CN102303906B - Ascorbic-acid-aided colloidal crystal template method used for preparing three-dimensionally ordered macroporous BiVO4 - Google Patents
Ascorbic-acid-aided colloidal crystal template method used for preparing three-dimensionally ordered macroporous BiVO4 Download PDFInfo
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- CN102303906B CN102303906B CN 201110222316 CN201110222316A CN102303906B CN 102303906 B CN102303906 B CN 102303906B CN 201110222316 CN201110222316 CN 201110222316 CN 201110222316 A CN201110222316 A CN 201110222316A CN 102303906 B CN102303906 B CN 102303906B
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- ordered macroporous
- bivo
- bivo4
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Abstract
The invention belongs to the technical field of functional materials, and relates to an ascorbic-acid-aided colloidal crystal template method used for preparing three-dimensionally ordered macroporous BiVO4. According to the invention, PMMA microsphere is adopted as a hard template (a colloidal crystal template), ascorbic acid is adopted as a surfactant (wherein a molar ratio of ammonium metavanadate to ascorbic acid is 1:1-2), a mixed liquid of ethylene glycol, methanol, nitric acid and deionized water is adopted as a solvent, and bismuth nitrate and ammonium metavanadate are adopted as metal sources. A mixed solution containing the surfactant, the solvent and the metal salts are used for infusing PMMA. Infused PMMA is roasted, and is used for preparing three-dimensionally ordered macroporous BiVO4 with a monoclinic scheelite structure. The method provided by the invention is characterized in that: the raw materials are cheap and easy to obtain; the preparing process is simple, the product form and the pore sizes are controllable, and the like. The three-dimensionally ordered macroporous BiVO4 with a monoclinic scheelite structure has a character of porous structure, and has a relatively high specific surface area. The product has good application prospect in respects such as photocatalysts, electrode materials, and ionophore materials.
Description
Technical field
The invention belongs to technical field of function materials, relate to a kind of three-dimensional ordered macroporous structure BiVO
4The preparation method, relating in particular to a kind of is the three-dimensional ordered macroporous BiVO that tensio-active agent prepares the monocline scheelite-type structure with the xitix
4Glue crystal template method.
Background technology
Pucherite is a kind of novel semiconductor material with visible light-responded ability, can be used as photocatalyst, ferroelasticity material, nontoxic yellow ultramarine, reversible thermochromic materials, electrode materials, ionic conductor material etc.In three kinds of crystalline structure of pucherite, the monocline scheelite-type structure demonstrates best photocatalysis performance.At present, can adopt solid phase method, sonochemical method, microwave method, hydrothermal method, the precipitator method, template to wait to prepare BiVO
4Studies show that BiVO
4Crystalline structure and pore structure its photocatalysis performance is had material impact.Therefore, the research and development preparation has the BiVO of monocline scheelite-type structure and vesicular structure
4Significant.
In recent years, people have explored some preparation porous BiVO
4Method.(H.Y.Jiang such as Jiang, et al., Appl.Catal.B, 2011,105:326～334) be source metal with Bismuth trinitrate and ammonium meta-vanadate, being tensio-active agent with amino dodecane, oleyl amine or oleic acid, is solvent with ethanol and ethylene glycol mixtures, adopts solvent-thermal method to synthesize the mesoporous BiVO of American football shape of monocline scheelite-type structure
4, behind radiation of visible light 4h, its Pyrogentisinic Acid's degradation rate is higher than 95%.Li etc. (G.S.Li, et al., Chem.Mater., 2008,20:3983～3992) are source metal with Bismuth trinitrate and ammonium meta-vanadate, are the order mesoporous BiVO that hard template synthesizes the monocline scheelite-type structure with mesoporous silicon KIT-6
4, and adopt Hydrothermal Preparation to go out the BiVO of atresia monocline scheelite-type structure
4, the result shows that both all are higher than P25 and order mesoporous BiVO to the degradation rate of methylene blue under radiation of visible light
4The degradation rate of methylene blue exceeded by hydrothermal method make BiVO
4One times.
