CN102989485B - S-doped BiVO4 visible light catalytic material and preparation method thereof - Google Patents

S-doped BiVO4 visible light catalytic material and preparation method thereof Download PDF

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CN102989485B
CN102989485B CN201210569641.XA CN201210569641A CN102989485B CN 102989485 B CN102989485 B CN 102989485B CN 201210569641 A CN201210569641 A CN 201210569641A CN 102989485 B CN102989485 B CN 102989485B
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visible light
precursor solution
solution
light catalytic
bivo
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CN102989485A (en
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王为民
张琳琅
傅正义
王皓
王玉成
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Wuhan University of Technology WUT
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Abstract

The invention relates to an S-doped BiVO4 visible light catalytic material and a preparation method of the S-doped BiVO4 visible light catalytic material. The preparation method comprises the following steps of: (1) precursor solution preparation: to be specific, respectively dissolving Bi(NO3) 3.5H2O and NH4VO3 in a right amount of acetic acid solution and deionized water, wherein the molar ratio of Bi(NO3) 3.5H2O to NH4VO3 is 1:1, and respectively mixing uniformly to obtain precursor solutions A and B, wherein a certain amount of thiourea and an emulsifier are added to the precursor solution B; (2) fully stirring the precursor solutions A and B, and mixing uniformly; (3) placing a uniformly mixed solution in a hyrothermal reaction kettle, preserving temperature for a period of time at a certain temperature; and (4) obtaining the S-doped BiVO4 visible light catalytic material after carrying out centrifugal washing and freeze drying on a reaction product in the reaction kettle. The preparation method is simple in technology and low in cost. The S-doped BiVO4 visible light catalytic material prepared by the method has an obvious degradation effect on a methylene blue solution.

Description

A kind of S doping BiVO 4visible light catalytic material and preparation method thereof
Technical field
The present invention relates to a kind of S element doping BiVO 4visible light catalytic dusty material and preparation method thereof, belongs to photocatalysis powder field of material preparation.
Background technology
21 century, the greatest problem of facing mankind was still the sustainable development of problem of environmental pollution and the energy.The exploitation of solar energy becomes the key of dealing with problems for this reason, and is expected to become as the Photocatalitic Technique of Semiconductor of pith wherein the effective means that solves environment and energy problem.
Semi-conducting material is chemical energy light energy conversion under the irradiation of light, promotes the synthetic of compound or makes degradation.Semiconductor catalyst has precipitous absorption edge in visible region, the narrow band gap that they have is conducive on electronics is from valence to conduction band, produces conduction band electron and valence band hole, carries out redox degradable organic pollutant or decomposition water and obtains Hydrogen Energy.And Hydrogen Energy becomes the clean energy resource that is hopeful to substitute existing fossil energy most because its fuel value is high, pollution-free.Photocatalysis simultaneously can be degraded and be eliminated toxic organic pollutant and inorganic pollution, do not produce secondary pollution, and it is low to have energy consumption, and speed is fast, non-selectivity, and the advantages such as deep oxidation mineralising, will become an approach that cheapness is feasible that solves environmental pollution.
Because some semiconductor light-catalysts are as TiO 2, NaTaO 3, the greater band gap such as ZnO, only there is response in ultraviolet light range, and the light energy of this wave band account for be irradiated to ground sunshine 5%, and wavelength reaches 43% of gross energy at the visible-range of 400 ~ 700nm, therefore the research of high-efficient visible-light photocatalyst is the key that realizes photocatalysis technology commercial application.At present, the research of novel visible photochemical catalyst has two large thinkings at present: one is to TiO 2, NaTaO 3, the means such as the wide bandgap semiconductor such as ZnO carries out modification makes its response wave length red shift to visible region, mainly contains metal/non-metal doping, the compound and metal complex sensitization of dye photoactivation, narrow gap semiconductor; Another kind is the novel visible light-responded conductor photocatalysis material of design, and wherein low-gap semiconductor preparation is to obtain one of Basic Ways of novel visible catalyst.Therefore, research worker has designed many composite metal oxides as visible light-responded novel photocatalyst, as Bi 2wO 6, InVO 4, AgAlO 2, CaIn 2o 4, BiVO 4deng, they all can be under the irradiation of visible ray catalytic decomposition organic matter.BiVO 4stable in properties, can resistance to strong acid and highly basic medium after surface stabilization is processed, and it has the performance of excellent organic solvent-resistant simultaneously, and BiVO 4response light wave-length coverage can reach 500 nm more than.Visual efficiency is high, catalytic decomposition organic matter ability is subject to extensive concern by force because it utilizes for this series material, is mainly used in photocatalysis Decomposition waste water and the polynary ring organic pollution of degraded.
