CN102500361A - Ternary neterogeny structural light degradation organic matter catalyst TiO2-Bi2MoO6/Bi3.64Mo0.36O6.55 and preparation method thereof - Google Patents
Ternary neterogeny structural light degradation organic matter catalyst TiO2-Bi2MoO6/Bi3.64Mo0.36O6.55 and preparation method thereof Download PDFInfo
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- CN102500361A CN102500361A CN2011103398375A CN201110339837A CN102500361A CN 102500361 A CN102500361 A CN 102500361A CN 2011103398375 A CN2011103398375 A CN 2011103398375A CN 201110339837 A CN201110339837 A CN 201110339837A CN 102500361 A CN102500361 A CN 102500361A
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Abstract
Disclosed is ternary neterogeny structural light degradation organic matter catalyst 5% TiO2-Bi2MoO6/Bi3.64Mo0.36O6.55, which consists titanium dioxide (TiO2) and two types of dibismuth trimolybdenum dodecaoxide (Bi2MoO6 and Bi3.64Mo0.36O6.55) with different structures, wherein the titanium dioxide is 5% of total mole number of bismuth elements. The ternary neterogeny structural light degradation organic matter catalyst 5% TiO2-Bi2MoO6/Bi3.64Mo0.36O6.55 has the advantages that the catalyst is the ternary neterogeny structural light degradation organic matter catalyst reported for the first time; 2, the catalyst is directly synthesized by a one-step hydrothermal method, is simple in operation, low in production cost, high in synthesis yield and purity, fine in repeatability, and meets requirements of batch production; 3, the catalyst is fine in thermal stability and is high in acid resistance and alkali resistance; and 4, the catalyst has a good photocatalytic degradation organic effect, and has a higher catalysis effect as compared with single titanium dioxide, dibismuth trimolybdenum dodecaoxide (Bi2MoO6 and Bi3.64Mo0.36O6.55) and an optional combination (TiO2-Bi2MoO6, TiO2-Bi3.64Mo0.36O6.55 and Bi2MoO6/Bi3.64Mo0.36O6.55) among the single titanium dioxide and the dibismuth trimolybdenum dodecaoxide (Bi2MoO6 and Bi3.64Mo0.36O6.55).
Description
Technical field
The present invention relates to a kind of light degradation catalytic organism agent and preparation method thereof, relate in particular to a kind of ternary heterojunction structure light degradation catalytic organism agent 5%TiO
2-Bi
2MoO
6/ Bi
3.64Mo
0.36O
6.55And preparation method thereof.
Background technology
Along with the live raising of life of the development of society and people, industrial wastewater and sanitary sewage account for the pith of environmental pollution, and becoming people must not irrespective major issue.In China, generally take physics method, chemical method and bioanalysis three major types for the processing of sewage.For example, noxious material is adsorbed in the physics method with active carbon, this method just pollutant from a phase transfer to another phase, itself is not thoroughly degraded pollutant, the processing of the active carbon after the absorption pollutant also is a problem; And chemical method often relates to the use chemical agent; In chemical reaction process, pollutant is carried out oxidation or deoxidization, degradation, change the form of pollutant, they are become the novel substance of nontoxic or little poison; Perhaps change into the form of easy and separated form water, thereby reach the purpose of processing.But this method needs a large amount of chemical agents, and operating cost is higher, is not suitable for extensive scope and uses, and simultaneously, also might produce secondary pollution.As everyone knows; Utilize the microbial metabolism effect; The method that makes organic pollution and inorganic nutrients thing in the waste water be converted into stable, harmless material is called biological treatment; This is current relatively more novel method for treating water, yet biodegradation still exists certain limitation, summarize get up to have following some: the effect of (1) bacterium has selectivity: (2) degradation speed is slow; Generally want several weeks or several months: (3) can only partly degrade to some noxious material, and possibly form virose intermediate product; (4) aromatic compound partly is difficult to be degraded.See from present domestic operation conditions; Though oneself is ripe for these three kinds of some technologies of processing method, and its limitation is respectively arranged, operating cost is also not very low; Treatment effeciency also is that height does not wait, and particularly can not remove some organic pollutions of low concentration in the water and bio-refractory effectively.Therefore, the environmental protection treatment technology of development novel practical remains the target that people pursue.
