CN107021525A - A kind of preparation method of high-purity birnessite type Mn oxide of efficient degradation of organic dye - Google Patents
A kind of preparation method of high-purity birnessite type Mn oxide of efficient degradation of organic dye Download PDFInfo
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- CN107021525A CN107021525A CN201610067326.5A CN201610067326A CN107021525A CN 107021525 A CN107021525 A CN 107021525A CN 201610067326 A CN201610067326 A CN 201610067326A CN 107021525 A CN107021525 A CN 107021525A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention discloses a kind of preparation method of high-purity birnessite with three dimensional micron floral structure of energy efficient degradation of organic dye.This method adds appropriate complexing agent using soluble manganese salt as manganese source in above-mentioned manganese salt solution, obtains high-purity birnessite with three dimensional micron floral structure in the basic conditions using air oxidation process.Birnessite degradating organic dye methylene blue (MB), methyl orange (MO) and rhodamine B (RhB) prepared by the above method test result indicates that：Without any oxidant such as hydrogen peroxide, persulfate, not by any auxiliary equipment such as ultrasound, microwave under the premise of, the efficient degradation to above-mentioned dyestuff can be only realized in acid condition.The preparation method raw material is cheap and easy to get, and preparation process is simple, time saving and energy saving, and what, effect simple to degradation of organic dyes condition significantly made the pollution of industrial organic dyestuff is treated as possibility.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity birnessite type Mn oxide of energy efficient degradation of organic dye, belong to material
Preparing technical field.
Background technology
Birnessite is a kind of two-dimensional layer Mn oxide, with unique crystal structure, its lamella by manganese oxygen octahedra altogether side or
Corner-sharing is constituted, and interlayer is by Na+Or other metal ions, and hydrone mutually occupies filling.The work(of birnessite its own and synthesis
Energy material is all widely used in terms of light, electricity, magnetic, catalysis.In recent years, the synthesis of birnessite is obtained with application study
Extensive attention is arrived.
At present, the synthesis of birnessite mainly has following several approach：(1) sol-gal process is used, is reduced using organic matter high
Potassium manganate；(2) in acid condition, hydrothermal decomposition potassium permanganate；(3) in the basic conditions, the soluble manganese salt of oxidizing process.
First two method needs the reaction time longer, or needs to post-process under hot conditions, takes time and effort；Prepared by the third method
Birnessite usually contains impurities phase.The deficiency that above method is present all limits the practical application of birnessite.The present invention is in water
On the basis of solution air oxidation process, the method that complexing agent is added in soluble manganese salt is successfully prepared high-purity birnessite,
The deficiency in the above method is overcome, and time saving and energy saving, favorable repeatability.Moreover, the birnessite of preparation is only in acidity
Under the conditions of can realize the efficient degradation to organic dyestuff methylene blue (MB), methyl orange (MO) and rhodamine B (RhB), be work
A large amount of processing of organic dyestuff provide possible in industry.
The content of the invention
The deficiency that the present invention exists for the preparation method of existing birnessite, it is proposed that one kind simply prepares high purity water sodium manganese
The method of ore deposit, and the birnessite in acid condition just can efficient degradation of organic dye RhB.The preparation method raw material is inexpensively easy
, preparation process is simple, repeatability is strong, and product purity is high, and without any oxidant such as hydrogen peroxide, persulfuric acid
Salt, in an acidic solution can efficient degradation RhB not by any supplementary means such as ultrasound, under conditions of microwave.
The preparation of a kind of high-purity birnessite of the present invention, it is characterised in that comprise the following steps：
A. soluble manganese salting liquid is uniformly mixed with complexing agent：Wherein the concentration of manganese salt is 0.12.0mol/L, the concentration of complexing agent
For 0.1~0.4mol/L；Manganese salt and EDTA-Na mol ratio are 1:1~5:1；
B. strong alkali solution is prepared, its concentration is 0.2~2.0mol/L；
C. under fast stirring, step b is matched somebody with somebody into solution to be added dropwise in step a mixed solutions；
D. continue to stir a period of time after reaction terminates；
E. filtering precipitation, is washed with deionized 3 times, certain time is dried under certain condition, product is obtained.
