CN102380367A - Control synthetic method of high-visible-light-activity mixed crystal type BiVO4 photocatalysts - Google Patents
Control synthetic method of high-visible-light-activity mixed crystal type BiVO4 photocatalysts Download PDFInfo
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Abstract
The invention discloses a control synthetic method of high-visible-light-activity mixed crystal type BiVO4 photocatalysts, which comprises the steps that: firstly, a certain amount of NH3VO4 and Bi(NO3)3.5H2O are taken according to the stoichiometric ratio and are respectively dissolved in NaOH solution and HNO3 solution to obtain clear solutions A and B; then, the solution A is gradually dripped into the solution B to generate yellow turbid liquid, next, the NaOH solution is used for regulating the pH value to 2 to 9, the mixed solution is transferred into a stainless steel reaction kettle using white polyfluortetraethylene as an inner lining after being stirred for 2 to 6h, and the reaction is carried out for 2 to 8h under the temperature condition of 120 to 180 DEG C; and after the complete reaction, deionized water and absolute ethyl alcohol are used for cleaning samples until filter liquid is neutral, and the drying is carried out for 4 to 8h under the condition of 60 to 100 DEG C. The control synthetic method has the advantages that the preparation process is simple, the cost is low, the crystal type proportion is controllable, the dispersibility of the mixed crystal type BiVO4 is good, the specific surface area is large, and the visible light activity is high.
Description
Technical field
The present invention relates to a kind of preparation method of photochemical catalyst, be specifically related to the synthetic high visible light catalytic activity mixed crystal type BiVO of a kind of employing hydrothermal technique control
4The method of catalyst belongs to the photocatalyst material field.
Background technology
Resource and environment are more and more obvious to the binding character of human social development, and solving resource and environmental problem is human the pressing for of sustainable development of realizing.Photocatalysis technology is that photochemical catalyst absorbs solar energy and is translated into the chemical reaction energy needed; Promote the carrying out of chemical reaction; A kind of catalytic reaction technology that self does not change is mainly used in photolysis water hydrogen and photocatalysis degradation organic contaminant, and it is low to have energy consumption; Easy to operate, characteristics such as non-secondary pollution.Early stage photochemical catalyst such as nano-TiO
2Energy gap is bigger; The photocatalysis response is only arranged under ultraviolet light; The content of solar spectrum medium ultraviolet light is less than 5%; And wavelength at the visible light content of (400～750) nm more than 43%, therefore how to utilize solar energy to carry out light-catalyzed reaction efficiently, exploitation has the interest that visible light-responded photochemical catalyst causes people day by day.
At present, is active standard comparative catalyst's catalytic performance often in the research both at home and abroad with DegussaP25, the TiO of the mixing crystalline structure that P25 is made up of rutile-type and Detitanium-ore-type
2(the rutile-type mass fraction is 25%, and the Detitanium-ore-type mass fraction is 75%) is than the TiO of single crystal form structure
2Has better photocatalysis effect.Research shows, because two kinds of mixing up of structure have increased TiO
2Intracell defect concentration has increased the concentration of carrier, and electronics, number of cavities are increased, and makes it have the stronger TiO that is captured in
2The ability of solution component (water, oxygen, organic matter) on surface, thus the catalytic performance of catalyst strengthened.
BiVO
4Have tetragonal crystal system scheelite type (scheelite-tetragonal), tetragonal crystal system zirconium silicate type (zircon-tetragnol) and three kinds of crystalline structures of monoclinic system scheelite type (scheelite-monoclinic); In early days enjoy people to pay close attention to, find that afterwards it also has a good application prospect in the visible light catalytic technical field as a kind of yellow uitramarine that does not contain poisonous element and good ionic conductivity ceramics and electrode material.Wherein, the BiVO of monocline phase
4Energy gap be 2.4 eV, its absorption spectrum can be extended to more than the 500nm, has visible light-responded preferably characteristic.Up to the present, the high BiVO of visible light activity in the existing report
4Photochemical catalyst all is single monocline scheelite type structure usually, does not see the mixed crystal type BiVO with high catalytic performance
4The synthetic report of photochemical catalyst.
