CN102989485A - 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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CN102989485A
CN102989485A CN201210569641XA CN201210569641A CN102989485A CN 102989485 A CN102989485 A CN 102989485A CN 201210569641X A CN201210569641X A CN 201210569641XA CN 201210569641 A CN201210569641 A CN 201210569641A CN 102989485 A CN102989485 A CN 102989485A
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visible light
precursor solution
light catalytic
solution
catalytic material
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CN102989485B (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 the 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 the effective means that solves environment and energy problem as the Photocatalitic Technique of Semiconductor of pith wherein.
Semi-conducting material is light energy conversion chemical energy under the irradiation of light, promotes the synthetic of compound or makes degradation.Semiconductor catalyst has precipitous absorption edge in the visible region, the narrow band gap that they have is conducive on electronics is from the valence to the 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.Simultaneously photocatalysis 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 such as TiO 2, NaTaO 3, the greater band gap such as ZnO, only in ultraviolet light range response is arranged, and the light energy of this wave band accounts for 5% of the sunshine that shines ground, and wavelength reaches 43% of gross energy at the visible-range of 400 ~ 700nm, so the research of high-efficient visible-light photocatalyst is the key that realizes the photocatalysis technology commercial application.At present, the research of novel visible photochemical catalyst has two large thinkings at present: a kind of is to TiO 2, NaTaO 3, 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 and mixes, dye photoactivation, narrow gap semiconductor is compound and the means such as metal complex sensitization; Another kind is the novel visible light-responded conductor photocatalysis material of design, and wherein the low-gap semiconductor preparation is to obtain one of Basic Ways of novel visible catalyst.Therefore, the research worker has designed many composite metal oxides as visible light-responded novel photocatalyst, such as Bi 2WO 6, InVO 4, AgAlO 2, CaIn 2O 4, BiVO 4Deng, they all can be under the irradiation of visible light the catalytic decomposition organic matter.BiVO 4Stable in properties can anti-strong acid and highly basic medium after processing through surface stabilization, and it has the performance of excellent organic solvent-resistant simultaneously, and BiVO 4The response light wave-length coverage can reach more than 500 nm.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 4Ability with visible light catalytic decomposition water and degradable organic pollutant, its response light wave-length coverage reaches on the 500nm, is showing good visible light photocatalytic degradation performance aspect the wastewater treatment as catalysis material.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 light, to have 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 both synthesize the higher BiVO of purity 4Powder body material, however numerous researchers find pure BiVO in experiment 4Catalytic effect can not satisfy growing industrial technology index request.In view of pure BiVO 4Adsorption capacity and the transfer ability of electron-hole pair relatively poor, many scholars begin one's study by modification, perhaps 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 4Introduce defective locations in the lattice or change degree of crystallinity, thereby at BiVO 4The band gap energy level in introduce defect level and impurity energy level, make the less photon excitation BiVO of energy 4Produce photoelectron, thereby change semi-conductive excitation wavelength.In addition, doping can cause the diffusion length of carrier to increase, and when the doping valence state is higher than the valence state of metal ion, thereby the trapping centre that can generate in the part light induced electron suppresses the compound of light induced electron and hole, improves BiVO 4Photocatalytic activity.Xu etc. have prepared the BiVO that series of rare earth (Ho, Sm, Yb, Eu, Gd, Nd, Ce, La) is mixed 4Photochemical catalyst, and under visible light, process methylene blue.Experiment shows, the BiVO after the doping 4Photocatalysis performance is significantly improved than original material.
Can be found out synthesis of high purity BiVO by above-mentioned analysis 4Powder also carries out the utilization rate that ion doping can significantly improve its catalytic activity and catalyst to it, makes BiVO 4In electronic energy excited by the long light of wavelength, and have not yet to see BiVO about the 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 a kind of S of preparation doping BiVO for the deficiency of above-mentioned prior art existence 4The S doping BiVO that the method for visible light catalytic material, the method obtain 4The photocatalysis performance of visible light catalytic material improves, and light degradation speed is accelerated.