The soluble manganese salt includes manganese sulfate, manganese nitrate, manganese chloride, manganese acetate etc.；Complexing agent includes trisodium citrate, second
Edetate disodium etc.；
The strong alkali solution is sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide；
The rate of addition of the aqueous slkali is 1~10mL/min；
It is described reaction terminate after under agitation ageing time be 2~48h；
2~24h is dried under the conditions of 30~80 DEG C after the precipitation filtering.
The application of high-purity birnessite prepared by the present invention, it is characterised in that the birnessite type Mn oxide of preparation is to organic dyestuff bag
Include but be not limited to methylene blue, rhodamine B, methyl orange etc. has notable degradation；And degradation process is only in acidity (pH<5)
Under the conditions of 10mg samples be that can be achieved to the efficient degradation of 50mL 10~100mg/L organic dyestuff, and this degradation process is no longer
Any other auxiliary agent is added, also not by any auxiliary equipment such as ultrasound, microwave.
Advantages of the present invention is mainly reflected in：
Raw material is cheap and easy to get, using air oxidation process, non-environmental-pollution, and preparation process is simple, time saving and energy saving to be easy to extensive life
Production；
Degradation condition is gentle, and effect is notable, catabolite non-secondary pollution thing；
Product purity is high, and possibility is provided for its application in other side.
Brief description of the drawings
Fig. 1, (a) and (b) is the XRD and FESEM figures of the product of embodiment 1 respectively；
Fig. 2, (a) and (b) is the XRD and FESEM figures of the product of embodiment 3 respectively；
Fig. 3, (a) and (b) is the XRD and FESEM figures of the product of embodiment 5 respectively；
Fig. 4, (a) and (b) is the XRD and FESEM figures of the product of embodiment 7 respectively；
Fig. 5, RhB UV, visible lights of being degraded by taking the gained birnessite of embodiment 1 as an example change over time collection of illustrative plates；
Fig. 6, (a), (b) and (c) are respectively by taking embodiment 3,5 and 7 gained birnessites as an example, MB, MO and RhB degraded
Rate changes with time.
Embodiment
The application of the present invention includes but is not limited only to following embodiment.
Embodiment 1：
First, 1.2g NaOH are weighed to be dissolved in 50mL deionized waters；Secondly, 1.352g (8mmol) is accurately weighed respectively
MnSO4·H2O, 2.992g (8mmol) EDTA-Na is dissolved in 25ml deionized waters；Under quick stirring, by NaOH solution
MnSO is added drop-wise to 3mL/min4With in EDTA-Na mixed solutions, after completion of dropping continuation stirring aging 2h, crossing diafiltration
Wash precipitation for several times, after be placed in 12h at 40 DEG C of vacuum drying chamber, obtain high-purity birnessite.
XRD detections are carried out to the sample of preparation, shown in such as Fig. 1 (a), product is high-purity birnessite, and crystallinity is higher,
Fig. 1 (b) schemes for its FESEM.It is accurate weigh 10mg samples and be added to fill in 50ml 10mg/L RhB volumetric flasks, surpass
Sound 5min makes sample be dispersed in solution, recycles H2SO4PH value of solution is adjusted to 1, the 1st, 3,5 and 10min
3mL is sampled, centrifuging and taking supernatant liquor measures its concentration using UV-vis, calculates its degradation rate.Its UV-vis such as Fig. 5 institutes
Show, at 10min ends, RhB has been completely degraded.
