CN102040246B - Method for synthesizing manganous-manganic oxide nano material at room temperature by using mild path - Google Patents

Method for synthesizing manganous-manganic oxide nano material at room temperature by using mild path Download PDF

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CN102040246B
CN102040246B CN 201010520394 CN201010520394A CN102040246B CN 102040246 B CN102040246 B CN 102040246B CN 201010520394 CN201010520394 CN 201010520394 CN 201010520394 A CN201010520394 A CN 201010520394A CN 102040246 B CN102040246 B CN 102040246B
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manganous
trimanganese tetroxide
oxide nano
room temperature
sodium hydroxide
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CN102040246A (en
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张俊豪
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Jiangsu University of Science and Technology
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Jiangsu University of Science and Technology
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Abstract

The invention discloses a method for synthesizing a manganous-manganic oxide nano material at room temperature by using a mild path, which comprises the steps of: mixing manganese acetate, sodium tetraborate and a sodium hydroxide solution under stirring at a temperature of 20-25 DEG C, reacting according to the following formula of 3Mn(Ac)2+Na2B4O7+1/2O2+16NaOH->Mn3O4+4Na3BO3+6NaAc+8H2O, washing products with alcohol and water, centrifugally separating and drying to obtain manganous-manganic oxide powder with square-phase manganous-manganic oxide nano diamonds as main components. The size of the square-phase manganous-manganic oxide nano diamonds is about 100nm. The method has the advantages of low reaction temperature, low cost of the raw materials, no pollution and attractive appearance of the obtained product, and is suitable for industrialized massive production.

