CN103896340A - Method for preparing trimanganese tetroxide nano particles with adjustable sizes by adopting solvothermal method - Google Patents

Method for preparing trimanganese tetroxide nano particles with adjustable sizes by adopting solvothermal method Download PDF

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CN103896340A
CN103896340A CN201210580491.2A CN201210580491A CN103896340A CN 103896340 A CN103896340 A CN 103896340A CN 201210580491 A CN201210580491 A CN 201210580491A CN 103896340 A CN103896340 A CN 103896340A
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solvent
size
product
room temperature
trimanganese tetroxide
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宋锐
杨金胜
徐焕斌
王旭
郭睿达
李秀梅
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China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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Abstract

The invention relates to a method for preparing trimanganese tetroxide nano particles with adjustable sizes by adopting a solvothermal method. The method comprises the following steps: respectively taking 0.490-0.980g of Mn(CH3COO)2.4H2O to dissolve into four beakers which just contain 5-10ml of deionized water to obtain colorless clear solutions; respectively adding 15-30ml of acetone, ethanol, N,N-dimethyl formamide and dimethyl sulfoxide reagent to each beaker according to the fixed volume ratio, and intensely agitating for 5-20 minutes at room temperature; respectively transferring the mixed solutions to four 25-50ml stainless steel reaction kettles, and putting into an oven at 60-140 DEG C to react for 6-24 hours; naturally cooling the product to room temperature; centrifugally washing by using distilled water and absolute ethyl alcohol for a plurality of times respectively; and putting the product in an oven at 60-80 DEG C to dry for 1-4 hours, so as to obtain brown powder. The trimanganese tetroxide nano particles prepared by the method are different in size.