Summary of the invention
The objective of the invention is: provide a kind of high visible active mixed crystal type BiVO
4The control synthetic method of photochemical catalyst, this preparation method are through the condition of control hydro-thermal reaction, and the mixed crystal type BiVO that is made up of monocline scheelite type and cubic zirconium silicate type is synthesized in control
4Photochemical catalyst, mixed crystal type BiVO
4Photochemical catalyst has good visible light-responded.
Technical solution of the present invention is this mixed crystal type BiVO
4The control synthetic method of photochemical catalyst may further comprise the steps:
A) take by weighing a certain amount of NH according to stoichiometric proportion
3VO
3And Bi (NO
3)
35H
2O is with NH
3VO
3Be dissolved in the NaOH solution of 2～4mol/L and process clear solution A, with Bi (NO
3)
35H
2O is dissolved in the HNO of 2～4mol/L
3Process clear solution B in the solution;
B) constantly under the condition of stirring above-mentioned clear solution A is being added drop-wise among the clear solution B gradually; Generate yellow suspension; Drip complete continued and stir 30min, the pH of NaOH solution regulation system that uses 2～4mol/L again continues to stir 2～6h between 2～9;
C) suspension of above-mentioned preparation being transferred to the white polytetrafluoroethylpipe is in the stainless steel cauldron of liner, and the volume compactedness is no more than 60%, puts into insulating box hydrothermal treatment consists 2～8h under 120～180 ℃ of conditions then;
D) the abstraction reaction product is filtered in the back that reacts completely, and the yellow mercury oxide that obtains is used deionized water and absolute ethanol washing 2～3 times successively, be neutral to pH value of filtrate, and drying 4～8h gets mixed crystal type BiVO in 60～100 ℃ of baking ovens
4Photochemical catalyst.
The present invention has the following advantages: 1, adopt hydrothermal synthesis method to prepare catalyst, need not any surfactant, technology is simple, and cost is lower, and crystalline structure is controlled; 2, the mixed crystal type BiVO of preparation
4Than single monocline type BiVO
4Have better catalytic effect, this does not have a kind of novel catalyst of reporting before being; 3, obtain different mixed crystal ratios through the control hydrothermal synthesizing condition
RBiVO
4Catalyst,
RBe mixed crystal type BiVO
4In monoclinic system percentages of ingredients example, calculate R=by the relative intensity at monocline (121) and cubic (200) peak
I Mono (121)/ (I
Mono (121)+
I Tetra (200)) * 100%, wherein, when
RGreater than 60% o'clock, mixed crystal type BiVO
4Have good visible light catalytic effect, the degradation rate of methylene blue is more than 90% behind the photocatalysis 2h.
Description of drawings
Fig. 1 is the BiVO of different crystal forms ratio
4XRD figure spectrum, the BiVO that obtains for embodiment 1 of a wherein
4(
R=0), the BiVO that obtains for embodiment 2 of b
4(
R=60.51%) BiVO that obtains for embodiment 3 of c,
4(
R=92.73%) BiVO that obtains for embodiment 4 of d,
4(
R=1).
Fig. 2 is the BiVO of different crystal forms ratio
4The UV-Vis spectrogram of sample, wherein a, b, c and d are respectively the UV-Vis spectrogram of embodiment 1,2,3 and 4 samples.
Fig. 3 is the BiVO of different crystal forms ratio
4With the relation of degradation rate, wherein a, b, c and d are respectively the catalytic degradation figure of embodiment 1,2,3 and 4 samples.
The specific embodiment
Below in conjunction with the practical implementation instance technical solution of the present invention is further described, these embodiment can not be interpreted as it is the restriction to technical solution.
Embodiment 1: synthetic according to following steps
R=0 BiVO
4Be the BiVO of pure tetragonal crystal system zirconium silicate structure
4:
A) take by weighing 0.9283g NH
3VO
4Be dissolved in the NaOH solution of 10mL 2mol/L and process clear solution A, take by weighing 3.8884g Bi (NO
3)
35H
2O is dissolved in the HNO of 10mL 2mol/L
3Process clear solution B in the solution;
B) constantly under the condition of stirring above-mentioned clear solution A is being added drop-wise among the clear solution B gradually, is generating yellow suspension, dripping complete continued and stir 30min, using the pH of the NaOH solution regulation system of 2mol/L again is 2, continues to stir 6h;
C) above-mentioned suspension being transferred to the white polytetrafluoroethylpipe is in the stainless steel cauldron of liner, puts into 120 ℃ of insulating box hydrothermal treatment consists 8h;
D) filter the abstraction reaction product, the yellow mercury oxide that obtains used deionized water and absolute ethanol washing 2～3 times successively, to pH value of filtrate be neutrality, dry 8h in 60 ℃ of baking ovens obtains
R=0 BiVO
4Catalyst.