BiVO 4have the ability of visible light catalytic decomposition water and degradable organic pollutant, its response light wave-length coverage reaches on 500nm, is showing good visible light photocatalytic degradation performance as catalysis material aspect wastewater treatment.BiVO 4visible light catalysis activity depend primarily on its crystal phase structure and preparation method.BiVO 4three kinds of structure monocline scheelite crystal formations, cubic Zircon cut crystal formation and cubic scheelite type crystal formations in only have monocline scheelite crystal formation under visible ray, to there is good photocatalysis performance, but under certain condition, three kinds of structures can transform each other mutually.BiVO 4its preparation method mainly contain: Hydrothermal Synthesis is sent out, solvent heat synthetic method, microwave process for synthesizing, high temperature solid phase synthesis and chemical precipitation method etc., and said method respectively has pluses and minuses, but can synthesize the BiVO that purity is higher 4powder body material, but numerous researchers find in experiment, pure BiVO 4catalytic effect can not meet growing industrial technology index request.In view of pure BiVO 4adsorption capacity and the transfer ability of electron-hole pair poor, many scholars begin one's study by modification, or prepare metal oxide and BiVO 4the hetero-junctions of pairing improves its activity, wherein for nanometer BiVO 4the ion doping of material is BiVO 4the research emphasis of modification.At BiVO 4in mix external ions may be at BiVO 4in lattice, introduce defective locations or change degree of crystallinity, thereby at BiVO 4band gap energy level in introduce defect level and impurity energy level, make the photon excitation BiVO that energy is less 4produce photoelectron, thereby change semi-conductive excitation wavelength.In addition, doping can cause the diffusion length of carrier to increase, and when doping valence state is during higher than the valence state of metal ion, thereby the trapping centre that can generate in part light induced electron suppresses the compound of light induced electron and hole, raising BiVO 4photocatalytic activity.Xu etc. have prepared the BiVO of series of rare earth (Ho, Sm, Yb, Eu, Gd, Nd, Ce, La) doping 4photochemical catalyst, and process methylene blue under visible ray.Experiment shows, the BiVO after doping 4photocatalysis performance is significantly improved compared with original material.
Can be found out synthesis of high purity BiVO by above-mentioned analysis 4powder the utilization rate that it is carried out to ion doping and can significantly improve its catalytic activity and catalyst, make BiVO 4in the light grown by wavelength of electronic energy excite, and have not yet to see the BiVO about S ion doping 4the research report of visible light catalytic material.
Summary of the invention
Technical problem to be solved by this invention is to provide one to prepare S doping BiVO for the deficiency of above-mentioned prior art existence 4the method of visible light catalytic material, the S doping BiVO that the method obtains 4the photocatalysis performance of visible light catalytic material improves, and light degradation speed is accelerated.
