:100.
Multiform looks Ho/BiVO 4the preparation method of composite photo-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 Ho (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 Ho 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 1.0MPa, 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, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains multiform looks Ho/BiVO 4composite photo-catalyst.
Fig. 2 is the multiform looks Ho/BiVO of embodiment 3 preparations 4the FE-SEM figure of composite photo-catalyst, as can be seen from the figure, its crystal morphology is irregular short cylinder and little bulk.
Embodiment 4:
Multiform looks Ho/BiVO 4composite photo-catalyst, its main component is BiVO 4, be cubic zircon phase structure, and BiVO 4lattice in contain Ho 3+, wherein the mol ratio of Ho element and Bi element is 8.70:100.
Multiform looks Ho/BiVO 4the preparation method of composite photo-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 Ho (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 Ho 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 1.0MPa, 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, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains multiform looks Ho/BiVO 4composite photo-catalyst.
Embodiment 5:
Multiform looks Ho/BiVO 4composite photo-catalyst, its main component is BiVO 4, be cubic zircon phase structure, and BiVO 4lattice in contain Ho 3+, wherein the mol ratio of Ho element and Bi element is 11.11:100.
Multiform looks Ho/BiVO 4the preparation method of composite photo-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 Ho (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 Ho 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 1.0MPa, 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, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains multiform looks Ho/BiVO 4composite photo-catalyst.
Embodiment 6:
Multiform looks Ho/BiVO 4composite photo-catalyst, its main component is BiVO 4, be cubic zircon phase structure, and BiVO 4lattice in contain Ho 3+, wherein the mol ratio of Ho element and Bi element is 13.64:100.
Multiform looks Ho/BiVO 4the preparation method of composite photo-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 Ho (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 Ho 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 1.0MPa, 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, then, at 75 ℃ of lower freeze-day with constant temperature 24h, obtains multiform looks Ho/BiVO 4composite photo-catalyst.
Fig. 3 is different Ho 3+the multiform looks Ho/BiVO prepared under addition 4the XRD collection of illustrative plates of composite photo-catalyst, wherein a is not for adding the pure phase BiVO of Ho 4the XRD collection of illustrative plates, do not add the pure phase BiVO of Ho 4be according to preparation method of the present invention, do not add Ho (NO in step 4 3) 36H 2o obtains; B～g is respectively the multiform looks Ho/BiVO of embodiment 1～embodiment 6 preparations 4the XRD collection of illustrative plates of composite photo-catalyst.In Fig. 3, 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 Ho 4all diffraction maximums and PDF card (JCPDS NO.75-1866) coincide, and illustrate that its crystalline phase is monocline scheelite phase, add the multiform looks Ho/BiVO after Ho 4all diffraction maximums of composite photo-catalyst are all coincide with PDF card (JCPDS NO.14-0133), illustrate that its crystalline phase is all cubic zircon phase.
Fig. 4 is different Ho 3+the multiform looks Ho/BiVO prepared under addition 4degradation rate-the time graph of the rhodamine B degradation of composite photo-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 Ho 4degradation curve, do not add the pure phase BiVO of Ho 4be according to preparation method of the present invention, do not add Ho (NO in step 4 3) 36H 2o obtains; B～g is respectively the multiform looks Ho/BiVO of embodiment 1～embodiment 6 preparations 4the degradation curve of composite photo-catalyst.The C/C of ordinate in Fig. 4 0for the concentration after certain rhodamine B degraded constantly and the ratio of its initial concentration.The multiform looks Ho/BiVO as can be seen from the figure prepared according to embodiment 1, embodiment 2 and embodiment 4 4the degradation effect of composite photo-catalyst is all lower than the pure phase BiVO that does not add Ho 4degradation effect, multiform looks Ho/BiVO prepared by other embodiment 4the degradation effect of composite photo-catalyst is all than pure phase BiVO 4good degrading effect, and the multiform looks Ho/BiVO of embodiment 3 preparation 4composite photo-catalyst degradation rate to rhodamine B under the irradiation of 120min reaches 96.78%, does not add the pure phase BiVO of Ho 4degradation rate to rhodamine B after the irradiation of 120min is only 37.26%.The multiform looks Ho/BiVO of embodiment 3 preparations 4composite photo-catalyst is than pure phase BiVO 4degradation rate after the 120min irradiation has improved 59.52%.Therefore the multiform looks Ho/BiVO that prepared by the present invention 4composite photo-catalyst can be used in degradation of organic substances, and can be applied to photocatalytic degradation environmental contaminants 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. multiform looks Ho/BiVO 4composite photo-catalyst is characterized in that: its main component is BiVO 4, be cubic zircon phase structure, and BiVO 4lattice in contain Ho 3+, wherein the mol ratio of Ho element and Bi element is (2.04～13.64): 100.