Embodiment 2: synthetic according to following steps
R=60.51% mixed crystal type BiVO
4:
A) take by weighing 0.9283g NH
3VO
4Be dissolved in the NaOH solution of 10mL 3mol/L and process clear solution A, take by weighing 3.8884g Bi (NO
3)
35H
2O is dissolved in the HNO of 10mL 3mol/L
3Process clear solution B in the solution;
B) constantly under the condition of stirring above-mentioned clear solution A is being added drop-wise among the clear solution B gradually, is generating yellow suspension, dripping complete continued and stir 30min, using the pH of the NaOH solution regulation system of 3mol/L again is 4, continues to stir 4h;
C) above-mentioned suspension being transferred to the white polytetrafluoroethylpipe is in the stainless steel cauldron of liner, puts into 140 ℃ of insulating box hydrothermal treatment consists 5h;
D) filter the abstraction reaction product, the yellow mercury oxide that obtains used deionized water and absolute ethanol washing 2～3 times successively, to pH value of filtrate be neutrality, dry 6h in 70 ℃ of baking ovens obtains the BiVO of R=60.51%
4Catalyst.
Embodiment 3: synthetic according to following steps
R=92.73% mixed crystal type BiVO
4:
A) take by weighing 0.9283g NH
3VO
4Be dissolved in the NaOH solution of 10mL 4mol/L and process clear solution A, take by weighing 3.8884g Bi (NO
3)
35H
2O is dissolved in the HNO of 10mL 4mol/L
3Process clear solution B in the solution;
B) constantly under the condition of stirring above-mentioned clear solution A is being added drop-wise among the clear solution B gradually, is generating yellow suspension, dripping complete continued and stir 30min, the pH of the 4mol/L NaOH solution regulation system of using again is 7, continues to stir 2h;
C) above-mentioned suspension being transferred to the white polytetrafluoroethylpipe is in the stainless steel cauldron of liner, puts into 160 ℃ of insulating box hydrothermal treatment consists 4h;
D) filter the abstraction reaction product, the yellow mercury oxide that obtains used deionized water and absolute ethanol washing 2～3 times successively, to pH value of filtrate be neutrality, dry 6h in 80 ℃ of baking ovens obtains the BiVO of R=92.73%
4Catalyst.
Embodiment 4: synthetic according to following steps
R=1 BiVO
4Be the BiVO of pure monoclinic system scheelite type structure
4:
A) take by weighing 0.9283g NH
3VO
4Be dissolved in the NaOH solution of 10mL 3mol/L and process clear solution A, take by weighing 3.8884g Bi (NO
3)
35H
2O is dissolved in the HNO of 10mL 3mol/L
3Process clear solution B in the solution;
B) constantly under the condition of stirring above-mentioned clear solution A is being added drop-wise among the clear solution B gradually, is generating yellow suspension, dripping complete continued and stir 30min, using the pH of the NaOH solution regulation system of 3mol/L again is 9, continues to stir 2h;
C) above-mentioned suspension being transferred to the white polytetrafluoroethylpipe is in the stainless steel cauldron of liner, puts into 180 ℃ of insulating box hydrothermal treatment consists 6h;
D) filter the abstraction reaction product, the yellow mercury oxide that obtains used deionized water and absolute ethanol washing 2～3 times successively, to pH value of filtrate be neutrality, dry 6h in 100 ℃ of baking ovens obtains the BiVO of pure monoclinic system scheelite type structure
4Catalyst.
In the quartz test tube of the 10mg/L methylene blue solution that fills 250mL, add 0.25g BiVO
4Catalyst stirs 30min and reaches adsorption equilibrium under no optical condition, be placed under the xenon lamp of 500W to carry out visible light photocatalytic degradation; Every separated 20min gets a solution and centrifugalizes, and surveys the absorbance of the upper strata stillness of night, contrasts their photocatalysis performance, according to Lambert-Beer's law, calculates methylene blue concentration, is calculated as follows the degradation rate of methylene blue: degradation rate %=
, A in the formula
0, A
i---be respectively the absorbance of degraded front and back methylene blue.
