CN107021525B - 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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- CN107021525B CN107021525B CN201610067326.5A CN201610067326A CN107021525B CN 107021525 B CN107021525 B CN 107021525B CN 201610067326 A CN201610067326 A CN 201610067326A CN 107021525 B CN107021525 B CN 107021525B
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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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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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 suitable 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 alkaline 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：Any oxidant such as hydrogen peroxide, persulfate are not being added, not by any ancillary equipment such as ultrasound, under the premise of microwave, can only realize the efficient degradation to above-mentioned dyestuff 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, significant effect simple to degradation of organic dyes condition 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
In technical field of material.
Background technology
Birnessite is a kind of two-dimensional layer Mn oxide, has unique crystal structure, its lamella is by manganese oxygen octahedra
Side or corner-sharing are formed altogether, and interlayer is by Na+Or other metal ions, and hydrone mutually occupies filling.Birnessite its own and
The functional material of synthesis is all widely used in light, electricity, magnetic, catalysis etc..In recent years, the synthesis and application of birnessite
Research has obtained extensive attention.
At present, the synthesis of birnessite mainly has following several approach：(1) sol-gal process is used, using organic matter also
Former potassium permanganate；(2) in acid condition, hydrothermal decomposition potassium permanganate；(3) in alkaline conditions, oxidizing process solubility manganese salt.
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.Deficiency all limits the practical application of birnessite existing for above method.The present invention exists
On the basis of aqueous solution air oxidation process, the method for addition complexing agent, is successfully prepared high purity water sodium manganese in soluble manganese salt
Ore deposit, overcomes the deficiency in the above method, and time saving and energy saving, favorable repeatability.Moreover, the birnessite of preparation is only in acid
The efficient degradation to organic dyestuff methylene blue (MB), methyl orange (MO) and rhodamine B (RhB) can be realized under the conditions of property, is
A large amount of processing of organic dyestuff provide possibility in industry.
The content of the invention
The present invention is for insufficient existing for the preparation method of existing birnessite, it is proposed that one kind simply prepares high-purity
The method of birnessite, and the birnessite in acid condition just can efficient degradation of organic dye RhB.The preparation method raw material
Cheap and easy to get, preparation process is simple, repeatability is strong, and product purity is high, and is not adding any oxidant such as hydrogen peroxide, mistake
Sulfate, 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：The wherein concentration of manganese salt is 0.12.0mol/L, complexing agent
Concentration be 0.1~0.4mol/L；Manganese salt and the molar ratio of EDTA-Na 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 solution to be added dropwise in step a mixed solutions；
D. stirring a period of time is continued after reaction；
E. filtering precipitation, is washed with deionized 3 times, dries certain time under certain condition, obtain product.
The solubility manganese salt includes manganese sulfate, manganese nitrate, manganese chloride, manganese acetate etc.；Complexing agent includes trisodium citrate,
Disodium ethylene diamine tetraacetate 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 that ageing time is 2~48h under agitation after reaction；
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 pair of preparation
Organic dyestuff, which includes but not limited to methylene blue, rhodamine B, methyl orange etc., has notable degradation；And degradation process only exists
Acidity (pH<5) 10mg samples are the efficient degradation that can be achieved to 50mL 10~100mg/L organic dyestuff under the conditions of, and this degrades
Process no longer adds any other auxiliary agent, also not by any ancillary equipment such as ultrasound, microwave.
Advantages of the present invention is mainly reflected in：
Raw material is cheap and easy to get, simple using air oxidation process, non-environmental-pollution, preparation process, time saving and energy saving to be easy to advise greatly
Mould produces；
Degradation condition is gentle, significant effect, catabolite non-secondary pollution thing；
Product purity is high, and possibility is provided for its application in other aspects.
Brief description of the drawings
Fig. 1, (a) and (b) are the XRD diagram and FESEM figures of 1 product of embodiment respectively；
Fig. 2, (a) and (b) are the XRD diagram and FESEM figures of 3 product of embodiment respectively；
Fig. 3, (a) and (b) are the XRD diagram and FESEM figures of 5 product of embodiment respectively；
Fig. 4, (a) and (b) are the XRD diagram and FESEM figures of 7 product of embodiment respectively；
Fig. 5, RhB UV, visible lights of degrading by taking 1 gained birnessite of embodiment 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, the degradation rate of MB, MO and RhB
Change with time.
Embodiment
The application range 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 with 3mL/
Min is added drop-wise to MnSO4After in EDTA-Na mixed solutions, being added dropwise and continuing to stir aging 2h, filtration washing precipitates for several times,
12h at 40 DEG C of vacuum drying chamber is placed on, obtains high-purity birnessite.
XRD detections are carried out to the sample of preparation, as shown in 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, ultrasonic 5min
Sample is dispersed in solution, recycle H2SO4Adjust pH value of solution and sample 3mL to 1, the 1st, 3,5 and 10min, in centrifuging and taking
Layer clear liquid, measures its concentration using UV-vis, calculates its degradation rate.Its UV-vis is as shown in figure 5, complete in 10min ends RhB
Degradable.
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；Under quick stirring, by NaOH solution with 6mL/
Min is added drop-wise to MnSO4After in EDTA-Na mixed solutions, being added dropwise and continuing to stir aging 2h, filtration washing precipitates for several times,
12h at 40 DEG C of vacuum drying chamber is placed on, obtains 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 with
6mL/min is added drop-wise to MnSO4After in EDTA-Na mixed solutions, being added dropwise and continuing to stir aging 2h, filtration washing precipitation number
It is secondary, 6h at 80 DEG C of vacuum drying chamber is placed on, obtains high-purity birnessite sample.