Fujishima in 1972 and Honda have delivered about TiO on the Nature magazine
2The paper of electrode glazing decomposition water indicates the beginning of photocatalysis New Times.Carey in 1976 etc. have reported under the irradiation of ultraviolet light, and the Polychlorinated biphenyls in the water, chloralkane etc. can be at TiO
2Effective dechlorination reaction takes place down in the existence of photochemical catalyst, and the report of this research makes people recognize the mineralising elimination function of semiconductor catalyst to organic pollution.Henceforth, utilize the pollutant in conductor photocatalysis degraded and the elimination environment just to become most active fields in the conductor photocatalysis research.But because TiO
2Broad stopband (3.2eV), can only respond the ultraviolet light below 387.5 nnl, then utilization ratio is lower to the visible light that accounts for the overwhelming majority in the solar spectrum, thereby has limited nano-TiO
2Industrial applications development.Therefore developing efficiently, the photochemical catalyst of visible light-inducing has profound significance.And the bismuth molybdate synthetic method is simple, and raw material are cheap, and visible light is had good absorption, becomes another focus of people's research.
Summary of the invention
The object of the present invention is to provide a kind of ternary heterojunction structure light degradation catalytic organism agent TiO
2-Bi
2MoO
6/ Bi
3.64Mo
0.36O
6.55And preparation method thereof, for organic catalytic degradation provides a kind of new material.Material of the present invention is to adopt Hydrothermal Preparation, and it is simple to operate, low production cost, productive rate are higher, and its photocatalytic degradation speed is high, is fit to the requirement that extension is produced.
The present invention realizes like this, it is characterized in that catalyst is by titanium dioxide (TiO
2) and the bismuth molybdate (Bi of two kinds of different structures
2MoO
6And Bi
3.64Mo
0.36O
6.55) form, wherein titanium dioxide is 5% of total bismuth element molal quantity.Under the inducing of visible light, the catalyst of 0.1 gram can be 10 with 100 ml concns
-5The rhodamine B of mol is degraded fully at 2 hours.
A kind of ternary heterojunction structure light degradation catalytic organism agent 5%TiO
2-Bi
2MoO
6/ Bi
3.64Mo
0.36O
6.55The preparation method be: earlier the bismuth nitrate of 5 mMs is uniformly dispersed in 15 ml deionized water, the ammonium molybdate solution with 10 milliliter of 0.25 mol slowly joins in the above-mentioned aqueous solution then, stirs to obtain A solution.With 0.125 mM butyl titanate add 10 milliliters ethanol, stir, obtain solution B.Then solution B is slowly fallen as in the solution A; Stirring at normal temperature 30 minutes adds the sodium hydroxide solution of 5 mol, with the pH value modulation 7.5 of solution; Above-mentioned solution is packed in 100 milliliters the agitated reactor of polytetrafluoroethylene (PTFE), put into 150 ℃ Muffle furnace calcining 5 hours then.Sample after the calcining is carried out putting into 300 ℃ of calcinings of Muffle furnace 5 hours after multiple times of filtration, the washing, obtain the target catalyst.
Advantage of the present invention is: 1, material preparation of the present invention is to adopt hydro-thermal method, and it is simple to operate, low production cost, productive rate are higher, and the also very high and good reproducibility of purity is fit to the requirement that extension is produced; 2, material Heat stability is good of the present invention, and acidproof, alkali resistance is strong; 3, the resulting catalyst of the present invention has the effect of photocatalytic degradation rhodamine B preferably.
Description of drawings
Fig. 1 is the X-ray powder diffraction figure of catalyst material of the present invention and two kinds of different structure bismuth molybdates.
Fig. 2 is the comparison diagram of catalyst of the present invention and other light degradation effects under visible light-inducing.
Fig. 3 is the Raman spectrogram of the titanium dioxide of the different amounts of catalyst cupport of the present invention.
