CN106186077B - Preparation and its application without coating agent manganese base nanoporous assembled material - Google Patents
Preparation and its application without coating agent manganese base nanoporous assembled material Download PDFInfo
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- CN106186077B CN106186077B CN201610655936.7A CN201610655936A CN106186077B CN 106186077 B CN106186077 B CN 106186077B CN 201610655936 A CN201610655936 A CN 201610655936A CN 106186077 B CN106186077 B CN 106186077B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention belongs to material science and field of environment engineering, and in particular to a kind of preparation and its application of no coating agent manganese base nanoporous assembled material.By the way that two water beetle acid manganese are dissolved in into methanol solution system, it is placed in autoclave, controlling reaction temperature and time, by one-step synthesis, is self-assembly of Mn3O4Presoma, then presoma is obtained into Mn by high-temperature calcination2O3Nano-porous materials.Mn produced by the present invention2O3Nano-porous materials participate in without organic-capping agent, cost is cheap, yield is high, it is green, phenol pollutant can be effectively removed, clearance is high, and a kind of easy, efficient method is provided for the processing of phenol pollutant, with good economic benefit and environmental benefit, large-scale production and application can be carried out.
Description
Technical field
The invention belongs to material science and field of environment engineering, and in particular to a kind of to be assembled without coating agent manganese base nanoporous
The preparation and its application of material.
Background technology
Phenol pollutant is one of important pollutant of industrialized production, due to its Stability Analysis of Structures, difficult degradation, toxicity
Greatly, the toxic pollutant of priority acccess control is become.Over the years, many researchers are using biodegradable, charcoal absorption and air
The methods of catalysis oxidation, degradation of phenol pollutant, but most methods are only applicable to discharge capacity is few, concentration is low processing, and locate
Manage time length, narrow application range, it is with high costs, can not be degradable, and the defects of easily bring secondary pollution, limit it
Development.
Nowadays, the nano-porous materials synthesized using transition metal oxide are fast to handle the correlation technique of organic pollution
Speed is risen, and wherein Mn oxide is gradually favored as a kind of environmentally friendly material by researchers.Research shows, due to
The architectural feature of itself, manganese base nano-porous materials have very strong absorption degradation performance to organic matter, use it for phenol
Pollutant process, good treatment effect can be obtained.At present, existing researcher synthesizes Mn2O3Nanotube, nanometer rods, nanometer
Cubic block etc. carrys out degradation of phenol type organic, but these synthetic methods much need coating agent to control Mn2O3Pattern, such as quilt
The polyvinylpyrrolidone (PVP) that numerous researchers use is exactly one of which.These organic-capping agent, it is green with Modern times call
Colour circle is protected and runed counter to.In addition, many synthetic methods prepare porous material with traditional masterplate method, these synthetic methods are more numerous
Trivial, complex process, operating difficulties, are unfavorable for popularization and application.
Therefore, the preparation method of further nano-scale porous material has great importance.The application utilizes two water beetles
Sour manganese and methanol solution system, in the case where not adding any organic-capping agent, by one-step synthesis, high-temperature calcination obtains spherical
Mn2O3Nanoporous microballoon.The application overcomes the shortcomings that traditional masterplate method prepares porous material, by being self-assembly of Mn3O4
Presoma, one-step synthesis, simple and effective.Main raw material(s) and used equipment involved by the application are simple and are easy to grasp
Work, cost are cheap, and without the participation of organic-capping agent, obtained Mn2O3Nano-porous materials are environment-friendly, can effectively drop
Phenol pollutant in Xie Shui, economic benefit and obvious environment benefit, there is good application value.
