CN103611556A - ZnO-BaTaO2N composite photocatalyst and preparation method thereof - Google Patents
ZnO-BaTaO2N composite photocatalyst and preparation method thereof Download PDFInfo
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- CN103611556A CN103611556A CN201310644490.4A CN201310644490A CN103611556A CN 103611556 A CN103611556 A CN 103611556A CN 201310644490 A CN201310644490 A CN 201310644490A CN 103611556 A CN103611556 A CN 103611556A
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Abstract
The invention discloses a ZnO-BaTaO2N composite photocatalyst and a preparation method thereof, belonging to the field of inorganic functional materials. The technical scheme is as follows: the ZnO-BaTaO2N composite photocatalyst is compounded from ZnO powder and BaTaO2N powder in a mole ratio of (5-15):1. The invention also discloses a preparation method of the ZnO-BaTaO2N composite photocatalyst. Compared with the prior art, the ZnO-BaTaO2N composite photocatalyst has the following advantages: the compounding of the ZnO and BaTaO2N can greatly widen the spectral response range of the ZnO, so that the ZnO has favorable absorptivity in the visible light region, thereby enhancing the utilization ratio of solar energy; the compounding of the ZnO and BaTaO2N can effectively reduce the compound probability between photogenerated electrons and holes, and enhance the photocatalytic activity of the ZnO.
Description
Technical field
The invention belongs to inorganic environment-friendly catalysis material technical field, be specifically related to a kind of ZnO-BaTaO
2n composite photo-catalyst and preparation method thereof.
Background technology
Due to quantum size effect, bulk effect, macro quanta tunnel effect etc., nano zinc oxide material has important using value in many fields such as power, optical, electrical, magnetic, sensitiveness, particularly at semiconductor photosensitive theoretical side as this challenging field of high efficiency photocatalyst, obtained in recent years people and paid attention to widely and study.Semi-conducting material can be realized luminous energy to chemical transformation of energy by illumination, therefore organic matter, the inorganic matter detoxification in degradation water, remove the aspects such as oxynitrides purifies air, Photocatalitic Technique of Semiconductor has all been obtained huge economy, environmental protection and social benefit, and is more and more valued by the people.
But ZnO energy gap is 3.2 eV, only under being less than the ultraviolet ray of 387 nm, wavelength just can excite its catalytic activity.In arriving the solar energy on ground, the energy of this wave band is less than 5% still, and the ratio of visible light part accounts for 45% left and right of solar energy.In addition, ZnO photochemical catalyst in photocatalytic process light induced electron and hole easily compound, catalytic efficiency is low.Therefore, how to widen ZnO photochemical catalyst spectral response range, improve the Focal point and difficult point that its photo-quantum efficiency becomes the research of photocatalysis section.
BaTaO
2n is a kind of transition metal oxynitride, and because divalence oxygen element part is replaced by the less trivalent nitrogen element of electronegativity, metal cation is more or less reduced, and crystal structure changes, BaTaO
2optical, electrical, magnetic that N thereby performance make new advances, mechanical property.Research shows, BaTaO
2the energy gap of N is 2.0 eV, and energy absorbing wavelength is less than the visible ray of 620 nm, is a kind of catalysis material with visible light-responded ability.In order to widen the spectrum of ZnO, ring scope, by itself and the BaTaO with ideal bandgap
2n is mutually compound, utilizes two kinds of energy level differences between semiconductor can make the photoproduction son that dams be injected on another kind of semi-conductive energy level by a kind of energy level of semiconductive particles, makes electric charge effectively separated, is the effective way that improves ZnO solar energy utilization ratio and photo-quantum efficiency.The conduction band potential E of ZnO photochemical catalyst
cB=-0.31 eV, valence band electromotive force E
vB=2.89 eV, and BaTaO
2the conduction band potential E of N photochemical catalyst
cB=-0.44 eV, valence band electromotive force E
vB=1.56 eV.At ZnO/CaTaO
2in N composite semiconductor, BaTaO
2the conduction band potential of N is more negative, and light induced electron is easily from the low BaTaO of energy level
2n conduction band moves on the ZnO conduction band that energy level is high, meanwhile, the corrigendum of the valence band electromotive force of ZnO, photohole easily moves to from the high ZnO valence band of energy level the BaTaO that energy level is low
2in N valence band, thereby improve the separative efficiency of photogenerated charge, expanded the spectral response range of ZnO.
Summary of the invention
The technical problem that the present invention solves has been to provide the ZnO-BaTaO that a kind of solar energy utilization ratio is high, photocatalytic activity is good
2n composite photo-catalyst.
Another technical problem that the present invention solves has been to provide a kind of simple to operate and ZnO-BaTaO of being easy to control
2the preparation method of N composite photo-catalyst.
Technical scheme of the present invention is: a kind of ZnO-BaTaO
2n composite photo-catalyst, it is characterized in that by ZnO and BaTaO
2compound and the ZnO-BaTaO that forms of N powder
2n composite photo-catalyst, wherein ZnO and BaTaO
2the mol ratio of N is 5-15:1.