The present invention is that 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: with Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the acetum, with NH 4VO 3Fully dissolve in the deionized water, and add thiocarbamide and emulsifying agent, thiocarbamide and NH 4VO 3Mol ratio be (4.8 ~ 5.2): 1, mix under the room temperature and obtain the precursor solution B, satisfy Bi (NO 3) 35H 2O and NH 4VO 3Mol ratio be 1:1, the volume of precursor solution A, B equates that the mass fraction of emulsifying agent in the precursor solution B is 2.8 ~ 3.1 wt%;
2) the precursor solution A is added dropwise in the precursor solution B, stirs 1.5 ~ 3h it is fully mixed, this moment, the pH of mixed solution was 1.3 ~ 1.7;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle and heat-treats, and heat treatment temperature is 130 ℃～150 ℃, and temperature retention time is 13h～17h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, with the washing of product powder and centrifugation, the product powder with centrifugation carries out freeze drying under-100～-80 ℃ again, be 24～48h drying time, namely obtains S doping BiVO 4The visible 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 described heat treatment of 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, the described washing of step 4) is centrifugal centrifugal with the deionized water washing with the product powder, then uses absolute ethanol washing centrifugal.
Press such scheme, the solvent medium of the centrifugal employing of the described washing of step 4) can also be the organic solvents such as methyl alcohol, isopropyl alcohol or toluene.
Press such scheme, the described centrifugal employing rotating speed of step 4) is 4500 ~ 6000r/min, and centrifugation time is 3 ~ 5min.
Press such scheme, the described freeze drying of step 4) is-90 ℃ of drying 24 ~ 48h.
Above-mentioned S doping BiVO 4The preparation method of visible light catalytic material, it comprises the steps:
1) preparation of precursor solution: with Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the acetum, with NH 4VO 3Fully dissolve in the deionized water, and add thiocarbamide and emulsifying agent, thiocarbamide and NH 4VO 3Mol ratio be (4.8 ~ 5.2): 1, fully mix under the room temperature and obtain the precursor solution B, satisfy Bi (NO 3) 35H 2O and NH 4VO 3Mol ratio be 1:1, the volume of precursor solution A, B equates that the mass fraction of emulsifying agent in the precursor solution B is 2.8 ~ 3.1 wt%;
2) the precursor solution A is added dropwise in the precursor solution B, stirs 1.5 ~ 3h it is fully mixed, the pH of mixed solution is 1.3 ~ 1.7;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle and heat-treats, and heat treatment temperature is 130 ℃～150 ℃, and temperature retention time is 13h～17h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, with the washing of product powder and centrifugation, the product powder with centrifugation carries out freeze drying under-80～-100 ℃ again, be 24～48h drying time, namely obtains S doping BiVO 4The visible 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 its further application because the transfer ability of adsorption capacity and electron-hole pair is relatively poor, the present invention adopts the hydro-thermal reaction method to prepare highly purified S doping BiVO 4Visible light catalytic material, this method prepare that speed is fast, efficient is high, reaction transforms fully.
2, with pure BiVO 4Compare the S doping BiVO that the present invention prepares 4The visible light catalytic material energy gap diminishes.
3, the S doping BiVO for preparing of the present invention 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, and is workable, and preparation cost is low, can prepare rapidly the S doping BiVO that meets instructions for use 4The heat-treatment furnace that visible light catalytic material, hydro-thermal reaction adopt has very large generality, is applicable to laboratory and industrial production.
Description of drawings
Fig. 1 is the pure BiVO that makes in the embodiment of the invention 1 4The SEM photo of visible light catalytic material.
Fig. 2 is the S doping BiVO that makes in the embodiment of the invention 2 4The FESEM photo of visible light catalytic material.
Fig. 3 is the S doping BiVO that makes in the embodiment of the invention 2 4The TEM photo of visible light catalytic material.
Fig. 4 is the S doping BiVO that makes in the embodiment of the invention 3 4The XRD collection of illustrative plates of visible light catalytic material.
Fig. 5 is the S doping BiVO that makes in the embodiment of the invention 4 4The XPS analysis collection of illustrative plates of visible light catalytic material.
Fig. 6 is prepared S doping BiVO among the embodiment of the invention 1 and the embodiment 5～7 4The photocatalytic speed figure of visible light catalytic material (abscissa is the time, and ordinate is concentration ratio, i.e. the ratio of instantaneous concentration and initial concentration).
The specific embodiment
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 not only is confined to the following examples.