Description

The method of the trimanganese tetroxide nano particle that a kind of solvent-thermal method preparation size is adjustable
Technical field
The invention belongs to the synthetic field of nano material, be specifically related to the method for the trimanganese tetroxide nano particle adjustable with solvent-thermal method preparation size.
Background technology
Transition metal oxide nano crystalline substance is owing to having and the pattern of material, unique character of Size dependence, and significant self-assembly ability is occupying more and more consequence in field widely.Wherein there is the Mn of mixed valence 3o 4nano material attracts tremendous attention in many-sided application such as magnetic, electronics, catalysis and biotechnology because of it.
The performance of nano material depends primarily on size, pattern and the crystal formation of material immanent structure.The controlledly synthesis of nano material and preparation are the bases of further investigation its character and Application and Development and crucial, and are also vital for the research of the growth of nanoparticle, assembling and the Related Mechanism such as compound.The Mn that traditional high-temperature calcination can only obtain macrobead or very easily reunite 3o 4product.In recent years, people are by adopting new technology of preparing, as thermal decomposition method, the hot method of hydrothermal/solvent, hydrolysis oxidation method, radiation method (microwave, gamma-rays, ultrasonic wave), vapour deposition, electroless plating, arc-over, high temperature sputter etc., obtain the Mn of a series of structures and excellent performance 3o 4novel material.In order to reduce temperature and size of particles, be also that soft chemical preparation process is more widely used in order to reduce preparation cost, to improve reactive behavior simultaneously.Wherein the hot method of hydrothermal/solvent, as important soft chemical means, is prepared Mn 3o 4nano material has following characteristics: nano material epigranular prepared by (1), narrow size distribution; (2) high, the size of particles of purity and pattern are controlled.
Most people uses the hot method of hydrothermal/solvent, adds NaOH or other alkaline matter to make precipitation agent in be everlasting water or alcohol solvent.The solvent-thermal method of having reported is prepared Mn 3o 4nanocrystalline is mainly to use KMnO 4in the alcohol solvent of low temperature, react, if the people such as Weixin Zhang are by the volume ratio of modulation second alcohol and water, find in the time that ethanol volume ratio is 60%, under the hydrothermal temperature condition of 160 ℃, react 8 hours, the rectangle for preparing the about 50nm of median size is nanocrystalline, but temperature of reaction is higher, raw material KMnO 4price is more expensive, and nanocrystalline particle size heterogeneity; Also there are a few peoples to synthesize Mn under other solvent thermal condition 3o 4nanocrystalline.If the people such as Li-Xia Yang are with MnCl 2for manganese source, using dimethyl formamide within 24 hours, to obtain median size at 140 ℃ of-160 ℃ of solvent thermal reactions is 20nm, Mn in irregular shape 3o 4nanocrystalline.In sum, the solvent thermal of domestic and foreign literature report is prepared Mn at present 3o 4nanocrystalline, temperature of reaction is high and the time is longer, needs index of modulation many in reaction process, only can obtain the product of single size, and what reaction mechanism was set forth neither be very clear.
Summary of the invention
The object of this invention is to provide the method for the adjustable trimanganese tetroxide nano particle of a kind of solvent-thermal method preparation size, solve solvent-thermal method and prepare Mn 3o 4nanocrystalline particle size cannot modulation situation, prove hausmannite Tetragonal Mn 3o 4nanotube sample not only can make in very wide temperature range but also within the scope of very wide solvent.Can realize Mn by changing type of solvent and solvent thermal reaction temperature 3o 4the controlled modulation of nano-particles size.
The hot method of mixed solvent that the present invention has used respectively different organic solvents and water to form at lower temperature, synthesizes the Mn that a series of sizes are different in closed reactor 3o 4nanoparticle, according to solvent for use kind difference, size of particles is different, presents regular alternation.Form the problems such as mechanism and discuss with regard to the reactional equation in preparation process, nanoparticle.Meanwhile, for solvent species, the reason of size of particles impact has been made and may reasonably have been explained.The coordination ability of solvent is by by weak order being by force: acetone > ethanol > DMF > methyl-sulphoxide, the coordination ability of acetone is the strongest, the Mn preparing 3o 4nano-particles size minimum, median size only has 5nm; Methyl-sulphoxide coordination ability is the most weak, the Mn preparing 3o 4nano-particles size maximum, median size only has 13nm.Further, when solvent species is identical, we select wherein a kind of solvent (take acetone as example), investigate the impact of temperature variation on nanotube sample size.Along with solvent thermal reaction temperature raises, obtain Mn 3o 4nanocrystalline size of particles increases.
The trimanganese tetroxide nano particle that solvent-thermal method preparation size of the present invention is adjustable, is characterized in that: comprise the following steps
Step 1 is got respectively 0.490g～0.980gMn (CH 3cOO) 24H 2o is dissolved in 4 beakers that fill 5ml～10ml deionized water, obtains colorless cleared solution;
Step 2 adds respectively 15ml～30ml acetone, ethanol, DMF and methyl-sulphoxide reagent, room temperature strong stirring (5～20) minute by fixed volume ratio in above-mentioned each beaker;
Step 3 is transferred to mixing solutions respectively in 4 25ml～50ml stainless steel cauldrons, is placed in 60 ℃～140 ℃ baking oven reactions (6～24) hour;
Step 4 product naturally cools to room temperature, uses respectively repeatedly centrifuge washing of distilled water, dehydrated alcohol;
Step 5 product is placed in 60 ℃～80 ℃ baking ovens dry (1～4) hour and obtains brown powder.
All products are Tetragonal hausmannite type mangano-manganic oxide nanocrystalline, and spacer is I41/amd (141), JCPDS No.18-0803.
Under condition of different temperatures, the product pattern that different solvents hot preparation obtains is uniform nano spherical particle.
Under 60 ℃～140 ℃ conditions, dimethylsulfoxide solvent thermal response, particle size range 3nm-8nm.
Under 60 ℃～140 ℃ conditions, solvent dimethylformamide thermal response, particle size range 5nm-10nm.
Under 60 ℃～140 ℃ conditions, alcohol solvent thermal response, particle size range 7nm-11nm.