Existing bibliographical information is crossed employing glue crystal template method and is prepared three-dimensional ordered macroporous complex metal oxides.For example: employing poly (methyl methacrylate) micro-spheres (PMMA) such as Kim are for the glue crystal template and made perofskite type oxide La in air atmosphere after 600 ℃ of roastings
0.7Ca
0.3MnO
3(Y.N.Kim, et al., Solid State Communications, 2003,128:339～343).Sadakane etc. (M.Sadakane, et al., Chem.Mater., 2005,17:3546～3551) adopt polystyrene microsphere (PS) to obtain the perofskite type oxide La of three-dimensional ordered macroporous structure for the glue crystal template in air atmosphere after 700 ℃ of roastings
1-xSr
xFeO
3(x=0～0.4).Up to now, domestic and foreign literature and patent still do not have and reported that adopting the PMMA microballoon was that the glue crystal template is the three-dimensional ordered macroporous BiVO that tensio-active agent prepares the monocline scheelite-type structure with the xitix
4Method.
Summary of the invention
The object of the present invention is to provide a kind of three-dimensional ordered macroporous BiVO of monocline scheelite-type structure
4The preparation method, be the glue crystal template with the PMMA microballoon of close packed array namely and be the three-dimensional ordered macroporous BiVO that the method for tensio-active agent prepares the monocline scheelite-type structure with the xitix
4
Ammonium meta-vanadate is joined in the mixing solutions that massfraction is 65% aqueous nitric acid and deionized water, the wherein corresponding 1mL aqueous nitric acid of every 10mmol ammonium meta-vanadate and 6mL deionized water, according to ammonium meta-vanadate: the xitix mol ratio is 1: (1-2) add xitix in the gained mixed solution, subsequently with mixed solution at 70 ℃ of magnetic agitation 0.5h, form uniform solution.After treating that solution fully cools off, add Bismuth trinitrate, ethylene glycol and anhydrous methanol, the mol ratio of Bismuth trinitrate and ammonium meta-vanadate is 1: 1, the corresponding 3mL ethylene glycol of every 10mmol Bismuth trinitrate and 6mL anhydrous methanol, the normal temperature lower magnetic force stirs 3h, form the homogeneous precursor solution, the impouring of gained precursor solution is equipped with in the container of PMMA hard template, flood about 3h, make it moistening fully, suction filtration subsequently, drying at room temperature 12h, in retort furnace, in air atmosphere, rise to 300 ℃ and under this temperature, keep 2h with the speed of 1 ℃/min from room temperature at last, continuation is warming up to 450 ℃ and after keeping 4h under this temperature with the phase same rate, can make the three-dimensional ordered macroporous BiVO of monocline scheelite-type structure
4
The present invention has features such as raw material is cheap and easy to get, and preparation process is simple, and product pattern and hole dimension are controlled.
The monocline scheelite-type structure BiVO of the present invention's preparation
4Characteristics and higher specific surface area with vesicular structure are having a good application prospect aspect photocatalyst, electrode materials, ionic conductor material etc.
The method that the present invention describes is that employing is hard template (glue crystal template) with the PMMA microballoon, be tensio-active agent with the xitix, mixed solution with ethylene glycol, methyl alcohol, nitric acid and deionized water is solvent, be source metal with Bismuth trinitrate and ammonium meta-vanadate, after will containing the mixing solutions dipping PMMA of above tensio-active agent, solvent and soluble metallic salt, preparation has the three-dimensional ordered macroporous BiVO of monocline scheelite-type structure after roasting
4Wherein xitix has played keying action for the target product that obtains three-dimensional ordered macroporous structure; Under the situation of not adding xitix, can not get having the BiVO of three-dimensional ordered macroporous structure
4Up to now, domestic and foreign literature and patent still do not have and reported that to adopt the PMMA microballoon be the glue crystal template and be the three-dimensional ordered macroporous BiVO that tensio-active agent prepares the monocline scheelite-type structure with the xitix
4Method.
Utilize instruments such as D8Advance type X-ray diffractometer (XRD), Zeiss Supra 55 type scanning electronic microscope (SEM), Micromeritics ASAP 2020 adsorption desorption analysers to characterize crystalline structure, particle morphology, pore structure and the specific surface area of gained target product.The result shows, according to the prepared BiVO of the inventive method
4Sample has monocline scheelite crystals structure, presents three-dimensional ordered macroporous structure, and macropore diameter is 170～185nm, and specific surface area is 18.1～23.6m
2/ g.