This embodiment of embodiment 1(is comparison example, does not namely add emulsion OP-10 and thiocarbamide):
A kind ofly prepare 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 by weighing material powder, with 5mmol Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the 25ml acetum, with 5mmol NH 4VO 3Fully dissolve in the 25ml deionized water, fully mix under the room temperature and obtain the precursor solution B;
2) the precursor solution A is added dropwise in the precursor solution B gradually, adopts magnetic agitation 2h under the room temperature, it is fully mixed, this moment, mixed solution pH was 1.4;
3) 3) with step 2) described mixed solution puts into hydrothermal reaction kettle, places in the high temperature resistance furnace and heat-treats, and heat treatment temperature is 140 ℃, and temperature retention time is 15h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, the product powder is mixed with deionized water, carry out centrifuge washing 4 times, then the product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 5 times, centrifuge speed is 4500r/min, each centrifugation time is 5min, the product powder after obtaining cleaning; The product powder is inserted again and carry out freeze drying in the freeze drier under-80 ℃, be 24h drying time, namely obtains pure BiVO after the drying 4The visible light catalytic powder body material is labeled as BiVO 4 - 1.
Prepared pure BiVO as can be seen from Figure 1 4The visible light catalytic powder body material is the octahedral terrace with edge, and particle surface is smooth, and particle size is larger, probably is 2-3 μ m; Its specific area is 0.17m by the BET determination of adsorption method 2/ g; To in the 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 are 100mL, and visible light catalytic powder body material dosage is 0.1g, and the light source of employing is the 350W xenon lamp, and other embodiment degradation conditions are identical therewith.
Embodiment 2:
A kind of S doping BiVO for preparing 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 by weighing material powder, with 5mmol Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the 25ml acetum, with 5mmol NH 4VO 3Fully dissolve in the 25ml deionized water, and add thiocarbamide and emulsifier op-10, wherein thiocarbamide and NH 4VO 3Mol ratio be 4.8:1, fully mix under the room temperature and obtain the precursor solution B, the mass fraction of emulsifying agent in the precursor solution B is 2.9wt%;
2) the precursor solution A is added dropwise in the precursor solution B gradually, adopts magnetic agitation 2h under the room temperature, it is fully mixed, this moment, mixed solution pH was 1.5;
3) 3) with step 2) described mixed solution puts into hydrothermal reaction kettle, places in the high temperature resistance furnace and heat-treats, and heat treatment temperature is 130 ℃, and temperature retention time is 14h, then with the stove cooling, obtains reaction product solution C;
3) reaction product solution C is carried out centrifugation, obtain the product powder, the product powder is mixed with deionized water, carry out centrifuge washing 3 times, then the product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 4 times, centrifuge speed is 5000r/min, each centrifugation time is 5min, the product powder after obtaining cleaning; The product powder is inserted again and carry out freeze drying in the freeze drier under-80 ℃, be 48h drying time, namely obtains S doping BiVO after the drying 4The visible 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 by the tiny BiVO of 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 loose the morphology of the aggregate as seen from Figure 3, mainly is deposited in together by some polyhedral nano particles to form, and the 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:
A kind of S doping BiVO for preparing 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 by weighing material powder, with 5mmol Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the 25ml acetum, with 5mmol NH 4VO 3Fully dissolve in the 25ml deionized water, and add thiocarbamide and emulsifier op-10, wherein, thiocarbamide and NH 4VO 3Mol ratio be 5:1, fully mix under the room temperature and obtain the precursor solution B, the mass fraction of emulsifying agent in the precursor solution B is 2.8wt%;
2) the precursor solution A is added dropwise in the precursor solution B gradually, adopts magnetic agitation 1.5h under the room temperature, it is fully mixed, this moment, mixed solution pH was 1.6;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle, places in the high temperature resistance furnace and heat-treats, and heat treatment temperature is 150 ℃, and temperature retention time is 16h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, the product powder is mixed with deionized water, carry out centrifuge washing 4 times, then the product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 4 times, centrifuge speed is 6000r/min, each centrifugation time is 3min, the product powder after obtaining cleaning; The product powder is inserted again and carry out freeze drying in the freeze drier under-90 ℃, be 24h drying time, namely obtains S doping BiVO after the drying 4The visible light catalytic powder body material.