The present invention for the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
A kind of S doping BiVO 4visible light catalytic material, it prepares in accordance with the following steps:
1) preparation of precursor solution: by Bi (NO 3) 35H 2o fully dissolves in acetum and obtains precursor solution A, by NH 4vO 3fully dissolve in deionized water, and add thiocarbamide and emulsifying agent, thiocarbamide and NH 4vO 3mol ratio be (4.8 ~ 5.2): 1, under room temperature, mix and obtain precursor solution B, meet Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, the volume of precursor solution A, B equates, the mass fraction of emulsifying agent in precursor solution B is 2.8 ~ 3.1 wt%;
2) precursor solution A is added dropwise in precursor solution B, stirs 1.5 ~ 3h it is fully mixed, now the pH of mixed solution is 1.3 ~ 1.7;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle and heat-treats, and heat treatment temperature is 130 DEG C～150 DEG C, and temperature retention time is 13h～17h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, by the washing of product powder centrifugation, then the product powder of centrifugation is carried out to freeze drying at-100～-80 DEG C, be 24～48h drying time, obtains S doping BiVO 4visible light catalytic powder body material.
Press such scheme, the volume fraction of described acetum is 36wt%.
Press such scheme, described emulsifying agent is OP-10.
Press such scheme, the heat treatment described in step 3) adopts resistance furnace, tube furnace, vacuum atmosphere oven etc. that the heating furnace of steady temperature field can be provided.
Press such scheme, wash described in step 4) centrifugally by centrifugal the washing of product powder deionized water, then use absolute ethanol washing centrifugal.
Press such scheme, the solvent medium of the centrifugal employing of washing described in step 4) can also be the organic solvents such as methyl alcohol, isopropyl alcohol or toluene.
Press such scheme, centrifugal employing rotating speed is 4500 ~ 6000r/min described in step 4), and centrifugation time is 3 ~ 5min.
Press such scheme, freeze drying is-90 DEG C of dry 24 ~ 48h described in step 4).
Above-mentioned S doping BiVO 4the preparation method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: by Bi (NO 3) 35H 2o fully dissolves in acetum and obtains precursor solution A, by NH 4vO 3fully dissolve in deionized water, and add thiocarbamide and emulsifying agent, thiocarbamide and NH 4vO 3mol ratio be (4.8 ~ 5.2): 1, under room temperature, fully mix and obtain precursor solution B, meet Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, the volume of precursor solution A, B equates, the mass fraction of emulsifying agent in precursor solution B is 2.8 ~ 3.1 wt%;
2) precursor solution A is added dropwise in precursor solution B, stirs 1.5 ~ 3h it is fully mixed, the pH of mixed solution is 1.3 ~ 1.7;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle and heat-treats, and heat treatment temperature is 130 DEG C～150 DEG C, and temperature retention time is 13h～17h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, by the washing of product powder centrifugation, then the product powder of centrifugation is carried out to freeze drying at-80～-100 DEG C, be 24～48h drying time, obtains S doping BiVO 4visible light catalytic powder body material.
Compared with prior art, the present invention has the following advantages:
1, BiVO 4a kind of comparatively ideal catalysis material, but pure BiVO 4limited it and further applied because the transfer ability of adsorption capacity and electron-hole pair is poor, the present invention adopts hydro-thermal reaction method to prepare highly purified S doping BiVO 4visible light catalytic material, this method prepares that speed is fast, efficiency is high, reaction transforms completely.
2, with pure BiVO 4compare the S doping BiVO that the present invention prepares 4visible light catalytic material energy gap diminishes.
3, the S doping BiVO that the present invention prepares 4visible light catalytic material has obvious degraded to the degraded of dyestuff, under radiation of visible light, the degradation rate of 20 minutes methyl blue solution can reach 59.7%, 100 minute can degrade 97%, can be widely used in the fields such as trade effluent processing, textile dyestuff degraded and conductor photocatalysis.
4, preparation technology of the present invention is simple, workable, and preparation cost is low, can prepare rapidly the S doping BiVO that meets instructions for use 4visible light catalytic material, the heat-treatment furnace that hydro-thermal reaction adopts has very large generality, is applicable to laboratory and industrial production.
Brief description of the drawings
Fig. 1 is the pure BiVO making in the embodiment of the present invention 1 4the SEM photo of visible light catalytic material.
Fig. 2 is the S doping BiVO making in the embodiment of the present invention 2 4the FESEM photo of visible light catalytic material.
Fig. 3 is the S doping BiVO making in the embodiment of the present invention 2 4the TEM photo of visible light catalytic material.