Brief description of drawings
Fig. 1 is the three-dimensional ordered macroporous BiVO of obtained monocline scheelite-type structure
4The XRD spectra of sample, wherein curve (a) and (b) and the XRD spectra that (c) is respectively embodiment 1, embodiment 2 and embodiment 3 samples;
Fig. 2 is the three-dimensional ordered macroporous BiVO of prepared monocline scheelite-type structure
4The SEM photo of sample, wherein figure (a) and (b) and the SEM photo that (c) is respectively embodiment 1, embodiment 2 and embodiment 3 samples.
Embodiment
In order further to understand the present invention, elaborate with embodiment below, and provide the three-dimensional ordered macroporous BiVO that accompanying drawing is described the monocline scheelite-type structure that the present invention obtains
4
Embodiment 1: take by weighing the 10mmol ammonium meta-vanadate, place the 50mL beaker, add the 1mL massfraction and be 65% aqueous nitric acid and the mixing solutions of 6mL deionized water, add the 10mmol xitix again, behind 70 ℃ of magnetic agitation 0.5h, form uniform solution.After treating that solution fully cools off, add the 10mmol Bismuth trinitrate, 3mL ethylene glycol and 6mL anhydrous methanol, the normal temperature lower magnetic force stirs 3h, forms the homogeneous precursor solution.The impouring of gained precursor solution is equipped with in the container of PMMA hard template, flood about 3h, make it moistening fully, suction filtration, drying at room temperature 12h subsequently, in retort furnace, in air atmosphere, rise to 300 ℃ and under this temperature, keep 2h with the speed of 1 ℃/min from room temperature at last, continuation is warming up to 450 ℃ and after keeping 4h under this temperature with the speed of 1 ℃/min, can make the three-dimensional ordered macroporous BiVO of monocline scheelite-type structure
4Macropore diameter is about 185nm, and specific surface area is 23.6m
2/ g.
Embodiment 2: take by weighing the 10mmol ammonium meta-vanadate, place the 50mL beaker, add the 1mL massfraction and be 65% aqueous nitric acid and the mixing solutions of 6mL deionized water, add the 15mmol xitix again, behind 70 ℃ of magnetic agitation 0.5h, form uniform solution.After treating that solution fully cools off, add the 10mmol Bismuth trinitrate, 3mL ethylene glycol and 6mL anhydrous methanol, the normal temperature lower magnetic force stirs 3h, forms the homogeneous precursor solution.The impouring of gained precursor solution is equipped with in the container of PMMA hard template, flood about 3h, make it moistening fully, suction filtration, drying at room temperature 12h subsequently, in retort furnace, in air atmosphere, rise to 300 ℃ and under this temperature, keep 2h with the speed of 1 ℃/min from room temperature at last, continuation is warming up to 450 ℃ and after keeping 4h under this temperature with the speed of 1 ℃/min, can make the three-dimensional ordered macroporous BiVO of monocline scheelite-type structure
4Macropore diameter is about 180nm, and specific surface area is 18.7m
2/ g.
Embodiment 3: take by weighing the 10mmol ammonium meta-vanadate, place the 50mL beaker, add the 1mL massfraction and be 65% aqueous nitric acid and the mixing solutions of 6mL deionized water, add the 20mmol xitix again, behind 70 ℃ of magnetic agitation 0.5h, form uniform solution.After treating that solution fully cools off, add the 10mmol Bismuth trinitrate, 3mL ethylene glycol and 6mL methyl alcohol, the normal temperature lower magnetic force stirs 3h, forms the homogeneous precursor solution.The impouring of gained precursor solution is equipped with in the container of PMMA hard template, flood about 3h, make it moistening fully, suction filtration, drying at room temperature 12h subsequently, in retort furnace, in air atmosphere, rise to 300 ℃ and under this temperature, keep 2h with the speed of 1 ℃/min from room temperature at last, continuation is warming up to 450 ℃ and after keeping 4h under this temperature with the speed of 1 ℃/min, can make the three-dimensional ordered macroporous BiVO of monocline scheelite-type structure
4Macropore diameter is about 170nm, and specific surface area is 18.1m
2/ g.