The content of the invention
It is an object of the invention to for insufficient existing for existing porous material preparation method, there is provided one kind is without coating agent
The preparation and its application of manganese base nanoporous assembled material.The present invention is self-assembly of Mn by one-step synthesis3O4Presoma, then
By Mn3O4Presoma high-temperature calcination obtains Mn2O3Nano-porous materials.Obtained Mn2O3Nano-porous materials are without organic-capping
Agent participates in, and cost is cheap, and yield is high, green, can effectively remove phenol pollutant, and clearance is high, is polluted for phenol
The processing of thing provides a kind of easy, efficient method, has good economic benefit and environmental benefit, can carry out extensive
Production application.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation of no coating agent manganese base nanoporous assembled material, including following raw material：Two water beetle acid manganese, methanol.
A kind of preparation method of no coating agent manganese base nanoporous assembled material：Two water beetle acid manganese are dissolved in methanol solution body
System, is evenly stirred until that solid is completely dissolved, is subsequently placed in autoclave.Controlling reaction temperature and time obtain Mn3O4Forerunner
Body；It is scrubbed again, dry；Mn after drying3O4Presoma carries out high-temperature calcination and Mn is made2O3Nano-porous materials.
Specifically, the preparation method of the no coating agent manganese base nanoporous assembled material, comprises the following steps：
（1）Bivalent manganese source is dissolved in methanol solution, stirs to solid be completely dissolved at room temperature, being configured to mass concentration is
5 ~ 50 mol/L manganese source solution；
（2）By step（1）Obtained manganese source solution is poured into autoclave, is placed in 100 ~ 250 DEG C of isothermal reactions 6 ~ 36
h；
（3）By reacted solution furnace cooling, it is centrifuged, washs, 50 ~ 75 DEG C of dryings are volatilized completely to moisture,
Obtain Mn3O4Presoma；
（4）By dried Mn3O4Presoma is placed in Muffle furnace, is calcined in air atmosphere；Control heating rate 1 ~ 7
℃·min-1, 500 ~ 800 DEG C of calcining heat, soaking time 6 ~ 24 h, Mn3O4Presoma is oxidized in atmosphere, and volume is received
Contracting, obtains Mn2O3Nanoporous microballoon.
According to above-mentioned technical proposal, the described preferred compound concentration of bivalent manganese source solution is 16 ~ 25 mol/L；Course of reaction
In, preferable isothermal reaction temperature is 150 ~ 200 DEG C, and preferable constant temperature time is 12 ~ 18 h；It is preferable dry in drying process
Dry temperature is 60 ~ 70 DEG C；In calcination process, preferable heating rate is 2 ~ 5 DEG C of min-1, preferable calcining heat be 550 ~
750 DEG C, preferably calcination time is 12 ~ 18 h.
The Mn prepared according to above-mentioned technical proposal2O3Nano-porous materials, applied to the processing of phenol pollutant, performance
Go out good removal effect.
Have particular application as：Pending phenol pollutant pH value is adjusted to acidity, will be without coating agent manganese base nanoporous
Assembled material is put into phenol pollutant, is stirred vigorously, and the reaction time is controlled within 2 h.
The remarkable advantage of the present invention is：
（1）Preparation method one-step synthesis：Using solvent-thermal method, by one-step synthesis, high-temperature calcination can obtain Mn2O3Receive
Rice porous material；Technological operation is simple, cost is low, efficiency high, is advantageous to large-scale production；
（2）Participated in without organic-capping agent：In preparation process, control Mn is participated in without organic-capping agent3O4Pattern, by certainly
Assembling can form well-regulated spherical morphology；
（3）It is green：Manganese is as a kind of environmentally friendly element, the environmental pollution compared with other precious metal elements
It is small, it is a kind of eco-friendly section bar material, obtained Mn2O3Whole spheroid is run through in its nanoscale duct of nano-porous materials, tool
There is larger specific surface area, the processing of Pyrogentisinic Acid's pollutant shows significant effect.