Fig. 4 is the S doping BiVO making in the embodiment of the present invention 3 4the XRD collection of illustrative plates of visible light catalytic material.
Fig. 5 is the S doping BiVO making in the embodiment of the present invention 4 4the XPS analysis collection of illustrative plates of visible light catalytic material.
Fig. 6 is prepared S doping BiVO in the embodiment of the present invention 1 and embodiment 5～7 4the photocatalytic speed figure (abscissa is the time, and ordinate is concentration ratio, i.e. the ratio of instantaneous concentration and initial concentration) of visible light catalytic material.
Detailed description of the invention
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with accompanying drawing, embodiment, but content of the present invention is not only confined to the following examples.
this embodiment of embodiment 1(is comparison example, does not add emulsion OP-10 and thiocarbamide):
One is prepared pure BiVO 4the method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: press Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, take material powder, by 5mmol Bi (NO 3) 35H 2o fully dissolves in 25ml acetum and obtains precursor solution A, by 5mmol NH 4vO 3fully dissolve in 25ml deionized water, under room temperature, fully mix and obtain precursor solution B;
2) precursor solution A is added dropwise in precursor solution B gradually, adopts magnetic agitation 2h under room temperature, it is fully mixed, now mixed solution pH is 1.4;
3) 3) by step 2) described mixed solution puts into hydrothermal reaction kettle, is placed in high temperature resistance furnace and heat-treats, and heat treatment temperature is 140 DEG C, and temperature retention time is 15h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, product powder is mixed with deionized water, carry out centrifuge washing 4 times, then product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 5 times, centrifuge speed is 4500r/min, each centrifugation time is 5min, obtains the product powder after cleaning; Product powder is inserted in freeze drier and at-80 DEG C, carry out freeze drying again, be 24h drying time, after being dried, obtains pure BiVO 4visible light catalytic powder body material, is labeled as BiVO 4 - 1.
Prepared pure BiVO as can be seen from Figure 1 4visible light catalytic powder body material is octahedral terrace with edge, and particle surface is smooth, and particle size is larger, is probably 2-3 μ m; Its specific area is 0.17m by BET determination of adsorption method 2/ g; To in methylene blue dye solution 20 minutes substantially without degraded, see Fig. 6; Degradation condition is the concentration 1 × 10 of methyl blue -5mol/L, volume is 100mL, and visible light catalytic powder body material dosage is 0.1g, and the light source of employing is 350W xenon lamp, and other embodiment degradation conditions are identical therewith.
embodiment 2:
One is prepared S doping BiVO 4the method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: press Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, take material powder, by 5mmol Bi (NO 3) 35H 2o fully dissolves in 25ml acetum and obtains precursor solution A, by 5mmol NH 4vO 3fully dissolve in 25ml deionized water, and add thiocarbamide and emulsifier op-10, wherein thiocarbamide and NH 4vO 3mol ratio be 4.8:1, under room temperature, fully mix and obtain precursor solution B, the mass fraction of emulsifying agent in precursor solution B is 2.9wt%;
2) precursor solution A is added dropwise in precursor solution B gradually, adopts magnetic agitation 2h under room temperature, it is fully mixed, now mixed solution pH is 1.5;
3) 3) by step 2) described mixed solution puts into hydrothermal reaction kettle, is placed in high temperature resistance furnace and heat-treats, and heat treatment temperature is 130 DEG C, and temperature retention time is 14h, then cooling with stove, obtains reaction product solution C;
3) reaction product solution C is carried out to centrifugation, obtain product powder, product powder is mixed with deionized water, carry out centrifuge washing 3 times, then product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 4 times, centrifuge speed is 5000r/min, each centrifugation time is 5min, obtains the product powder after cleaning; Product powder is inserted in freeze drier and at-80 DEG C, carry out freeze drying again, be 48h drying time, obtains S doping BiVO after being dried 4visible light catalytic powder body material.