As can be seen from Figure 4, gained S doping BiVO 4The visible light catalytic powder body material is the BiVO of pure monoclinic form 4, the adding of S does not affect BiVO 4Structure; The combination of Bi4f7/2 can be 159.1eV in this material 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 the BiVO that is doped to of S element success 4In, products therefrom is S doping BiVO really 4The visible 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:
A kind of S doping BiVO for preparing 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 by weighing material powder, with 5mmol Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the 25ml acetum, with 5mmol NH 4VO 3Fully dissolve in the 25ml deionized water, and add thiocarbamide and emulsifier op-10, wherein thiocarbamide and NH 4VO 3Mol ratio be 5.2:1, fully mix under the room temperature and obtain the precursor solution B, the mass fraction of emulsifying agent in the precursor solution B is 2.9wt%;
2) the precursor solution A is added dropwise in the precursor solution B gradually, adopts magnetic agitation 3h under the room temperature, it is fully mixed, this moment, mixed solution pH was 1.3;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle, places in the high temperature resistance furnace and heat-treats, and heat treatment temperature is 150 ℃, and temperature retention time is 15h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, the product powder is mixed with deionized water, carry out time centrifuge washing, then the product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 3 times, centrifuge speed is 4500r/min, each centrifugation time is 5min, the product powder after obtaining cleaning; The product powder is inserted again and carry out freeze drying in the freeze drier under-90 ℃, be 48h drying time, namely obtains S doping BiVO after the drying 4The visible 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:
A kind of S doping BiVO for preparing 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 by weighing material powder, with 5mmol Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the 25ml acetum, with 5mmol NH 4VO 3Fully dissolve in the 25ml deionized water, and add a certain amount of thiocarbamide and emulsifier op-10, wherein thiocarbamide and NH 4VO 3Mol ratio be 5:1, fully mix under the room temperature and obtain the precursor solution B, the mass fraction of emulsifying agent in the precursor solution B is 3wt%;
2) the precursor solution A is added dropwise in the precursor solution B gradually, adopts magnetic agitation 2h under the room temperature, it is fully mixed, this moment, mixed solution pH was;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle, places in the high temperature resistance furnace and heat-treats, and heat treatment temperature is 140 ℃, and temperature retention time is 15h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, the product powder is mixed with deionized water, carry out centrifuge washing 3 times, then the product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 5 times, centrifuge speed is 5500r/min, each centrifugation time is 5min, the product powder after obtaining cleaning; The product powder is inserted again and carry out freeze drying in the freeze drier under-90 ℃, be 24h drying time, namely obtains S doping BiVO after the drying 4The visible 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, saw Fig. 6.
Embodiment 6:
A kind of S doping BiVO for preparing 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 by weighing material powder, with 5mmol Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the 25ml acetum, with 5mmol NH 4VO 3Fully dissolve in the 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, fully mix under the room temperature and obtain the precursor solution B, the mass fraction of emulsifying agent in the precursor solution B is 3.1wt%;
2) the precursor solution A is added dropwise in the precursor solution B gradually, adopts magnetic agitation 2h under the room temperature, it is fully mixed, this moment, mixed solution pH was;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle, places in the high temperature resistance furnace and heat-treats, and heat treatment temperature is 170 ℃, and temperature retention time is 15h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, the product powder is mixed with deionized water, carry out centrifuge washing 3 ~ 5 times, then the 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, the product powder after obtaining cleaning; The product powder is inserted again and carry out freeze drying in the freeze drier under-90 ℃, be 24h drying time, namely obtains S doping BiVO after the drying 4The visible 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, saw Fig. 6.
Embodiment 7:
A kind of S doping BiVO for preparing 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 by weighing material powder, with 5mmol Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the 25ml acetum, with 5mmol NH 4VO 3Fully dissolve in the 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, fully mix under the room temperature and obtain the precursor solution B, the mass fraction of emulsifying agent in the precursor solution B is 3wt%;
2) the precursor solution A is added dropwise in the precursor solution B gradually, adopts magnetic agitation 2h under the room temperature, it is fully mixed, this moment, mixed solution pH was;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle, places in the high temperature resistance furnace and heat-treats, and heat treatment temperature is 110 ℃, and temperature retention time is 15h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, the product powder is mixed with deionized water, carry out centrifuge washing 3 times, then the product powder is mixed with absolute ethyl alcohol, carry out centrifuge washing 3 times, centrifuge speed is 5000r/min, each centrifugation time is 5min, the product powder after obtaining cleaning; The product powder is inserted again and carry out freeze drying in the freeze drier under-100 ℃, be 48h drying time, namely obtains S doping BiVO after the drying 4The visible 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, saw Fig. 6.