Embodiment 2：
First, 2.4g NaOH are weighed to be dissolved in 50mL deionized waters；Secondly, 1.352g (8mmol) is accurately weighed respectively
MnSO4·H2O, 2.992g (8mmol) EDTA-Na is dissolved in 25ml deionized waters；It is under quick stirring, NaOH is molten
Liquid is added drop-wise to MnSO with 6mL/min4With in EDTA-Na mixed solutions, after completion of dropping continuation stirring aging 2h, filtering
Washing precipitation for several times, after be placed in 12h at 40 DEG C of vacuum drying chamber, obtain high-purity birnessite.
Embodiment 3：
First, 1.2g NaOH are weighed to be dissolved in 50mL deionized waters；Secondly, 2.704g (16mmol) is accurately weighed respectively
MnSO4·H2O, 4.984g (16mmol) EDTA-Na is dissolved in 100ml deionized waters；Under quick stirring, by NaOH
Solution is added drop-wise to MnSO with 6mL/min4With in EDTA-Na mixed solutions, completion of dropping continues to stir after aging 2h, mistake
Filter washing precipitate for several times, after be placed in 6h at 80 DEG C of vacuum drying chamber, obtain high-purity birnessite sample.
XRD detections are carried out to the sample of preparation, shown in such as Fig. 2 (a), product is high-purity birnessite, and crystallinity is higher,
Fig. 2 (b) schemes for its FESEM.It is accurate weigh 10mg samples and be added to fill 50ml 10mg/L MB (methylene blue) capacity
In bottle, ultrasonic 5min makes sample be dispersed in solution, recycles H2SO4PH value of solution is adjusted to 1, the 1st, 3,5
3mL is sampled with 10min, centrifuging and taking supernatant liquor measures its concentration using UV-vis, calculates its degradation rate.MB drop
Solution rate changes with time as shown in Fig. 6 (a).In 5min, degradation rate reaches that more than 96%, 10min is then degradable.
Embodiment 4：
First, 1.2g NaOH are weighed to be dissolved in 50mL deionized waters；Secondly, 2.704g (16mmol) is accurately weighed respectively
MnSO4·H2O, 2.992g (8mmol) EDTA-Na is dissolved in 100ml deionized waters；It is under quick stirring, NaOH is molten
Liquid is added drop-wise to MnSO with 6mL/min4With in EDTA-Na mixed solutions, completion of dropping continues to stir after aging 12h, mistake
Filter washing precipitate for several times, after be placed in 6h at 80 DEG C of vacuum drying chamber, obtain high-purity birnessite sample.
Embodiment 5：
First, 1.2g NaOH are weighed to be dissolved in 50mL deionized waters；Secondly, 0.676g (4mmol) is accurately weighed respectively
MnSO4·H2O, 2.992g (8mmol) EDTA-Na is dissolved in 50ml deionized waters；It is under quick stirring, NaOH is molten
Liquid is added drop-wise to MnSO with 6mL/min4With in EDTA-Na mixed solutions, completion of dropping continues to stir after aging 24h, mistake
Filter washing precipitate for several times, after be placed in 6h at 80 DEG C of vacuum drying chamber, obtain high-purity birnessite sample.
XRD detections are carried out to the sample of preparation, shown in such as Fig. 3 (a), product is high-purity birnessite, and crystallinity is higher,
Fig. 3 (b) schemes for its FESEM.It is accurate weigh 10mg samples and be added to fill 50ml 10mg/L MO (methyl orange) capacity
In bottle, ultrasonic 5min makes sample be dispersed in solution, recycles H2SO4PH value of solution is adjusted to 1, the 1st, 3,5
3mL is sampled with 10min, centrifuging and taking supernatant liquor measures its concentration using UV-vis, calculates its degradation rate.MO drop
Solution rate changes with time as shown in Fig. 6 (b).In 5min, degradation rate reaches that more than 95%, 10min is then degradable.