ZnO-BaTaO of the present invention
2the preparation method of N composite photo-catalyst, it is characterized in that comprising the following steps: (1) by tantalum pentoxide, brium carbonate and acetone in molar ratio the ratio of 1:2:15 join in agate mortar and to grind evenly, then sample is evenly laid on corundum boat, pack in tube-type atmosphere furnace, under ammonia atmosphere, 950 ℃ of calcinings obtain BaTaO for 20 hours
2n powder; (2) preparation liquor zinci chloridi adds citric acid solution to form transparent mixed solution A under the condition stirring in liquor zinci chloridi, and in mixed solution A, the mol ratio of citric acid and zinc chloride is 1.5:1; (3) under stirring condition by step (1) gained BaTaO
2n powder joins mixed solution A and obtains mixed solution B, zinc chloride and BaTaO in mixed solution B
2the mol ratio of N powder is 5-15:1, then mixed solution B is kept in the water-bath of 60 ℃ 24 hours obtaining to wet gel, and wet gel is dried to obtain xerogel through 110 ℃; (4) step (3) gained xerogel is transferred in Muffle furnace and after 2 hours, obtained having the ZnO-BaTaO of high catalytic activity 400-500 ℃ of maintenance
2n composite photo-catalyst.
ZnO-BaTaO of the present invention
2the preparation method of N composite photo-catalyst, is characterized in that: in described step (2), the molar concentration of liquor zinci chloridi is 0.1-0.3mol/L.ZnO-BaTaO of the present invention
2the preparation method of N composite photo-catalyst, is characterized in that: in described step (2), the molar concentration of citric acid solution is 0.1mol/L.
The present invention compared with prior art has following remarkable advantage: 1, ZnO and BaTaO
2the compound spectral response range that can greatly widen ZnO of N, makes ZnO in visible region, have good absorption, has improved the utilization rate of solar energy; 2, ZnO and BaTaO
2the compound probability of recombination that can effectively reduce light induced electron and hole of N, improves ZnO photocatalytic activity; 3, ZnO-BaTaO of the present invention
2the preparation method of N composite photo-catalyst is simple, easy to control.
Accompanying drawing explanation
Fig. 1 is under the high voltage mercury lamp radiation of 300 W, the ZnO/BaTaO that the embodiment of the present invention 1 is prepared
2n composite photo-catalyst and the commercial ZnO photochemical catalyst correlation curve (operating condition: catalytic amount: 0.5 g/L to rhodamine B degraded situation; The concentration of rhodamine B: 50 mg/L).
The specific embodiment
Below in conjunction with embodiment, further describe the present invention.Be noted that the present invention is not limited to following each embodiment.
Embodiment 1
(1) tantalum pentoxide, brium carbonate and the acetone that amount of substance is respectively to 0.0005mol, 0.001mol, 0.075mol joins in agate mortar and grinds evenly, then sample is evenly laid on corundum boat, pack in tube-type atmosphere furnace, under ammonia atmosphere, 950 ℃ of calcinings obtain BaTaO for 20 hours
2n powder;
(2) compound concentration is liquor zinci chloridi and the citric acid solution of 0.1mol/L, under the condition stirring, is to form transparent mixed solution A during 0.1mol/L citric acid solution joins the liquor zinci chloridi that 50mL molar concentration is 0.1mol/L by 75mL molar concentration;
(3) under stirring condition by step (1) gained BaTaO
2n powder joins mixed solution A and obtains mixed solution B, then mixed solution B is kept in the water-bath of 60 ℃ 24 hours obtaining to wet gel, and wet gel is dried to obtain xerogel through 110 ℃;
(4) step (3) gained xerogel is transferred in Muffle furnace and after 2 hours, obtained having the ZnO-BaTaO of high catalytic activity 400 ℃ of maintenances
2n composite photo-catalyst.The ZnO-BaTaO preparing as seen from Figure 1
2n composite photo-catalyst and TiO
2photochemical catalyst is compared has higher degradation rate under identical degradation time, so ZnO-BaTaO
2n composite photo-catalyst has not only improved photocatalytic activity, has good photocatalysis effect, has also improved the utilization ratio to solar energy simultaneously.
Embodiment 2
(1) tantalum pentoxide, brium carbonate and the acetone that amount of substance is respectively to 0.0005mol, 0.001mol, 0.075mol joins in agate mortar and grinds evenly, then sample is evenly laid on corundum boat, pack in tube-type atmosphere furnace, under ammonia atmosphere, 950 ℃ of calcinings obtain BaTaO for 20 hours
2n powder;
(2) preparation molar concentration is that 0.2mol/L liquor zinci chloridi and molar concentration are 0.1mol/L citric acid solution, under the condition stirring, is to form transparent mixed solution A during 0.1mol/L citric acid solution joins the liquor zinci chloridi that 50mL molar concentration is 0.2mol/L by 150mL molar concentration;
(3) under stirring condition by step (1) gained BaTaO
2n powder joins mixed solution A and obtains mixed solution B, then mixed solution B is kept in the water-bath of 60 ℃ 24 hours obtaining to wet gel, and wet gel is dried to obtain xerogel through 110 ℃;
(4) step (3) gained xerogel is transferred in Muffle furnace and after 2 hours, obtained having the ZnO-BaTaO of high catalytic activity 450 ℃ of maintenances
2n composite photo-catalyst.