Brief description of the drawings
Fig. 1 is that the embodiment of the present invention 1 calcines preceding a）Mn3O4Presoma and b after calcining）Mn2O3The XRD of nano-porous materials
Figure；
Fig. 2 is Mn made from the embodiment of the present invention 13O4The SEM figures of presoma；
Fig. 3 is Mn made from the embodiment of the present invention 12O3The SEM figures of nano-porous materials；
Fig. 4 is Mn made from the embodiment of the present invention 22O3The SEM figures of nano-porous materials；
Fig. 5 is Mn made from the embodiment of the present invention 32O3The SEM figures of nano-porous materials；
Fig. 6 is Mn made from the embodiment of the present invention 42O3The SEM figures of nano-porous materials；
Fig. 7 is that obtained Mn is respectively adopted in Application Example 1 and Application Example 22O3Nano-porous materials and commercialization
Mn2O3The curve that powder Pyrogentisinic Acid's pollutants removal rate changes over time.
Embodiment
Below in conjunction with drawings and Examples, the object, technical solution and advantage of the application are further illustrated, make the application
Become apparent from understanding.It should be appreciated that specific embodiment described herein is not used to limit this hair only to explain the present invention
It is bright.
Embodiment 1
Mn2O3The preparation of nano-porous materials：
（1）0.1810 g two water beetle acid manganese are dissolved in 60 mL methanol solution, stirred at room temperature completely molten to solid
Solution, manganese source solution is made；
（2）Above-mentioned solution is poured into 100 mL autoclave, be placed in 180 DEG C of baking oven, be incubated 18 h；
（3）By reacted solution furnace cooling, centrifuge, and wash 3 times with ethanol and deionized water and obtain Mn3O4
Presoma；
（4）By Mn3O4Presoma is placed in thermostatic drying chamber, is dried under the conditions of 60 DEG C, until moisture volatilizees completely；
（5）By dried Mn3O4Presoma is placed in Muffle furnace, is calcined in air atmosphere；Control 5 DEG C of heating rate
min-1, 500 DEG C of calcining heat, the h of soaking time 12, obtain Mn2O3Nano-porous materials.
According to embodiment 1, with using X-ray diffraction analysis thing phase respectively after calcining before product is calcined, its X-ray diffraction is such as
Shown in Fig. 1.Analysis determines that the thing before calcining is mutually Mn3O4, the thing after calcining is mutually Mn2O3.It is electric with the scanning after calcining before calcining
Sub- microscope is as shown in Figures 2 and 3.It can be seen that before product calcining, it is piled into by many tiny nano particles
Mn3O4Spherical structure.Mn is formed after calcining2O3Loose structure, and remain Mn3O4Presoma pattern, its nanoscale duct are run through
Whole spheroid.
Embodiment 2
Mn2O3The preparation of nano-porous materials：
（1）0.1810 g two water beetle acid manganese are dissolved in 60 mL methanol solution, stirred at room temperature completely molten to solid
Solution, manganese source solution is made；
（2）Above-mentioned solution is poured into 100 mL autoclave, be placed in 180 DEG C of baking oven, be incubated 18 h；
（3）By reacted solution furnace cooling, centrifuge, and wash 3 times with ethanol and deionized water and obtain Mn3O4
Presoma；
（4）By Mn3O4Presoma is placed in thermostatic drying chamber, is dried under the conditions of 60 DEG C, until moisture volatilizees completely；
（5）By dried Mn3O4Presoma is placed in Muffle furnace, is calcined in air atmosphere, controls heating rate 5
℃·min-1, 600 DEG C of calcining heat, the h of soaking time 12, obtain Mn2O3Nano-porous materials.
According to embodiment 2, its SEM is as shown in figure 4, it can be seen that the Mn2O3Product is porous
The microballoon of structure.Relative to embodiment 1, Mn made from embodiment 22O3The duct of nanoporous microballoon is bigger, and this is due to calcining
Temperature raises so that the amount of contraction increase of microsphere particle, therefore duct accordingly expands.