As can be seen from Figure 2, gained S doping BiVO 4the whole pattern of visible light catalytic powder body material presents dumbbell shaped, is the BiVO tiny by particle 4assemble this dumbbell shaped BiVO 4formation be crystal nucleation with these two process actings in conjunction of growth after the result that forms; This material mainly exists with the morphology of the aggregate loosening as seen from Figure 3, is mainly deposited in together and is formed by some polyhedral nano particles, and nano particle diameter is about 50nm.
Measure S doping BiVO 4the specific area of visible light catalytic powder body material is: 13.05m 2/ g, can degrade 50.42% in 20 minutes to methylene blue dye solution.
embodiment 3:
One is prepared S doping BiVO 4the method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: press Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, take material powder, by 5mmol Bi (NO 3) 35H 2o fully dissolves in 25ml acetum and obtains precursor solution A, by 5mmol NH 4vO 3fully dissolve in 25ml deionized water, and add thiocarbamide and emulsifier op-10, wherein, thiocarbamide and NH 4vO 3mol ratio be 5:1, under room temperature, fully mix and obtain precursor solution B, the mass fraction of emulsifying agent in precursor solution B is 2.8wt%;
2) precursor solution A is added dropwise in precursor solution B gradually, adopts magnetic agitation 1.5h under room temperature, it is fully mixed, now mixed solution pH is 1.6;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle, is placed in high temperature resistance furnace and heat-treats, and heat treatment temperature is 150 DEG C, and temperature retention time is 16h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, product powder is mixed with deionized water, carry out centrifuge washing 4 times, then product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 4 times, centrifuge speed is 6000r/min, each centrifugation time is 3min, obtains the product powder after cleaning; Product powder is inserted in freeze drier and at-90 DEG C, carry out freeze drying again, be 24h drying time, obtains S doping BiVO after being dried 4visible light catalytic powder body material.
As can be seen from Figure 4, gained S doping BiVO 4visible light catalytic powder body material is the BiVO of pure monoclinic form 4, adding of S do not affect BiVO 4structure; In this material, the combination of Bi4f7/2 can be 159.1eV as can be known from Fig. 5,164.5eV, and the combination of Bi4f5/2 can be 164.5eV, and the combination of S2p3/2 can be 163.6eV, and this is respectively Bi 3+and S 2-corresponding spectrum peak, illustrates that S element is successfully doped to BiVO 4in, products therefrom is S doping BiVO really 4visible light catalytic powder body material.
Measure S doping BiVO 4the specific area of visible light catalytic powder body material is: 12.97m 2/ g, can degrade 47.31% in 20 minutes to methylene blue dye solution.
embodiment 4:
One is prepared S doping BiVO 4the method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: press Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, take material powder, by 5mmol Bi (NO 3) 35H 2o fully dissolves in 25ml acetum and obtains precursor solution A, by 5mmol NH 4vO 3fully dissolve in 25ml deionized water, and add, thiocarbamide and emulsifier op-10, wherein thiocarbamide and NH 4vO 3mol ratio be 5.2:1, under room temperature, fully mix and obtain precursor solution B, the mass fraction of emulsifying agent in precursor solution B is 2.9wt%;
2) precursor solution A is added dropwise in precursor solution B gradually, adopts magnetic agitation 3h under room temperature, it is fully mixed, now mixed solution pH is 1.3;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle, is placed in high temperature resistance furnace and heat-treats, and heat treatment temperature is 150 DEG C, and temperature retention time is 15h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, product powder is mixed with deionized water, carry out time centrifuge washing, then product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 3 times, centrifuge speed is 4500r/min, each centrifugation time is 5min, obtains the product powder after cleaning; Product powder is inserted in freeze drier and at-90 DEG C, carry out freeze drying again, be 48h drying time, obtains S doping BiVO after being dried 4visible light catalytic powder body material.