Fig. 1 is the BiVO of different crystal forms ratio
4XRD figure spectrum, we can find out from figure, through the control hydrothermal reaction condition, can obtain the BiVO of different crystal forms ratio
4, wherein a is single cubic zirconium silicate type BiVO
4, b is mixed crystal type BiVO
4The percentage composition R of monocline component is 60.51%, and c is mixed crystal type BiVO
4The percentage composition R of monocline component is 92.73%, and d is single monoclinic system type BiVO
4
Fig. 2 be the different crystal forms ratio BiVO
4The UV-Vis spectrogram of sample, the BiVO of as can be seen from the figure single cubic zirconium silicate type
4(sample absorbing wavelength a) is minimum; Mixed crystal type catalyst sample b (R=60.51%) for preparing and sample c (R=92.73%) have bigger absorbing wavelength than single monoclinic system type catalyst sample d; And the absorbing wavelength of sample c is explained the mixed crystal type BiVO of preparation greater than sample b
4Than single monoclinic system type BiVO
4Have better visible light-responded.
Fig. 3 is the BiVO of different crystal forms ratio
4To methylene blue solution visible light catalytic 2h degradation curve figure, the catalyst that can find out the different crystal forms ratio has nothing in common with each other the BiVO of single cubic zirconium silicate type to the absorption and the catalytic effect of methylene blue
4(sample a) adsorption equilibrium capacity is 24.42%, and the degradation rate of methylene blue is 51.59% behind the photocatalysis 2h; Single monoclinic system type BiVO
4(sample d) adsorption capacity is 23.07%, and the degradation rate of methylene blue is 86.49% behind the photocatalysis 2h; The adsorbent solution amount of mixed crystal type sample c (R=60.51%) and d (R=92.73%) is respectively 33.63% and 30.28%, and the degradation rate of methylene blue is respectively 92.61% and 94.83% behind the photocatalysis 2h; Explanation is for the methylene blue system, and the mixed crystal type catalyst has better adsorption effect and catalytic effect than the catalyst of single crystal form.
Claims (7)
1. the active mixed crystal type BiVO of high visible
4The control synthetic method of photochemical catalyst is characterized in that this mixed crystal type BiVO
4The control synthetic method of photochemical catalyst may further comprise the steps: take by weighing a certain amount of NH according to stoichiometric proportion
3VO
3And Bi (NO
3)
35H
2O is dissolved in the clear solution a and the HNO that make in the NaOH solution that configures respectively
3The clear solution b that makes in the solution; Constantly under the condition of stirring above-mentioned clear solution a is being added drop-wise among the clear solution b gradually then; Generate yellow suspension; Between 2 ~ 9, behind stirring 2 ~ 6h suspension being transferred to the white polytetrafluoroethylpipe is in the stainless steel cauldron of liner, puts into baking oven hydrothermal treatment consists 4 ~ 8h under 120 ~ 180 ℃ of conditions with NaOH solution regulation system pH; After reacting completely with the yellow mercury oxide that obtains with deionized water and absolute ethanol washing, in 60 ~ 100 ℃ of baking ovens, can obtain needed catalyst in dry several hours at last.
2. according to the active mixed crystal type BiVO of the described a kind of high visible of claim 1
4The control synthetic method of photochemical catalyst is characterized in that: described reagent is NH
3VO
3, Bi (NO
3)
35H
2O, NaOH, HNO
3, it is pure to be analysis.
3. according to the active mixed crystal type BiVO of the described a kind of high visible of claim 1
4The control synthetic method of photochemical catalyst is characterized in that: described NaOH and HNO
3The concentration of solution is controlled at 2 ~ 4mol/L.
4. according to the active mixed crystal type BiVO of the described a kind of high visible of claim 1
4The control synthetic method of photochemical catalyst is characterized in that: deionized water and absolute ethanol washing 2 ~ 3 times are used in the washing of the yellow mercury oxide that obtains at last successively, to pH value of filtrate be neutrality.