In Fig. 21, catalyst 2, Bi
2MoO
6/ Bi
3.64Mo
0.36O
6.553, Bi
2MoO
6
4、5%TiO
2-Bi
2MoO
6 5、Bi
3.64Mo
0.36O
6.55 6、5%TiO
2-Bi
3.64Mo
0.36O
6.55。
The specific embodiment
Synthesizing of catalyst material of the present invention:
Earlier the bismuth nitrate of 5 mMs is uniformly dispersed in 15 ml deionized water, the ammonium molybdate solution with 10 milliliter of 0.25 mol slowly joins in the above-mentioned aqueous solution then, stirs to obtain A solution.With 0.125 mM butyl titanate add 10 milliliters ethanol, stir, obtain solution B.Then B solution is slowly fallen as among the A; Stirring at normal temperature 30 minutes adds the sodium hydroxide solution of 5 mol, with the pH value modulation 7.5 of solution; Above-mentioned solution is packed in 100 milliliters the agitated reactor of polytetrafluoroethylene (PTFE), put into 150 ℃ Muffle furnace calcining 5 hours then.Sample after the calcining is carried out putting into 300 ℃ of calcinings of Muffle furnace 5 hours after multiple times of filtration, the washing, obtain the target catalyst.
Like Fig. 1, Fig. 2, shown in Figure 3, through the X-ray powder diffraction test shows, the diffraction pattern of catalyst of the present invention is the mixture (Bi of the bismuth molybdate of two kinds of different structures
2MoO
6And Bi
3.64Mo
0.36O
6.55), and the peak of titanium dioxide does not appear in the diffraction pattern, this can explain that catalyst material of the present invention is not the mixture of bismuth molybdate and titanium dioxide.Do not find the peak of tangible titanium dioxide in addition in the Raman spectrum test shows in its spectrogram.Titanium dioxide is 5% (mol ratio) of total bismuth element molal quantity in the XRF test shows catalyst material of the present invention.Therefore combining the provable catalyst material of the present invention of above test is to be that 5% titanium dichloride load is at bismuth molybdate (Bi by mol ratio
2MoO
6And Bi
3.64Mo
0.36O
6.55) the ternary heterojunction structure new material that forms.Under the condition of visible light, 0.1 the gram catalyst system can with 100 milliliters 10
-5The rhodamine B of mol is degraded fully at 2 hours.Preparation is to adopt one step hydro thermal method, and it is simple to operate, low production cost, synthetic productive rate are higher, and the also very high and good reproducibility of purity is fit to the requirement that extension is produced; Material Heat stability is good of the present invention, and acidproof, alkali resistance is strong; The resulting material of the present invention has photocatalysis to degrade organic matter effect preferably, for the organic pollution in the later light degradation sewage provides the new material source.
Claims (2)
1. ternary heterojunction structure light degradation catalytic organism agent 5%TiO
2-Bi
2MoO
6/ Bi
3.64Mo
0.36O
6.55, it is by the Bi of titanium dioxide and two kinds of different structures
2MoO
6With Bi
3.64Mo
0.36O
6.55Form, wherein titanium dioxide is 2.5% of total bismuth element molal quantity, under the inducing of visible light, rhodamine B is had good degradation effect.
2. the described ternary heterojunction structure of claim 1 light degradation catalytic organism agent 5%TiO
2-Bi
2MoO
6/ Bi
3.64Mo
0.36O
6.55The preparation method, it is characterized in that: earlier the bismuth nitrate of 5 mMs is uniformly dispersed in 15 ml deionized water, the ammonium molybdate solution with 10 milliliter of 0.25 mol slowly joins in the above-mentioned aqueous solution then; Stirring obtains A solution, with 0.125 mM butyl titanate add 10 milliliters ethanol, stir; Obtain solution B, then solution B is slowly fallen as in the solution A stirring at normal temperature 30 minutes; The sodium hydroxide solution that adds 5 mol; With the pH value of solution modulation 7.5, above-mentioned solution is packed in 100 milliliters the agitated reactor of polytetrafluoroethylene (PTFE), put into 150 ℃ Muffle furnace calcining 5 hours then; Sample after the calcining is carried out putting into 300 ℃ of calcinings of Muffle furnace 5 hours after multiple times of filtration, the washing, obtain the target catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801340A (en) * | 2013-07-24 | 2014-05-21 | 南昌航空大学 | Photocatalytic degradation organic matter pollutant catalyst TiO2/Co4S4.23Se3.77 as well as preparation method thereof |