2. multiform looks Ho/BiVO according to claim 1 4composite photo-catalyst is characterized in that: spherical or irregular short cylinder and the little bulk of its pattern for being formed by particle agglomeration.
3. multiform looks Ho/BiVO 4the preparation method of composite photo-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 Ho (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 Ho 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 1.0MPa, 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 multiform looks Ho/BiVO 4composite photo-catalyst.
4. multiform looks Ho/BiVO according to claim 3 4the preparation method of composite photo-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 multiform looks of claim 3 or 4 Ho/BiVO 4the preparation method of composite photo-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. multiform looks Ho/BiVO according to claim 3 4the preparation method of composite photo-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 multiform looks of claim 3 or 6 Ho/BiVO 4the preparation method of composite photo-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. multiform looks Ho/BiVO according to claim 3 4the preparation method of composite photo-catalyst is characterized in that: in described step 5, the packing ratio of microwave hydrothermal reaction kettle is 55%.
9. multiform looks Ho/BiVO according to claim 3 4the preparation method of composite photo-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. multiform looks Ho/BiVO according to claim 1 4the application of composite photo-catalyst aspect the photocatalytic degradation environmental contaminants.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104001496A (en) * 2014-06-11 2014-08-27 福州大学 BiVO4 nanosheet composite photocatalyst, and preparation method and application thereof
CN104445400A (en) * 2014-11-28 2015-03-25 陕西科技大学 Non-stoichiometric broom-like bismuth vanadate fiber and preparation method thereof
CN104437554A (en) * 2014-12-05 2015-03-25 武汉理工大学 Sheet-shaped WS2-supported BiVO4 visible light catalytic material and preparation method thereof
CN106379934A (en) * 2016-11-23 2017-02-08 湖州师范学院 Method for preparing Ho2TiO5 powder

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004024936A (en) * 2002-06-21 2004-01-29 Japan Science & Technology Corp New synthetic method for fine powder of visible light-responsive bismuth vanadate, photocatalyst of fine powder of new visible light-responsive bismuth vanadate and cleaning method using the same
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004024936A (en) * 2002-06-21 2004-01-29 Japan Science & Technology Corp New synthetic method for fine powder of visible light-responsive bismuth vanadate, photocatalyst of fine powder of new visible light-responsive bismuth vanadate and cleaning method using the same
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUI XU等: "Preparation，Characterization and Photocatalytic Activities of Lanthanide Oxide-loaded BiVO4 Catalysts", 《18TH INTERNATIONAL SYMPOSIUM ON FINE CHEMISTRY AND FUNCTIONAL POLYMERS (FCFP-XVIII) & IUPAC 4TH INTERNATIONAL SYMPOSIUM ON NOVEL MATERIALS AND SYNTHESIS (NMS-IV)》, 26 April 2010 (2010-04-26) *
许晖: "可见光响应型钒酸盐系列光催化材料的合成及其性能研究", 《万方学位论文》, 22 December 2010 (2010-12-22) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104001496A (en) * 2014-06-11 2014-08-27 福州大学 BiVO4 nanosheet composite photocatalyst, and preparation method and application thereof
CN104001496B (en) * 2014-06-11 2015-12-02 福州大学 A kind of BiVO 4nanometer sheet composite photocatalyst and its preparation method and application
CN104445400A (en) * 2014-11-28 2015-03-25 陕西科技大学 Non-stoichiometric broom-like bismuth vanadate fiber and preparation method thereof
CN104445400B (en) * 2014-11-28 2016-06-15 陕西科技大学 A kind of non-stoichiometric broom shape pucherite fiber and preparation method thereof
CN104437554A (en) * 2014-12-05 2015-03-25 武汉理工大学 Sheet-shaped WS2-supported BiVO4 visible light catalytic material and preparation method thereof
CN104437554B (en) * 2014-12-05 2016-08-17 武汉理工大学 Lamellar WS2load BiVO4visible light catalytic material and preparation method thereof
CN106379934A (en) * 2016-11-23 2017-02-08 湖州师范学院 Method for preparing Ho2TiO5 powder

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