Measure S doping BiVO 4the specific area of visible light catalytic powder body material is: 13.77m 2/ g, can degrade 52.8% in 20 minutes to methylene blue dye solution.
embodiment 5:
One is prepared S doping BiVO 4the method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: press Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, take material powder, by 5mmol Bi (NO 3) 35H 2o fully dissolves in 25ml acetum and obtains precursor solution A, by 5mmol NH 4vO 3fully dissolve in 25ml deionized water, and add a certain amount of thiocarbamide and emulsifier op-10, wherein thiocarbamide and NH 4vO 3mol ratio be 5:1, under room temperature, fully mix and obtain precursor solution B, the mass fraction of emulsifying agent in precursor solution B is 3wt%;
2) precursor solution A is added dropwise in precursor solution B gradually, adopts magnetic agitation 2h under room temperature, it is fully mixed, now mixed solution pH is;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle, is placed in high temperature resistance furnace and heat-treats, and heat treatment temperature is 140 DEG C, and temperature retention time is 15h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, product powder is mixed with deionized water, carry out centrifuge washing 3 times, then product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 5 times, centrifuge speed is 5500r/min, each centrifugation time is 5min, obtains the product powder after cleaning; Product powder is inserted in freeze drier and at-90 DEG C, carry out freeze drying again, be 24h drying time, obtains S doping BiVO after being dried 4visible light catalytic powder body material, is labeled as BiVO 4 - 5.
Measure S doping BiVO 4the specific area of visible light catalytic powder body material is: 14.1m 2/ g, can degrade 59.7% in 20 minutes to methylene blue dye solution, sees Fig. 6.
embodiment 6:
One is prepared S doping BiVO 4the method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: press Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, take material powder, by 5mmol Bi (NO 3) 35H 2o fully dissolves in 25ml acetum and obtains precursor solution A, by 5mmol NH 4vO 3fully dissolve in 25ml deionized water, and add a certain amount of thiocarbamide and emulsifier op-10, wherein urea and NH 4vO 3mol ratio be 5.8:1, under room temperature, fully mix and obtain precursor solution B, the mass fraction of emulsifying agent in precursor solution B is 3.1wt%;
2) precursor solution A is added dropwise in precursor solution B gradually, adopts magnetic agitation 2h under room temperature, it is fully mixed, now mixed solution pH is;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle, is placed in high temperature resistance furnace and heat-treats, and heat treatment temperature is 170 DEG C, and temperature retention time is 15h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, product powder is mixed with deionized water, carry out centrifuge washing 3 ~ 5 times, then product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 3 ~ 5 times, centrifuge speed is 4500r/min, each centrifugation time is 5min, obtains the product powder after cleaning; Product powder is inserted in freeze drier and at-90 DEG C, carry out freeze drying again, be 24h drying time, obtains S doping BiVO after being dried 4visible light catalytic powder body material, is labeled as BiVO 4 - 6.
Measure S doping BiVO 4the specific area of visible light catalytic powder body material is: 10.01m 2/ g, can degrade 23.8% in 20 minutes to methylene blue dye solution, sees Fig. 6.
embodiment 7:
One is prepared S doping BiVO 4the method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: press Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, take material powder, by 5mmol Bi (NO 3) 35H 2o fully dissolves in 25ml acetum and obtains precursor solution A, by 5mmol NH 4vO 3fully dissolve in 25ml deionized water, and add a certain amount of thiocarbamide and emulsifier op-10, wherein thiocarbamide and NH 4vO 3mol ratio be 4.5:1, under room temperature, fully mix and obtain precursor solution B, the mass fraction of emulsifying agent in precursor solution B is 3wt%;
2) precursor solution A is added dropwise in precursor solution B gradually, adopts magnetic agitation 2h under room temperature, it is fully mixed, now mixed solution pH is;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle, is placed in high temperature resistance furnace and heat-treats, and heat treatment temperature is 110 DEG C, and temperature retention time is 15h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, product powder is mixed with deionized water, carry out centrifuge washing 3 times, then product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 3 times, centrifuge speed is 5000r/min, each centrifugation time is 5min, obtains the product powder after cleaning; Product powder is inserted in freeze drier and at-100 DEG C, carry out freeze drying again, be 48h drying time, obtains S doping BiVO after being dried 4visible light catalytic powder body material, is labeled as BiVO 4 - 7.