Embodiment 6：
First, 3.6g NaOH are weighed to be dissolved in 50mL deionized waters；Secondly, 0.676g (4mmol) is accurately weighed respectively
MnSO4·H2O, 2.992g (8mmol) EDTA-Na is dissolved in 50ml deionized waters；It is under quick stirring, NaOH is molten
Liquid is added drop-wise to MnSO with 8mL/min4With in EDTA-Na mixed solutions, completion of dropping continues to stir after aging 48h, mistake
Filter washing precipitate for several times, after be placed in 12h at 60 DEG C of vacuum drying chamber, obtain high-purity birnessite sample.
Embodiment 7：
First, 3.6g NaOH are weighed to be dissolved in 50mL deionized waters；Secondly, 3.380g (20mmol) is accurately weighed respectively
MnSO4H2O, 2.992g (8mmol) EDTA-Na is dissolved in 50ml deionized waters；It is under quick stirring, NaOH is molten
Liquid is added drop-wise to MnSO4 with 8mL/min and in EDTA-Na mixed solutions, completion of dropping continues to stir after aging 24h, mistake
Filter washing precipitate for several times, after be placed in 24h at 30 DEG C of vacuum drying chamber, obtain high-purity birnessite sample.
XRD detections are carried out to the sample of preparation, shown in such as Fig. 4 (a), product is high-purity birnessite, and crystallinity is higher,
Fig. 4 (b) schemes for its FESEM.It is accurate weigh 10mg samples and be added to fill in 50ml 10mg/L RhB volumetric flasks, surpass
Sound 5min makes sample be dispersed in solution, recycles H2SO4PH value of solution is adjusted to 1, the 1st, 3,5 and 10min
3mL is sampled, centrifuging and taking supernatant liquor measures its concentration using UV-vis, calculates its degradation rate.RhB degradation rate is at any time
Between change such as Fig. 6 (c) shown in.In 5min, degradation rate reaches that more than 97%, 10min is then degradable.
Claims (5)
1. a kind of preparation method of high-purity birnessite type Mn oxide with three dimensional micron floral structure of energy efficient degradation of organic dye, preparation method comprises the following steps：
A. soluble manganese salting liquid is uniformly mixed with complexing agent：Wherein soluble manganese salinity is 0.1~2.0mol/L, and complexing agent concentration is 0.1~0.4mol/L；Soluble manganese salt and the mol ratio of complexing agent are 1:1~5:1；
B. strong alkali solution is prepared, its concentration is 0.2~2.0mol/L；
C. under fast stirring, step b is matched somebody with somebody into solution to be added dropwise in step a mixed solutions；
D. continue to stir aging for a period of time after reaction terminates；
E. filtering precipitation, is washed with deionized 3 times, certain time is dried under certain condition, product is obtained.
2. preparation method according to claim 1, it is characterised in that soluble manganese salt is manganese sulfate, manganese nitrate, manganese chloride, manganese acetate etc.；Complexing agent be citric acid, trisodium citrate/potassium/rubidium/caesium/etc. citric acid univalent metal salt, ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate etc..
3. preparation method according to claim 1, it is characterised in that strong alkali solution is sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide etc.；The rate of addition of strong base solution is 1~10mL/min.
4. preparation method according to claim 1, it is characterised in that 2~24h of aging under agitation after reaction terminates；2~24h is dried after filtering under the conditions of 30~80 DEG C.