Under 60 ℃～140 ℃ conditions, acetone solvent thermal response, particle size range 9nm-16nm.
Temperature of reaction identical (as being 100 ℃), size of particles difference when solvent is different, four kinds of solvents selecting and Mn 2+coordination ability be not both and cause the Mn that obtains 3o 4the basic reason that nano-particles size is different.Represent ligand molecular with R, methyl-sulphoxide molecule coordination ability is the strongest, forms intermediate [Mn (OH) xr 6-x] 2-xcoordination compound is maximum, and the nucleus that thermal degradation generates is corresponding also maximum, at Mn 2+sum is all in identical situation, a large amount of Mn 2+participate in nucleation, for the Mn growing 2+amount tail off, so the seeded growth after nucleation is slow, finally cause the Mn generating 3o 4the size minimum of nanocrystal.Otherwise acetone molecules coordination ability is the most weak, more difficult and Mn 2+form complex compound, decompose the nucleus obtaining few, a large amount of Mn 2+do not participate in nucleation, but for grain growing, thereby obtain the nanoparticle of large-size.
Acetone solvent thermal response, the size of particles difference of the mangano-manganic oxide nanocrystalline that change temperature of reaction obtains, nanocrystal surface activity is higher, the grain growth of solvent thermal process is mainly take interfacial diffusion as main, and suitable temperature and pressure that in autoclave, solvent thermal condition provides are conducive to Mn within the specific limits 3o 4nanocrystalline growth.So along with the rising grain growing speed of temperature of reaction will be accelerated, size of particles increases.
Use SQUID sample that the present invention is prepared to carry out magnetic property test, result shows, the coercive force numerical value of sample reduces with size of particles and increases, and particle diameter is less, and the coercive force of sample is larger.The wherein Mn of dimethylsulfoxide solvent hot preparation 3o 4nanocrystalline coercive force, up to 6851Oe, is potential high-quality hard magnetic material.
Beneficial effect of the present invention:
(1) illustrate theoretically the reaction mechanism that solvent-thermal method is prepared transition metal oxide nano crystalline substance, disclosed first the reason of the nano-particles size difference that different organic solvents hot method obtains.
(2) X-ray diffraction result shows (seeing accompanying drawing 3), the mangano-manganic oxide nanocrystalline preparing by method of the present invention, and better crystallinity degree, output is high; Transmission electron microscope photo can be seen (seeing accompanying drawing 1,2), the less also homogeneous more of product that size of particles is prepared than other solvent thermal processes;
(3) solvent thermal temperature of the present invention is than other solvent thermal processes lower (can lower than 100 ℃), and the time used is shorter, thereby more saves from the energy;
(4) this preparation method only needs cheap starting raw material and simple synthetic route, and cost is low, and reproducible, in proportion expanding production; Product postprocessing is easy, pollution-free;
(5) magnetic property test result shows, trimanganese tetroxide sample prepared by this invention has good magnetic property, and relevant with the dimensional effect of particle.When trimanganese tetroxide nano size of particles is less, the coercive force of crystal is larger.The corresponding relation of size of particles and magnetic property is in table 1.
Table 1
Figure BDA00002668593600041
Accompanying drawing explanation
Fig. 1. the Mn of different solvents thermal synthesis in the time of 100 ℃ 3o 4the transmission electron microscope photo of sample.
A) acetone; B) ethanol; C) DMF; D) methyl-sulphoxide.
Fig. 2 a-e) take acetone as solvent, the Mn synthesizing under condition of different temperatures 3o 4the transmission electron microscope photo of nanotube sample.
Fig. 3 (under 100 ℃ of conditions) standby Mn of the hot legal system of different solvents 3o 4the X-ray diffraction spectrum of nanotube sample
A. acetone; B. ethanol; C.N, dinethylformamide; D. methyl-sulphoxide
Embodiment
Embodiment 1
Step 1 is got respectively 0.490gMn (CH 3cOO) 24H 2o is dissolved in 4 beakers that fill 5ml deionized water, obtains colorless cleared solution;
Step 2 adds respectively 15ml acetone, ethanol, DMF and methyl-sulphoxide reagent in above-mentioned each beaker, room temperature strong stirring 10 minutes;
Step 3 is transferred to mixing solutions respectively in 4 25ml stainless steel cauldrons, is placed in 100 ℃ of baking ovens and reacts 12 hours;
Step 4 product naturally cools to room temperature, uses respectively repeatedly centrifuge washing of distilled water, dehydrated alcohol;
Step 5 product is placed in 60 ℃ of baking ovens and within dry 4 hours, obtains brown powder.
Product size of particles changes sees accompanying drawing 1
Embodiment 2
Step 1 is by 0.490g Mn (CH 3cOO) 24H 2o is dissolved in 5ml deionized water, obtains colorless cleared solution;
Step 2 adds 15ml acetone with transfer pipet in above-mentioned solution, magnetic agitation 10 minutes;
Step 3 is transferred to homogeneous mixture solotion in 25ml stainless steel cauldron, in 60 ℃ of baking ovens, reacts 12 hours;
Step 4 product naturally cools to room temperature, uses respectively repeatedly centrifuge washing of distilled water, dehydrated alcohol;
Step 5 product is placed in 60 ℃ of baking ovens and within dry 4 hours, obtains brown powder.
Embodiment 3
Step 1 is by 0.490g Mn (CH 3cOO) 24H 2o is dissolved in 5ml deionized water, obtains colorless cleared solution;
Step 2 adds 15ml acetone with transfer pipet in above-mentioned solution, magnetic agitation 10 minutes;
Step 3 is transferred to homogeneous mixture solotion in 25ml stainless steel cauldron, in 100 ℃ of baking ovens, reacts 12 hours;
Step 4 product naturally cools to room temperature, uses respectively repeatedly centrifuge washing of distilled water, dehydrated alcohol;
Step 5 product is placed in 60 ℃ of baking ovens and within dry 4 hours, obtains brown powder.
Embodiment 4
Step 1 is by 0.490g Mn (CH 3cOO) 24H 2o is dissolved in 5ml deionized water, obtains colorless cleared solution;
Step 2 adds 15ml acetone with transfer pipet in above-mentioned solution, magnetic agitation 10 minutes;
Step 3 is transferred to homogeneous mixture solotion in 25ml stainless steel cauldron, in 140 ℃ of baking ovens, reacts 12 hours;
Step 4 product naturally cools to room temperature, uses respectively repeatedly centrifuge washing of distilled water, dehydrated alcohol;
Step 5 product is placed in 60 ℃ of baking ovens and within dry 4 hours, obtains brown powder.
Product size of particles changes sees Fig. 2.