Description

Utilize the method for the synthetic manganic manganous oxide nano-material of soft line room temperature
Technical field
The invention belongs to the manganic manganous oxide nano-material preparing technical field, relate in particular under a kind of room temperature synthetic take the Tetragonal trimanganese tetroxide nano cube method as main trimanganese tetroxide powder.
Background technology
Bibliographical information trimanganese tetroxide powder has certain purposes aspect the environmental pollutions such as large G﹠W slowing down.The powder of Holland " current catalysis " (Catalysis Today 47 (1-4): 161-167,1999) report trimanganese tetroxide has preferably catalytic activity to the oxidation of methane and carbon monoxide; U.S.'s " catalysis magazine " (Journal of Catalysis, 157 (2): 706-712,1995.) has reported that trimanganese tetroxide shows preferably catalytic effect in the reduction process of oil of mirbane; Holland " applied catalysis B: environment " (Applied Catalysis B:Environmental, 16(1) 43-51,1998) report that trimanganese tetroxide also has reasonable catalytic activity in the combustion processes of organic compound.
U.S.'s " chemical material " (Chemistry of Materials, 22 (14): 4232-4236,2010.) has reported under dodecanol and oleyl amine existence condition, 200 ℃ of Hydrothermal Synthesis Tetragonal trimanganese tetroxide nano posts.This preparation method not only needs higher temperature, also has organism to exist, easily contaminate environment, and cost that need to be higher.Another piece U.S. " chemical material " (Chemistry of Materials, 20 (9): 2890-2894,2008.) report is with manganous acetate and K 2S 2O 8Be raw material, 120 ℃ of Hydrothermal Synthesiss are of a size of the Mn of 100 nm 3O 4Particle.Although this method exists without the need for the machine thing, but still need higher temperature, also can cause sulphide staining.Britain's " polyhedron " (Polyhedron, 28 (11): 2119-2122,2009.) has reported at ambient temperature, with Mn (ac) 2And Mn (acac) 3Mix with egg white and deionized water, after the presoma drying, obtain to be of a size of the Mn of 150～2000 nm 800 ℃ of roastings 3O 4Particle.U.S.'s " crystal growth and design " (Crystal Growth ﹠amp; Design, 8 (1): 358-362,2008.) report MnCl 2And Na 2CO 3Griding reaction generates MnCO 3, then with the MnCO that obtains 3After NaCl and nonyl benzene ether mix, 850 ℃ of heat treated." the physical chemistry B magazine " of the U.S. (Journal of Physical Chemistry B, 110 (48): 24450-24456,2006.) reported with Mn (acac) 3, Mn (acac) 2In acetone, mix to make presoma with SBA-15, again with the roasting 5 hours in 500 ℃ of exposure airs of the precursor that makes.These three kinds of methods have common characteristics, and not only process is complicated, and need higher thermal treatment temp, are unfavorable for suitability for industrialized production.Holland's " crystal growth magazine " report adopts the ultrasonic radiation method to make Mn 3O 4Nanocrystalline.This method although process is simple, needs ultrasonic radiation, also is unfavorable for scale operation.Therefore, at low temperatures, the cheap a large amount of Mn of preparation 3O 4Nanocrystalline, the application in the environmental pollution field has the meaning of particularly important to the expansion trimanganese tetroxide.
Summary of the invention
The deficiency that temperature of reaction is high, raw material is expensive and process is complicated for the prior art existence, the present invention proposes a kind of method of utilizing the synthetic manganic manganous oxide nano-material of soft line room temperature, have the reaction conditions gentleness, raw material is easy to get and the simple advantage of process.
Technical scheme of the present invention is: a kind of method of utilizing the synthetic manganic manganous oxide nano-material of soft line room temperature, under 20～25 ℃, under stirring manganous acetate, sodium tetraborate and sodium hydroxide solution are mixed, and press the following formula reaction:
3Mn(Ac) 2?+?Na 2B 4O 7+?1/2O 2+16NaOH→Mn 3O 4?+?4Na 3BO 3+6NaAc+8H 2O
Obtain after washing, separation, the drying take Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder.
Preferred version is: manganous acetate, sodium tetraborate and sodium hydroxide is the amount hybrid reaction 20 hours ± 5 hours of 1:0.25～3:5～20 in molar ratio.
More preferably scheme is the amount mixing of manganous acetate, sodium tetraborate and sodium hydroxide 1: 0.5 in molar ratio～2: 7.5～15.
Most preferably scheme is: the amount of manganous acetate, sodium tetraborate and sodium hydroxide 1: 0.8 in molar ratio～1.2: 9～12 is mixed.
Beneficial effect:
1. the present invention is owing to having adopted room temperature liquid phase stirring reaction, and temperature of reaction is low than prior art, and reaction process is simple and easy to control, and raw material is cheaply pollution-free, and the products therefrom pattern is relatively good, is easy to scale operation and is applied to the processing of environmental pollution.
Method of the present invention obtain take Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder, the mean sizes of its nano cubic block is about 100 nanometers.
3. method of the present invention is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 be adopt the inventive method preparation take the X-ray diffraction spectra (XRD) of Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder.
Fig. 2 is take the infrared spectra (IR) of Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder.
Fig. 3 is take the low power transmission electron microscope photo of Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder.
Fig. 4 is take the high power transmission electron microscope photo of Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder.
Fig. 5 is take the electron diffraction photo of Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder.
Fig. 6 is take the high resolution transmission electron microscopy photo of Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder.
Embodiment
A kind of method of utilizing the synthetic manganic manganous oxide nano-material of soft line room temperature at 20～25 ℃, under stirring is mixed manganous acetate, sodium tetraborate and sodium hydroxide solution, presses the following formula reaction:
3Mn(Ac) 2?+?Na 2B 4O 7+?1/2O 2+16NaOH→Mn 3O 4?+?4Na 3BO 3+6NaAc+8H 2O
Product ethanol and water washing, centrifugation and drying, namely obtaining Tetragonal trimanganese tetroxide nano cubic block is main trimanganese tetroxide powder.
Preferred version is: manganous acetate, sodium tetraborate and sodium hydroxide is the amount hybrid reaction 20 hours ± 0.5 hour of 1:0.25～3:5～20 in molar ratio.
More preferably scheme is: the amount of manganous acetate, sodium tetraborate and sodium hydroxide 1: 0.5 in molar ratio～2: 7.5～15 is mixed.
Most preferably scheme is: the amount of manganous acetate, sodium tetraborate and sodium hydroxide 1: 0.8 in molar ratio～1.2: 9～12 is mixed.
Embodiment 1:
Solution reaction with manganous acetate, sodium tetraborate and sodium hydroxide prepares take Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder.
Respectively 2mmol manganous acetate and 2mmol sodium tetraborate are dissolved in the deionized water of 20mL, stir and form uniform solution, then sodium tetraborate solution slowly is added drop-wise in the manganous acetate solution, and continuing under the stirring, add rapidly 20mmol sodium hydroxide in the top mixing solutions, under the room temperature, reacted while stirring 20 hours; Product ethanol and water washing, centrifugation and drying, namely obtaining cubic trimanganese tetroxide nano cubic block is main trimanganese tetroxide powder.40 ℃ of lower vacuum-dryings 6 hours, obtain at last the brown ceramic powder product.
Adopt Japanese Rigaku D/max- γA type X-ray powder diffraction (XRD) instrument carries out material phase analysis, Cu to powder K α( λ=1.54178), graphite monochromator, pipe is pressed and electric current is respectively 40 kV and 20 mA, sweep velocity 10.0 oMin -1
Fig. 1 is the X-ray diffraction spectra of the product of embodiment 1 preparation.As seen from Figure 1,2 θ have 11 stronger diffraction peaks at 10-70 in the x-ray diffraction spectra, and position and intensity all are consistent with Tetragonal trimanganese tetroxide standard powdery diffractometry card.But all diffraction peak indexs are the trimanganese tetroxide of simple tetragonal grid, are consistent with the result of Tetragonal trimanganese tetroxide standard powdery diffractometry card (JCPDS# 24-0734).If temperature of reaction is lower than 15 ℃, the crystallinity that then can not get trimanganese tetroxide product or product is bad.Experiment can obtain repeatability and the reasonable product of crystallinity when temperature of reaction was room temperature (20～25 ℃).If temperature of reaction is higher than 60 ℃, then be unfavorable for the generation of nano cubic block, product mostly is the larger trimanganese tetroxide particle of size.On the other hand, if the reaction times is too short, then impure the or reaction of the product that obtains of experiment not exclusively, what impact is overlong time do not have to product, but impact produces, so the common better suited reaction times is about 20 hours.As seen from Figure 1, test the Tetragonal trimanganese tetroxide that resulting product mainly is the well-crystallized; From the XRD style, also contain a small amount of impurity in the product.
Under the room temperature condition, adopt the EQUINOX55 infrared spectrometer that powder is further confirmed:
From the infrared spectrum of Fig. 2, can find out, at 629 and 528 cm -1Two absorption peaks at place are corresponding to four sides position and octahedral position Mn-O vibronic coupling; 413 cm -1The stretching vibration of the corresponding octahedral position of the absorption peak at place, FT-IR spectrum shows that further the product of acquisition is the trimanganese tetroxide powder.
Use pattern, particle size and the crystalline structure of JEOL 2010 type high resolution transmission electron microscopies (HRTEM) and observation product:
From TEM photo Fig. 3 of product as seen, adopt the inventive method to prepare the particle size of trimanganese tetroxide nano cubic block product even, productive rate is high; Fig. 4 is the transmission Photomicrograph of two cubic blocks, and the result shows, the size of cubic block is about 100 nanometers; Fig. 5 is the selected area electron diffraction photo of trimanganese tetroxide nano cubic block, and its zone axis is＜001 〉; Fig. 4 is the HRTEM photo of trimanganese tetroxide cubic block, and its interplanar distance is about 0.287 nm, corresponding to { the 200} face of cubic trimanganese tetroxide.
Above analysis has confirmed that product that experiment obtains is that well-crystallized's Tetragonal trimanganese tetroxide nano cubic block is main trimanganese tetroxide powder.
Embodiment 2:
Prepare take Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder with manganous acetate, sodium tetraborate and sodium hydroxide solution reaction.
1: 1.5: 12 in molar ratio amount is mixed manganous acetate, sodium tetraborate and sodium hydroxide solution, under 20 ℃ and agitation condition, reacts 15 hours; Product ethanol and water washing, centrifugation and drying, namely obtaining Tetragonal trimanganese tetroxide nano cubic block is main trimanganese tetroxide powder.
Embodiment 3:
Prepare take Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder with manganous acetate, sodium tetraborate and sodium hydroxide solution reaction.
1: 3: 12 in molar ratio amount is mixed manganous acetate, sodium tetraborate and sodium hydroxide solution, under 25 ℃ and agitation condition, reacts 25 hours; Product ethanol and water washing, centrifugation and drying, namely obtaining cubic trimanganese tetroxide nano cubic block is main trimanganese tetroxide powder.
Embodiment 4:
Prepare take Emission in Cubic trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder with manganous acetate, sodium tetraborate and sodium hydroxide solution reaction.
1: 0.25: 5 in molar ratio amount is mixed manganous acetate, sodium tetraborate and sodium hydroxide solution, under room temperature and agitation condition, reacts 22 hours; Product ethanol and water washing, centrifugation and drying, namely obtaining cubic trimanganese tetroxide nano cubic block is main trimanganese tetroxide powder.