5. according to the method described in claim 1, it is characterised in that the birnessite type Mn oxide of preparation has notable degradation to organic dyestuff methylene blue, rhodamine B, methyl orange etc.；Degradation process is only in acidity (pH<5) 10mg samples are that the efficient degradation to 50mL 10~100mg/L organic dyestuff can be achieved under the conditions of, and this degradation process no longer adds any other auxiliary agent, also not by any auxiliary equipment such as ultrasound, microwave.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108128839A (en) * | 2018-01-03 | 2018-06-08 | 中国农业大学 | A kind of method for treating water of carbon-based auxiliary agent fortifying catalytic persulfate |
| CN110386624A (en) * | 2019-08-19 | 2019-10-29 | 西安理工大学 | The preparation method of ultraviolet photosensitive calcium manganese oxygen colloidal sol and its film fine-pattern |
| CN110759457A (en) * | 2019-10-30 | 2020-02-07 | 武汉大学 | Method for removing organic pollutants in water based on perovskite oxide |
| CN111470540A (en) * | 2020-03-18 | 2020-07-31 | 北京化工大学 | Method for inducing oxygen vacancy content in metal oxide to be improved by complexation effect |
| CN113842890A (en) * | 2021-10-28 | 2021-12-28 | 南华大学 | Preparation method and application of clay-mineral-based metal manganese chelate |
| CN115212870A (en) * | 2022-07-14 | 2022-10-21 | 西南交通大学 | Cesium-doped sodium type layered manganese dioxide VOCs catalyst and preparation method and application thereof |
| CN116062795A (en) * | 2023-03-09 | 2023-05-05 | 浙江师范大学 | Preparation method, product and application of doped birnessite nanometer flower ball |
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| CN101700912A (en) * | 2009-11-17 | 2010-05-05 | 湘潭大学 | Preparation method of silky nano-MnO2 |
| CN106495226A (en) * | 2016-11-07 | 2017-03-15 | 江苏理工学院 | A kind of octahedra Mn3O4 and its microwave synthesis method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7232782B2 (en) * | 2002-03-06 | 2007-06-19 | Enviroscrub Technologies Corp. | Regeneration, pretreatment and precipitation of oxides of manganese |
| CN101700912A (en) * | 2009-11-17 | 2010-05-05 | 湘潭大学 | Preparation method of silky nano-MnO2 |
| CN106495226A (en) * | 2016-11-07 | 2017-03-15 | 江苏理工学院 | A kind of octahedra Mn3O4 and its microwave synthesis method |
Cited By (12)
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| CN108128839A (en) * | 2018-01-03 | 2018-06-08 | 中国农业大学 | A kind of method for treating water of carbon-based auxiliary agent fortifying catalytic persulfate |
| CN108128839B (en) * | 2018-01-03 | 2020-12-01 | 中国农业大学 | Water treatment method for strengthening and catalyzing persulfate by carbon-based auxiliary agent |
| CN110386624A (en) * | 2019-08-19 | 2019-10-29 | 西安理工大学 | The preparation method of ultraviolet photosensitive calcium manganese oxygen colloidal sol and its film fine-pattern |
| CN110386624B (en) * | 2019-08-19 | 2022-02-08 | 西安理工大学 | Preparation method of ultraviolet light-sensitive calcium-manganese oxygen sol and film micro-pattern thereof |
| CN110759457A (en) * | 2019-10-30 | 2020-02-07 | 武汉大学 | Method for removing organic pollutants in water based on perovskite oxide |
| CN111470540A (en) * | 2020-03-18 | 2020-07-31 | 北京化工大学 | Method for inducing oxygen vacancy content in metal oxide to be improved by complexation effect |
| CN113842890A (en) * | 2021-10-28 | 2021-12-28 | 南华大学 | Preparation method and application of clay-mineral-based metal manganese chelate |
| CN113842890B (en) * | 2021-10-28 | 2023-11-28 | 南华大学 | Preparation method and application of clay mineral-based metal manganese chelate |
| CN115212870A (en) * | 2022-07-14 | 2022-10-21 | 西南交通大学 | Cesium-doped sodium type layered manganese dioxide VOCs catalyst and preparation method and application thereof |
| CN115212870B (en) * | 2022-07-14 | 2023-09-01 | 西南交通大学 | Cesium doped sodium layered manganese dioxide VOCs catalyst and preparation method and application thereof |
| CN116062795A (en) * | 2023-03-09 | 2023-05-05 | 浙江师范大学 | Preparation method, product and application of doped birnessite nanometer flower ball |
| CN116062795B (en) * | 2023-03-09 | 2024-01-30 | 浙江师范大学 | Preparation method, product and application of doped birnessite nanometer flower ball |
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