XRD detections are carried out to the sample of preparation, as shown in 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 in 50ml 10mg/L MB (methylene blue) volumetric flask,
Ultrasonic 5min makes sample be dispersed in solution, recycles H2SO4Adjust pH value of solution to 1, the 1st, 3,5 and 10min sample 3mL,
Centrifuging and taking supernatant liquor, measures its concentration using UV-vis, calculates its degradation rate.The degradation rate of MB changes with time such as Fig. 6
(a) shown in.It is then degradable that in 5min, degradation rate, which reaches more than 96%, 10min,.
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；Under quick stirring, by NaOH solution with 6mL/
Min is added drop-wise to MnSO4After in EDTA-Na mixed solutions, being added dropwise and continuing to stir aging 12h, filtration washing precipitates for several times,
6h at 80 DEG C of vacuum drying chamber is placed on, obtains 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；Under quick stirring, by NaOH solution with 6mL/
Min is added drop-wise to MnSO4After in EDTA-Na mixed solutions, being added dropwise and continuing to stir aging 24h, filtration washing precipitates for several times,
6h at 80 DEG C of vacuum drying chamber is placed on, obtains high-purity birnessite sample.
XRD detections are carried out to the sample of preparation, as shown in 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 in 50ml 10mg/L MO (methyl orange) volumetric flask, surpass
Sound 5min makes sample be dispersed in solution, recycles H2SO4Adjust pH value of solution to 1, the 1st, 3,5 and 10min sample 3mL, from
The heart takes supernatant liquor, measures its concentration using UV-vis, calculates its degradation rate.The degradation rate of MO changes with time such as Fig. 6 (b)
It is shown.It is then degradable that in 5min, degradation rate, which reaches more than 95%, 10min,.
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；Under quick stirring, by NaOH solution with 8mL/
Min is added drop-wise to MnSO4After in EDTA-Na mixed solutions, being added dropwise and continuing to stir aging 48h, filtration washing precipitates for several times,
12h at 60 DEG C of vacuum drying chamber is placed on, obtains 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；Under quick stirring, by NaOH solution with 8mL/
Min is added drop-wise in MnSO4 and EDTA-Na mixed solutions, is added dropwise after continuing to stir aging 24h, and filtration washing precipitates for several times,
24h at 30 DEG C of vacuum drying chamber is placed on, obtains high-purity birnessite sample.
XRD detections are carried out to the sample of preparation, as shown in 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, ultrasonic 5min
Sample is dispersed in solution, recycle H2SO4Adjust pH value of solution and sample 3mL to 1, the 1st, 3,5 and 10min, in centrifuging and taking
Layer clear liquid, measures its concentration using UV-vis, calculates its degradation rate.The degradation rate of RhB changes with time as shown in Fig. 6 (c).
It is then degradable that in 5min, degradation rate, which reaches more than 97%, 10min,.
Claims (5)
- A kind of 1. system of high-purity birnessite type Mn oxide with three dimensional micron floral structure of energy efficient degradation of organic dye Preparation Method, preparation method comprise the following steps：A. soluble manganese salting liquid is uniformly mixed with complexing agent：Its complexing agent is citric acid, trisodium citrate, citric acid three Potassium, three rubidium of citric acid, three caesium of citric acid, ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate；Soluble manganese salinity for 0.1~ 2.0mol/L, complexing agent concentration are 0.1~0.4mol/L；Soluble manganese salt and the molar 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 solution to be added dropwise in step a mixed solutions；D. continue to stir aging for a period of time after reaction；E. filtering precipitation, is washed with deionized 3 times, dries certain time under certain condition and obtains product.
- 2. preparation method according to claim 1, it is characterised in that soluble manganese salt is manganese sulfate, manganese nitrate, chlorination Manganese, manganese acetate.
- 3. preparation method according to claim 1, it is characterised in that strong alkali solution is sodium hydroxide, potassium hydroxide, hydrogen Rubidium oxide and cesium hydroxide；The rate of addition of strong base solution is 1~10mL/min.
- 4. preparation method according to claim 1, it is characterised in that after reaction under agitation aging 2~ 24h；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 characterized in that, the birnessite type Mn oxide prepared is sub- to organic dyestuff Methyl blue, rhodamine B, methyl orange have notable degradation；Degradation process is in pH<Under conditions of 5,10mg samples can be achieved To the efficient degradation of 50mL 10~100mg/L organic dyestuff, and this degradation process no longer adds any other auxiliary agent, does not also borrow Help ultrasound and microwave.
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| 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 |
| 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 |
| CN111470540B (en) * | 2020-03-18 | 2021-06-22 | 北京化工大学 | Method for inducing oxygen vacancy content in metal oxide to be improved by complexation effect |
| CN113842890B (en) * | 2021-10-28 | 2023-11-28 | 南华大学 | Preparation method and application of clay mineral-based metal manganese chelate |
| 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 |
| 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 |
| CN118079953A (en) * | 2024-04-23 | 2024-05-28 | 江西农业大学 | Birnessite-sulfite photocatalyst and application thereof |
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| 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 |
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| 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 |
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