5. according to the active mixed crystal type BiVO of the described a kind of high visible of claim 1
4The control synthetic method of photochemical catalyst is characterized in that: through pH=2 ~ 9 of the hierarchy of control, obtain the BiVO of different crystal forms ratio
4
6. according to the active mixed crystal type BiVO of the described a kind of high visible of claim 1
4The control synthetic method of photochemical catalyst is characterized in that: the hydro-thermal synthesis temperature is between 120 ~ 180 ℃.
7. according to the active mixed crystal type BiVO of the described a kind of high visible of claim 1
4The control synthetic method of photochemical catalyst is characterized in that: the mixed crystal ratio
R=60.51 ~ 92.73 o'clock, mixed crystal type BiVO
4Than single monoclinic system type BiVO
4Has better visible light catalytic performance.
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Cited By (9)
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| 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 |
| CN102897835A (en) * | 2012-09-29 | 2013-01-30 | 绍兴文理学院 | Preparation method of BiVO4 |
| CN102989485A (en) * | 2012-12-25 | 2013-03-27 | 武汉理工大学 | S-doped BiVO4 visible light catalytic material and preparation method thereof |
| CN103240107A (en) * | 2013-04-27 | 2013-08-14 | 天津大学 | Silver phosphate-bismuth vanadate multiplex photocatalyst and preparation method thereof |
| CN103372424A (en) * | 2012-04-12 | 2013-10-30 | 沈阳理工大学 | Synthetic method for high-activity N-F co-doped bismuth vanadate visible light photocatalytic material |
| CN104117370A (en) * | 2014-06-26 | 2014-10-29 | 北京工业大学 | Three-dimensional ordered macroporous (3DOM) BiVO4 loaded AgBr and Pd photocatalyst, preparation and application |
| CN108479750A (en) * | 2018-03-21 | 2018-09-04 | 辽宁石油化工大学 | A kind of preparation method of microspheroidal pucherite catalysis material |
| CN109433185A (en) * | 2018-12-10 | 2019-03-08 | 北华大学 | One step hydro thermal method prepares vanadic acid indium/isomerism knot composite bismuth vanadium photocatalyst |
| CN109865512A (en) * | 2019-03-05 | 2019-06-11 | 西安理工大学 | A method of preparing α-bismuth niobate photocatalyst |
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| CN103372424A (en) * | 2012-04-12 | 2013-10-30 | 沈阳理工大学 | Synthetic method for high-activity N-F co-doped bismuth vanadate visible light photocatalytic material |
| CN103372424B (en) * | 2012-04-12 | 2016-09-28 | 沈阳理工大学 | A kind of synthetic method of high activity N-F codope pucherite visible-light photocatalysis material |
| 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 |
| CN102897835A (en) * | 2012-09-29 | 2013-01-30 | 绍兴文理学院 | Preparation method of BiVO4 |
| CN102989485A (en) * | 2012-12-25 | 2013-03-27 | 武汉理工大学 | S-doped BiVO4 visible light catalytic material and preparation method thereof |
| CN102989485B (en) * | 2012-12-25 | 2014-12-03 | 武汉理工大学 | S-doped BiVO4 visible light catalytic material and preparation method thereof |
| CN103240107A (en) * | 2013-04-27 | 2013-08-14 | 天津大学 | Silver phosphate-bismuth vanadate multiplex photocatalyst and preparation method thereof |
| CN104117370A (en) * | 2014-06-26 | 2014-10-29 | 北京工业大学 | Three-dimensional ordered macroporous (3DOM) BiVO4 loaded AgBr and Pd photocatalyst, preparation and application |
| CN108479750A (en) * | 2018-03-21 | 2018-09-04 | 辽宁石油化工大学 | A kind of preparation method of microspheroidal pucherite catalysis material |
| CN109433185A (en) * | 2018-12-10 | 2019-03-08 | 北华大学 | One step hydro thermal method prepares vanadic acid indium/isomerism knot composite bismuth vanadium photocatalyst |
| CN109865512A (en) * | 2019-03-05 | 2019-06-11 | 西安理工大学 | A method of preparing α-bismuth niobate photocatalyst |
| CN109865512B (en) * | 2019-03-05 | 2022-02-01 | 西安理工大学 | Method for preparing alpha-bismuth niobate photocatalyst |
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