Claims (3)

1. a method of utilizing the synthetic manganic manganous oxide nano-material of soft line room temperature is characterized in that, under 20～25 ℃ of lower stirrings manganous acetate, sodium tetraborate and sodium hydroxide solution is mixed, and presses the following formula reaction:
3Mn(Ac) 2+Na 2B 4O 7+1/2O 2+16NaOH→Mn 3O 4+4Na 3BO 3+6NaAc+8H 2O
Obtain after washing, separation, the drying take Tetragonal trimanganese tetroxide nano cubic block as main trimanganese tetroxide powder;
Manganous acetate, sodium tetraborate and sodium hydroxide is the amount hybrid reaction 20 hours ± 5 hours of 1:0.25～3:5～20 in molar ratio.
2. utilize as claimed in claim 1 the method for the synthetic manganic manganous oxide nano-material of soft line room temperature, it is characterized in that, the amount of manganous acetate, sodium tetraborate and sodium hydroxide 1: 0.5 in molar ratio～2: 7.5～15 is mixed.
3. utilize as claimed in claim 1 the method for the synthetic manganic manganous oxide nano-material of soft line room temperature, it is characterized in that, the amount of manganous acetate, sodium tetraborate and sodium hydroxide 1: 0.8 in molar ratio～1.2: 9～12 is mixed.
CN 201010520394 2010-10-27 2010-10-27 Method for synthesizing manganous-manganic oxide nano material at room temperature by using mild path Expired - Fee Related CN102040246B (en)

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CN103274469B (en) * 2013-06-05 2015-05-27 浙江大学 Trimanganese tetroxide nanocrystal and preparation method thereof
CN106430317A (en) * 2016-09-18 2017-02-22 陕西科技大学 Preparation method of flaky nano-Mn3O4
CN108585050B (en) * 2018-07-19 2020-03-20 郝新丽 Low-temperature green synthesis method of manganous-manganic oxide nanoring
CN114477297A (en) * 2021-12-30 2022-05-13 贵州梅岭电源有限公司 Preparation method of manganous-manganic oxide precursor of lithium manganate positive electrode material

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CN101219809A (en) * 2007-12-12 2008-07-16 中国科学院长春应用化学研究所 Process for producing mangano-manganic oxide nanocrystalline with controllable sizing and shape
CN101565208A (en) * 2009-05-21 2009-10-28 上海交通大学 Method for preparing manganic manganous oxide nano-material

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CN101219809A (en) * 2007-12-12 2008-07-16 中国科学院长春应用化学研究所 Process for producing mangano-manganic oxide nanocrystalline with controllable sizing and shape
CN101565208A (en) * 2009-05-21 2009-10-28 上海交通大学 Method for preparing manganic manganous oxide nano-material

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