Embodiment 3
Mn2O3The preparation of nano-porous materials：
（1）0.2715 g two water beetle acid manganese are dissolved in 60 mL methanol solution, stirred at room temperature completely molten to solid
Solution, manganese source solution is made；
（2）Above-mentioned solution is poured into 100 mL autoclave, be placed in 180 DEG C of baking oven, be incubated 18 h；
（3）Reacted solution furnace cooling, centrifuge, and wash 3 times with ethanol and deionized water and obtain Mn3O4Before
Drive body；
（4）By Mn3O4Presoma is placed in thermostatic drying chamber, is dried under the conditions of 60 DEG C, until moisture volatilizees completely；
（5）By dried Mn3O4Presoma is placed in Muffle furnace, is calcined in air atmosphere.Control 5 DEG C of heating rate
min-1, 600 DEG C of calcining heat, the h of soaking time 12, obtain Mn2O3Nano-porous materials.
According to embodiment 3, its SEM is as shown in figure 5, it can be seen that the Mn2O3Product is porous
The microballoon of structure.Relative to embodiment 1 and implement 2, Mn made from embodiment 32O3Many strippings are dispersed with around nanoporous microballoon
The shell fallen, it forms Mn2O3The process of nanoporous microballoon, which belongs to, to pip.
Embodiment 4
Mn2O3The preparation of nano-porous materials：
（1）0.2715 g two water beetle acid manganese are dissolved in 60 mL methanol solution, stirred at room temperature completely molten to solid
Solution, manganese source solution is made；
（2）Above-mentioned solution is poured into 100 mL autoclave, be placed in 180 DEG C of baking oven, be incubated 18 h；
（3）By reacted solution furnace cooling, centrifuge, and wash 3 times with ethanol and deionized water and obtain Mn3O4
Presoma；
（4）By Mn3O4Presoma is placed in thermostatic drying chamber, is dried under the conditions of 60 DEG C, until moisture volatilizees completely；
（5）By dried Mn3O4Presoma is placed in Muffle furnace, and step calcination is carried out in air atmosphere；First control heating
2 DEG C of min of speed-1, 550 DEG C of calcining heat, the h of soaking time 6, then control 5 DEG C of min of heating rate-1, calcining heat
750 DEG C, the h of soaking time 6, continue to calcine, obtain Mn2O3Nano-porous materials.
According to embodiment 4, its SEM is as shown in fig. 6, it can be seen that the Mn2O3Product is stratiform
The microballoon of loose structure, and duct is larger；Due to using step calcination in calcination process, and calcining heat is higher so that Mn2O3
Stratiform loose structure is presented in microballoon, and duct becomes big.
Application Example 1
By the Mn of the gained of embodiment 22O3Nano-porous materials are used to remove phenol pollutant, comprise the following steps that：
（1）Prepare 200 mgL-1Phenol solution, with HCl adjust pH value of solution=2；
（2）By the Mn of preparation2O3Nano-porous materials are put into above-mentioned phenol solution, control the Mn of input2O3Concentration is
0.6 g·L-1, it is stirred vigorously；
（3）By the different periods, the UV absorption of phenol in water is tested respectively with ultraviolet-visible spectrophotometer
Value, calculate the clearance of phenol.
Application Example 2
By the Mn of commercialization2O3Powder removes phenol pollutant, comprises the following steps that：
（1）Prepare 200 mgL-1Phenol solution, with HCl adjust pH value of solution=2；
（2）By the Mn of commercialization2O3Powder is put into above-mentioned phenol solution, controls the Mn of input2O3The gL of concentration 0.6-1,
It is stirred vigorously；
（3）By the different periods, the UV absorption of phenol in water is tested respectively with ultraviolet-visible spectrophotometer
Value, calculate the clearance of phenol.
According to use above embodiment 1, the data of Application Example 2, phenol clearance curve as shown in Figure 7 is obtained.