Claims (1)
1. one kind prepares three-dimensional ordered macroporous BiVO
4The auxiliary glue crystal template method of xitix, it is characterized in that, may further comprise the steps: ammonium meta-vanadate is joined in the mixing solutions that massfraction is 65% aqueous nitric acid and deionized water, the wherein corresponding 1mL aqueous nitric acid of every 10mmol ammonium meta-vanadate and 6mL deionized water, according to ammonium meta-vanadate: the xitix mol ratio is 1:(1-2) in the gained mixed solution, add xitix, subsequently with mixed solution at 70 ℃ of magnetic agitation 0.5h, form uniform solution; After treating that solution fully cools off, add Bismuth trinitrate, ethylene glycol and anhydrous methanol, the mol ratio of Bismuth trinitrate and ammonium meta-vanadate is 1:1, the corresponding 3mL ethylene glycol of every 10mmol Bismuth trinitrate and 6mL anhydrous methanol, the normal temperature lower magnetic force stirs 3h, form the homogeneous precursor solution, the impouring of gained precursor solution is equipped with in the container of PMMA hard template, dipping 3h, make it moistening fully, suction filtration subsequently, drying at room temperature 12h, in retort furnace, in air atmosphere, rise to 300 ℃ and under this temperature, keep 2h with the speed of 1 ℃/min from room temperature at last, continuation is warming up to 450 ℃ and after keeping 4h under this temperature with the phase same rate, can make the three-dimensional ordered macroporous BiVO of monocline scheelite-type structure
4Prepared three-dimensional ordered macroporous BiVO
4Sample has monocline scheelite crystals structure, presents three-dimensional ordered macroporous structure, and macropore diameter is 170～185nm, and specific surface area is 18.1～23.6m
2/ g.
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| CN102872853A (en) * | 2012-09-26 | 2013-01-16 | 北京工业大学 | Three-dimensional ordered macroporous InVO4 visible light-responsive photocatalyst, preparation and application |
| CN104084188A (en) * | 2014-06-26 | 2014-10-08 | 北京工业大学 | Visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and application of photo-catalyst |
| CN104117370B (en) * | 2014-06-26 | 2016-07-06 | 北京工业大学 | Three-dimensional ordered macroporous BiVO4 loaded Ag Br and Pd photocatalyst, preparation and application |
| CN104084200B (en) * | 2014-06-26 | 2016-06-29 | 北京工业大学 | Three-dimensional ordered macroporous InVO4-BiVO4Carried noble metal nano-photocatalyst, preparation and application |
| CN104084215B (en) * | 2014-06-26 | 2016-08-24 | 北京工业大学 | One prepares three-dimensional ordered macroporous BiVO4the Fe of load2o3with noble metal photochemical catalyst and preparation method |
| CN104148051B (en) * | 2014-07-16 | 2016-08-17 | 河南师范大学 | The biomimetic synthesis method of pucherite nano visible light catalyst |
| CN109621953A (en) * | 2018-12-28 | 2019-04-16 | 北京工业大学 | A kind of three-dimensional ordered macroporous pucherite supported ruthenium catalyst of high-efficiency photocatalysis oxidization benzyl alcohol |
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| CN1872406A (en) * | 2006-06-30 | 2006-12-06 | 中国科学院上海硅酸盐研究所 | Method for preparing visible light catalyst of Nano crystal BiVO4 in high activity through ultrasound chemistry |
| CN101717116A (en) * | 2009-12-18 | 2010-06-02 | 北京工业大学 | Surface active agent assisting alcohol-hydrothermal method for preparing anthoid BiVO4 |
| CN101746825A (en) * | 2009-12-18 | 2010-06-23 | 北京工业大学 | Organic solvent-water heating method for preparing football-shaped mesoporous BiVO4 |
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| CN1872406A (en) * | 2006-06-30 | 2006-12-06 | 中国科学院上海硅酸盐研究所 | Method for preparing visible light catalyst of Nano crystal BiVO4 in high activity through ultrasound chemistry |
| CN101717116A (en) * | 2009-12-18 | 2010-06-02 | 北京工业大学 | Surface active agent assisting alcohol-hydrothermal method for preparing anthoid BiVO4 |
| CN101746825A (en) * | 2009-12-18 | 2010-06-23 | 北京工业大学 | Organic solvent-water heating method for preparing football-shaped mesoporous BiVO4 |
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