Embodiment 3
(1) tantalum pentoxide, brium carbonate and the acetone that amount of substance is respectively to 0.0005mol, 0.001mol, 0.075mol joins in agate mortar and grinds evenly, then sample is evenly laid on corundum boat, pack in tube-type atmosphere furnace, under ammonia atmosphere, 950 ℃ of calcinings obtain BaTaO for 20 hours
2n powder;
(2) preparation molar concentration is that 0.3mol/L liquor zinci chloridi and molar concentration are 0.1mol/L citric acid solution, under the condition stirring, is to form transparent mixed solution A during 0.1mol/L citric acid solution joins the liquor zinci chloridi that 50mL molar concentration is 0.3mol/L by 300mL molar concentration;
(3) under stirring condition by step (1) gained BaTaO
2n powder joins mixed solution A and obtains mixed solution B, then mixed solution B is kept in the water-bath of 60 ℃ 24 hours obtaining to wet gel, and wet gel is dried to obtain xerogel through 110 ℃;
(4, step (3) gained xerogel is transferred in Muffle furnace to the ZnO-BaTaO that obtains having high catalytic activity at 500 ℃ after keeping 2 hours
2n composite photo-catalyst.
Above embodiment has described basic principle of the present invention, principal character and advantage.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and description, describes just illustrates principle of the present invention; do not departing under the scope of the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.
Claims (4)
1. a ZnO-BaTaO
2n composite photo-catalyst, it is characterized in that by ZnO and BaTaO
2compound and the ZnO-BaTaO that forms of N powder
2n composite photo-catalyst, wherein ZnO and BaTaO
2the mol ratio of N is 5-15:1.
2. a ZnO-BaTaO claimed in claim 1
2the preparation method of N composite photo-catalyst, it is characterized in that comprising the following steps: (1) by tantalum pentoxide, brium carbonate and acetone in molar ratio the ratio of 1:2:15 join in agate mortar and to grind evenly, then sample is evenly laid on corundum boat, pack in tube-type atmosphere furnace, under ammonia atmosphere, 950 ℃ of calcinings obtain BaTaO for 20 hours
2n powder; (2) preparation liquor zinci chloridi adds citric acid solution to form transparent mixed solution A under the condition stirring in liquor zinci chloridi, and in mixed solution A, the mol ratio of citric acid and zinc chloride is 1.5:1; (3) under stirring condition by step (1) gained BaTaO
2n powder joins mixed solution A and obtains mixed solution B, zinc chloride and BaTaO in mixed solution B
2the mol ratio of N powder is 5-15:1, then mixed solution B is kept in the water-bath of 60 ℃ 24 hours obtaining to wet gel, and wet gel is dried to obtain xerogel through 110 ℃; (4) step (3) gained xerogel is transferred in Muffle furnace and after 2 hours, obtained having the ZnO-BaTaO of high catalytic activity 400-500 ℃ of maintenance
2n composite photo-catalyst.
3. ZnO-BaTaO according to claim 2
2the preparation method of N composite photo-catalyst, is characterized in that: in described step (2), the molar concentration of liquor zinci chloridi is 0.1-0.3mol/L.
4. ZnO-BaTaO according to claim 2
2the preparation method of N composite photo-catalyst, is characterized in that: in described step (2), the molar concentration of citric acid solution is 0.1mol/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314477A1 (en) * | 2000-08-28 | 2003-05-28 | Japan Science and Technology Corporation | Photocatalyst comprising metal oxynitride responsive to visible light |
| CN101204652A (en) * | 2007-12-19 | 2008-06-25 | 中国科学院上海硅酸盐研究所 | High efficiency semiconductor photocatalysis and preparation method thereof |
| CN102000591A (en) * | 2010-11-03 | 2011-04-06 | 哈尔滨工业大学 | Composite photocatalyst and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314477A1 (en) * | 2000-08-28 | 2003-05-28 | Japan Science and Technology Corporation | Photocatalyst comprising metal oxynitride responsive to visible light |
| CN101204652A (en) * | 2007-12-19 | 2008-06-25 | 中国科学院上海硅酸盐研究所 | High efficiency semiconductor photocatalysis and preparation method thereof |
| CN102000591A (en) * | 2010-11-03 | 2011-04-06 | 哈尔滨工业大学 | Composite photocatalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YOUNG-IL KIM，ET AL.: "Characterization of the Structural, Optical, and Dielectric Properties of Oxynitride Perovskites AMO2N(A＝Ba, Sr, Ca; M＝Ta, Nb)", 《CHEM. MATER.》, vol. 16, no. 7, 9 March 2004 (2004-03-09), pages 1267 - 1276 * |
| 苑亚斐: "氧化锌复合纳米材料的制备及其光催化性质的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, 15 October 2012 (2012-10-15) * |
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