As can be seen from Figure 7, with the extension of time, Mn2O3Nano-porous materials and commercial Mn2O3Powder all makes phenol concentration constantly reduce.
After 1 h, Mn2O3Nano-porous materials make the clearance of phenol pollutant reach 87%, reach 99% after 2 h；However, for
Commercial Mn2O3Powder, after 1 h, the clearance of phenol pollutant is only up to reaching 58% after 35%, 2 h.It is prepared by the contrast present invention
Obtained Mn2O3Nano-porous materials and commercial Mn2O3Powder, the Mn that the present invention is prepared2O3Nano-porous materials are to benzene
Mn of the removal capacity of phenol pollutant than commercialization2O3Increase significantly.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (4)
1. a kind of preparation method of no coating agent manganese base nanoporous assembled material, it is characterised in that comprise the following steps：
（1）Two water beetle acid manganese are dissolved in methanol, stirs to solid be completely dissolved at room temperature, be configured to manganese source solution；
（2）By step（1）Obtained solution is poured into autoclave, carries out isothermal reaction；
（3）By step（2）Reacted solution furnace cooling, be centrifuged, wash, dry until moisture volatilize completely, obtain
To Mn3O4Presoma；
（4）By step（3）The Mn being dried to obtain3O4Presoma is placed in Muffle furnace, and step calcination is carried out in air atmosphere, first
Control 2 DEG C of min of heating rate-1, 550 DEG C of calcining heat, the h of soaking time 6, then control 5 DEG C of min of heating rate-1,
750 DEG C of calcining heat, the h of soaking time 6, continues to calcine, obtains Mn2O3Nano-porous materials, obtain Mn2O3Nanoporous material
Material.
2. a kind of preparation method of no coating agent manganese base nanoporous assembled material according to claim 1, its feature exist
In：Step（1）The concentration of described manganese source solution is 5 ~ 50 mol/L.
3. a kind of preparation method of no coating agent manganese base nanoporous assembled material according to claim 1, its feature exist
In：Step（2）Described isothermal reaction is specially：In 100 ~ 250 DEG C of h of isothermal reaction 6 ~ 36.
4. a kind of preparation method of no coating agent manganese base nanoporous assembled material according to claim 1, its feature exist
In：Step（3）Described drying temperature is 50 ~ 75 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1290657A (en) * | 1999-09-30 | 2001-04-11 | 杜祖德 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
| CN103657641A (en) * | 2013-11-18 | 2014-03-26 | 太原理工大学 | Preparation method of catalyst for removing phenolic compounds in water |
| CN105417586A (en) * | 2015-12-29 | 2016-03-23 | 中国科学院过程工程研究所 | Preparation method for manganic manganous oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0011684D0 (en) * | 2000-05-15 | 2000-07-05 | Eveready Battery Inc | Porous manganese dioxide and method of preparation thereof |
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2016
- 2016-08-11 CN CN201610655936.7A patent/CN106186077B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1290657A (en) * | 1999-09-30 | 2001-04-11 | 杜祖德 | Monohydrated mangnese sulfate pyrolysizing process for producing mangness dioxide |
| CN103657641A (en) * | 2013-11-18 | 2014-03-26 | 太原理工大学 | Preparation method of catalyst for removing phenolic compounds in water |
| CN105417586A (en) * | 2015-12-29 | 2016-03-23 | 中国科学院过程工程研究所 | Preparation method for manganic manganous oxide |
Non-Patent Citations (2)
| Title |
|---|
| Double-Shelled Mn2O3 Hollow Spheres and Their Application in Water Treatment;Jie Cao等;《EurJIC》;20100208;第1172-1176页 * |
| Low-Temperature Hydrothermal Synthesis of Mn3O4 and MnOOH Single Crystals:Determinant Influence of Oxidants;Chi-Chang Hu 等;《Chemistry of Materials》;20080416;第20卷(第9期);第2890-2894页 * |
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