Claims (1)

1. a method for the adjustable trimanganese tetroxide nano particle of solvent-thermal method preparation size, is characterized in that:
Comprise the following steps
(1) get respectively 0.490g～0.980gMn (CH 3cOO) 24H 2o is dissolved in 4 beakers that fill 5ml～10ml deionized water, obtains colorless cleared solution;
(2) in above-mentioned each beaker, add respectively 15ml～30ml acetone, ethanol, DMF and methyl-sulphoxide reagent, room temperature strong stirring (5～20) minute by fixed volume ratio;
(3) mixing solutions is transferred to respectively in 4 25ml～50ml stainless steel cauldrons, is placed in 60 ℃～140 ℃ baking oven reactions (6～24) hour;
(4) product naturally cools to room temperature, uses respectively repeatedly centrifuge washing of distilled water, dehydrated alcohol;
(5) product is placed in 60 ℃～80 ℃ baking ovens dry (1～4) hour and obtains brown powder.
CN201210580491.2A 2012-12-27 2012-12-27 Method for preparing trimanganese tetroxide nano particles with adjustable sizes by adopting solvothermal method Pending CN103896340A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005060610A2 (en) * 2003-12-11 2005-07-07 The Trustees Of Columbia University In The City Ofnew York Nano-sized particles, processes of making, compositions and uses thereof
CN101439876A (en) * 2008-12-25 2009-05-27 中国科学院长春应用化学研究所 Method for preparing manganomanganic oxide nanocrystalline by multi-solvent combined two-phase process
CN102259928A (en) * 2011-05-20 2011-11-30 浙江大学 Method for preparing Mn3O4 nano-particles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005060610A2 (en) * 2003-12-11 2005-07-07 The Trustees Of Columbia University In The City Ofnew York Nano-sized particles, processes of making, compositions and uses thereof
CN101439876A (en) * 2008-12-25 2009-05-27 中国科学院长春应用化学研究所 Method for preparing manganomanganic oxide nanocrystalline by multi-solvent combined two-phase process
CN102259928A (en) * 2011-05-20 2011-11-30 浙江大学 Method for preparing Mn3O4 nano-particles

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
LI-XIA YANG, ET AL.: "Controlled synthesis of Mn3O4 and MnCO3 in a solvothermal system", 《MATERIALS RESEARCH BULLETIN》, vol. 44, 25 March 2009 (2009-03-25) *
宋锐: "过渡金属氧化物纳米晶的软化学合成和表征", 《中国博士学位论文全文数据库工程科技I辑》, 15 August 2010 (2010-08-15) *
梁军等: "纳米四氧化三锰的溶剂热合成", 《石油化工应用》, vol. 30, no. 8, 31 August 2011 (2011-08-31), pages 4 - 5 *
范武刚等: "二甲基亚砜介质中纳米Mn3O4的合成", 《无机材料学报》, vol. 21, no. 4, 31 July 2006 (2006-07-31) *

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Application publication date: 20140702