| CN103962158A (en) * | 2014-04-30 | 2014-08-06 | 南昌航空大学 | Ternary hetero-structured photo-degradation organic catalyst WS2-Bi2WO6/Bi3.84W0.16O6.24 and preparation method thereof |
| CN105536772A (en) * | 2015-12-23 | 2016-05-04 | 东南大学 | Preparation method for heterojunction nano-photocatalysis material and application of material |
| CN106984299A (en) * | 2017-05-27 | 2017-07-28 | 北方民族大学 | Hydrothermal Synthesiss three-dimensional Bi4MoO9/TiO2The method of nanostructure heterojunction |
| CN109589966A (en) * | 2019-01-21 | 2019-04-09 | 合肥学院 | A kind of hetero-junctions TiO2@Bi3.64Mo0.36O6.55The preparation method of nano composite photo-catalyst |
| CN114249544A (en) * | 2022-03-01 | 2022-03-29 | 青岛理工大学 | Z-shaped heterojunction composite photo-anode membrane, one-step hydrothermal preparation method and application thereof |
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2011
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801340A (en) * | 2013-07-24 | 2014-05-21 | 南昌航空大学 | Photocatalytic degradation organic matter pollutant catalyst TiO2/Co4S4.23Se3.77 as well as preparation method thereof |
| CN103801340B (en) * | 2013-07-24 | 2015-12-02 | 南昌航空大学 | A kind of photocatalysis to degrade organic matter contaminant catalyst TiO 2/ Co 4s 4.23se 3.77and preparation method thereof |
| CN103962158A (en) * | 2014-04-30 | 2014-08-06 | 南昌航空大学 | Ternary hetero-structured photo-degradation organic catalyst WS2-Bi2WO6/Bi3.84W0.16O6.24 and preparation method thereof |
| CN103962158B (en) * | 2014-04-30 | 2015-12-02 | 南昌航空大学 | A kind of ternary heterojunction light degradation catalytic organism agent WS 2-Bi 2wO 6/ Bi 3.84w 0.16o 6.24and preparation method thereof |
| CN105536772B (en) * | 2015-12-23 | 2018-03-20 | 东南大学 | A kind of preparation method of hetero-junctions nano-photocatalyst material and the application of the material |
| CN105536772A (en) * | 2015-12-23 | 2016-05-04 | 东南大学 | Preparation method for heterojunction nano-photocatalysis material and application of material |
| CN106984299A (en) * | 2017-05-27 | 2017-07-28 | 北方民族大学 | Hydrothermal Synthesiss three-dimensional Bi4MoO9/TiO2The method of nanostructure heterojunction |
| WO2018218728A1 (en) * | 2017-05-27 | 2018-12-06 | 北方民族大学 | Method for hydrothermal synthesis of three-dimensional bi4moo9/tio2 nanostructured heterojunction |
| CN106984299B (en) * | 2017-05-27 | 2019-04-23 | 北方民族大学 | Hydrothermal synthesis three-dimensional Bi4MoO9/TiO2The method of nanostructure heterojunction |
| US10486138B2 (en) * | 2017-05-27 | 2019-11-26 | Beifang Minzu University | Method for hydrothermal synthesis of three dimensional Bi4MoO9/TiO2 nanostructure heterojunction |
| CN109589966A (en) * | 2019-01-21 | 2019-04-09 | 合肥学院 | A kind of hetero-junctions TiO2@Bi3.64Mo0.36O6.55The preparation method of nano composite photo-catalyst |
| CN114249544A (en) * | 2022-03-01 | 2022-03-29 | 青岛理工大学 | Z-shaped heterojunction composite photo-anode membrane, one-step hydrothermal preparation method and application thereof |
| CN114249544B (en) * | 2022-03-01 | 2022-05-20 | 青岛理工大学 | Z-type heterojunction composite photo-anode membrane, one-step hydrothermal preparation method and application thereof |
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Inventor after: Zou Jianping Inventor after: Zhang Longzhu Inventor after: Xing Qiuju Inventor after: Lin Fangcheng Inventor after: Ding Lin Inventor after: Dai Shunchen Inventor before: Zhang Longzhu Inventor before: Zou Jianping Inventor before: Lin Fangcheng Inventor before: Ding Lin Inventor before: Dai Shunchen Inventor before: Xing Qiuju |
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Free format text: CORRECT: INVENTOR; FROM: ZHANG LONGZHU ZOU JIANPING LIN FANGCHENG DING LIN DAI SHUNCHEN XING QIUJU TO: ZOU JIANPING ZHANG LONGZHU XING QIUJU LIN FANGCHENG DING LIN DAI SHUNCHEN |