Measure S doping BiVO 4the specific area of visible light catalytic powder body material is 7.13m 2/ g, can degrade 17.35% in 20 minutes to methylene blue dye solution, sees Fig. 6.
As can be seen from Figure 6, pure BiVO 4visible light catalytic powder body material to MBD solution substantially without degraded, the S BiVO that adulterates 4visible light catalytic powder body material has degraded to a certain degree to MBD solution, as S doping BiVO 4the Hydrothermal Synthesis temperature of visible light catalytic powder body material is 140 DEG C, and temperature retention time is 15h(embodiment 5), it is 97% that 20min can reach 59.7%, 100min degradation rate to the degraded of MBD solution.

Claims (6)

1. a S doping BiVO 4visible light catalytic material, is characterized in that it prepares in accordance with the following steps:
1) preparation of precursor solution: by Bi (NO 3) 35H 2o fully dissolves in acetum and obtains precursor solution A, by NH 4vO 3fully dissolve in deionized water, and add thiocarbamide and emulsifying agent, thiocarbamide and NH 4vO 3mol ratio be (4.8 ~ 5.2): 1, under room temperature, fully mix and obtain precursor solution B, meet Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, the volume of precursor solution A, B equates, the mass fraction of emulsifying agent in precursor solution B is 2.8 ~ 3.1 wt%; Described emulsifying agent is OP-10;
2) precursor solution A is added dropwise in precursor solution B, stirs 1.5 ~ 3h it is fully mixed, the pH of mixed solution is 1.3 ~ 1.7;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle and heat-treats, and heat treatment temperature is 130 DEG C～150 DEG C, and temperature retention time is 13h～17h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, by the washing of product powder centrifugation, then the product powder of centrifugation is carried out to freeze drying at-100 DEG C～-80 DEG C, be 24～48h drying time, obtains S doping BiVO 4visible light catalytic powder body material.
2. a kind of S doping BiVO according to claim 1 4visible light catalytic material, the volume fraction that it is characterized in that described acetum is 36wt%.
3. a kind of S doping BiVO according to claim 1 4visible light catalytic material, is characterized in that the washing described in step 4) is centrifugal by centrifugal the washing of product powder deionized water, then uses absolute ethanol washing centrifugal.
4. a kind of S doping BiVO according to claim 1 4visible light catalytic material, is characterized in that described in step 4) that centrifugal employing rotating speed is 4500 ~ 6000r/min, and centrifugation time is 3 ~ 5min.
5. a kind of S doping BiVO according to claim 1 4visible light catalytic material, is characterized in that: described in step 4), freeze drying is-90 DEG C of dry 24 ~ 48h.
6. a kind of S doping BiVO claimed in claim 1 4the preparation method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: by Bi (NO 3) 35H 2o fully dissolves in acetum and obtains precursor solution A, by NH 4vO 3fully dissolve in deionized water, and add thiocarbamide and emulsifying agent, thiocarbamide and NH 4vO 3mol ratio be (4.8 ~ 5.2): 1, under room temperature, fully mix and obtain precursor solution B, meet Bi (NO 3) 35H 2o and NH 4vO 3mol ratio be 1:1, the volume of precursor solution A, B equates, the mass fraction of emulsifying agent in precursor solution B is 2.8 ~ 3.1 wt%;
2) precursor solution A is added dropwise in precursor solution B, stirs 1.5 ~ 3h it is fully mixed, the pH of mixed solution is 1.3 ~ 1.7;
3) by step 2) described mixed solution puts into hydrothermal reaction kettle and heat-treats, and heat treatment temperature is 130 DEG C～150 DEG C, and temperature retention time is 13h～17h, then cooling with stove, obtains reaction product solution C;
4) reaction product solution C is carried out to centrifugation, obtain product powder, by the washing of product powder centrifugation, then the product powder of centrifugation is carried out to freeze drying at-100 DEG C～-80 DEG C, be 24～48h drying time, obtains S doping BiVO 4visible light catalytic powder body material.
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