As can be seen from Figure 6, pure BiVO 4The visible light catalytic powder body material to MBD solution substantially without the degraded, S doping BiVO 4The visible light catalytic powder body material has to a certain degree degraded to MBD solution, as S doping BiVO 4The Hydrothermal Synthesis temperature of visible light catalytic powder body material is 140 ℃, 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 (7)

1. S doping BiVO 4Visible light catalytic material is characterized in that it prepares in accordance with the following steps:
1) preparation of precursor solution: with Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the acetum, with NH 4VO 3Fully dissolve in the deionized water, and add thiocarbamide and emulsifying agent, thiocarbamide and NH 4VO 3Mol ratio be (4.8 ~ 5.2): 1, fully mix under the room temperature and obtain the precursor solution B, satisfy Bi (NO 3) 35H 2O and NH 4VO 3Mol ratio be 1:1, the volume of precursor solution A, B equates that the mass fraction of emulsifying agent in the precursor solution B is 2.8 ~ 3.1 wt%;
2) the precursor solution A is added dropwise in the precursor solution B, stirs 1.5 ~ 3h it is fully mixed, the pH of mixed solution is 1.3 ~ 1.7;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle and heat-treats, and heat treatment temperature is 130 ℃～150 ℃, and temperature retention time is 13h～17h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, with the washing of product powder and centrifugation, the product powder with centrifugation carries out freeze drying under-100 ℃～-80 ℃ again, be 24～48h drying time, namely obtains S doping BiVO 4The visible 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 described emulsifying agent is OP-10.
4. a kind of S doping BiVO according to claim 1 4Visible light catalytic material is characterized in that the described washing of step 4) is centrifugal centrifugal with the deionized water washing with the product powder, then uses absolute ethanol washing centrifugal.
5. a kind of S doping BiVO according to claim 1 4Visible light catalytic material is characterized in that the described centrifugal employing rotating speed of step 4) is 4500 ~ 6000r/min, and centrifugation time is 3 ~ 5min.
6. a kind of S doping BiVO according to claim 1 4Visible light catalytic material is characterized in that: the described freeze drying of step 4) is-90 ℃ of drying 24 ~ 48h.
7. 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: with Bi (NO 3) 35H 2O fully dissolves in and obtains the precursor solution A in the acetum, with NH 4VO 3Fully dissolve in the deionized water, and add thiocarbamide and emulsifying agent, thiocarbamide and NH 4VO 3Mol ratio be (4.8 ~ 5.2): 1, fully mix under the room temperature and obtain the precursor solution B, satisfy Bi (NO 3) 35H 2O and NH 4VO 3Mol ratio be 1:1, the volume of precursor solution A, B equates that the mass fraction of emulsifying agent in the precursor solution B is 2.8 ~ 3.1 wt%;
2) the precursor solution A is added dropwise in the precursor solution B, stirs 1.5 ~ 3h it is fully mixed, the pH of mixed solution is 1.3 ~ 1.7;
3) with step 2) described mixed solution puts into hydrothermal reaction kettle and heat-treats, and heat treatment temperature is 130 ℃～150 ℃, and temperature retention time is 13h～17h, then with the stove cooling, obtains reaction product solution C;
4) reaction product solution C is carried out centrifugation, obtain the product powder, with the washing of product powder and centrifugation, the product powder with centrifugation carries out freeze drying under-100 ℃～-80 ℃ again, be 24～48h drying time, namely obtains S doping BiVO 4The visible light catalytic powder body material.
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CN104226212A (en) * 2014-09-30 2014-12-24 天津大学 Preparation of Bi2WO6 spherical cluster with exposed {010} crystal plane families
CN107537469A (en) * 2016-06-27 2018-01-05 张家港市杨舍丝印工艺厂 A kind of preparation method of bismuth tungstate Quito member heterojunction photocatalyst
CN106540750A (en) * 2016-10-21 2017-03-29 山东大学 With visible light-responded small numerator modified catalysis material and preparation method
CN106540750B (en) * 2016-10-21 2019-01-29 山东大学 With visible light-responded small numerator modified catalysis material and preparation method
CN109174135A (en) * 2018-10-22 2019-01-11 重庆大学 A kind of preparation method of sulfur doping bismuth molybdate nano-sheet visible light catalyst
CN109174135B (en) * 2018-10-22 2021-08-10 重庆大学 Preparation method of sulfur-doped bismuth molybdate nanosheet-shaped visible-light-driven photocatalyst
CN114525063A (en) * 2022-03-31 2022-05-24 广东卡百利新材料科技有限公司 Odorless anti-formaldehyde water-based interior wall coating and preparation method thereof

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