CN103991907B - A kind of preparation method of manganous carbonate nanofiber ball - Google Patents

A kind of preparation method of manganous carbonate nanofiber ball Download PDF

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CN103991907B
CN103991907B CN201410191556.3A CN201410191556A CN103991907B CN 103991907 B CN103991907 B CN 103991907B CN 201410191556 A CN201410191556 A CN 201410191556A CN 103991907 B CN103991907 B CN 103991907B
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manganous
solution
inner bag
reactor
carbonate
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CN103991907A (en
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杨琳琳
王永刚
王晓峰
王玉江
徐国辉
林海燕
罗伟
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Luoyang Institute of Science and Technology
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Luoyang Institute of Science and Technology
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Abstract

The invention discloses a kind of preparation method of manganous carbonate nanofiber ball.Manganous chloride tetrahydrate mixes with Seignette salt to react by the present invention mutually, forms manganous tartrate precipitation, more this manganous tartrate precipitation is mixed mutually with solution of potassium carbonate loads in reactor, 50 ~ 200 ounder C, insulation carries out hydrothermal treatment consists in 3 ~ 10 hours, allows reactor naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, after filtration, oven dry, obtains manganous carbonate nanofiber ball.The present invention has that technique is simple, morphology controllable, good crystallinity, purity are high, have unique self-assembled structures, and with low cost, do not use and anyly have the advantages such as contaminated surface promoting agent.

Description

A kind of preparation method of manganous carbonate nanofiber ball
Technical field
The present invention relates to a kind of preparation method of manganous carbonate nanofiber ball, particularly relate to the manganous carbonate nanofiber ball preparation method of a kind of manganous tartrate precipitation as reaction precursor.
Background technology
Manganous carbonate (MnCO3) is a kind of very important inorganic materials, it is not only the main raw material producing soft magnetic ferrite, and much all there is field application widely at electronics, catalyzer, pigment, medicine, pottery etc., thus become one of study hotspot in recent years.As everyone knows, the performance of nano material depends on the factor such as pattern and size of its nanocrystal, the nano material thus with special appearance all can show the performance of some excellences, therefore, the manganous carbonate crystal preparing novel in shape all has very important significance in theoretical basis research and practical application.
At present to the control of manganous carbonate crystal morphology usually by be tensio-active agent, tensio-active agent is generally cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, polyoxyethylene glycol, polyvinylpyrrolidone etc.Due to a large amount of uses of tensio-active agent, can make to produce the foam that pile up like a mountain in river, the tensio-active agent that allowed people recognize is to the tremendous influence of environment.The water nutrition problem that a large amount of uses of tensio-active agent cause simultaneously still annoyings us, it has been recognized that the major issue that environmental problem will be following nano-functional material preparation development.
Summary of the invention
The object of the invention is the deficiency in order to solve the problems of the technologies described above existence, there is provided that a kind of technique is simple, morphology controllable, good crystallinity, purity are high, have unique self-assembled structures, and with low cost, do not use any preparation method having the manganous carbonate nanofiber ball of contaminated surface promoting agent.
The preparation method of manganous carbonate nanofiber ball of the present invention, concrete steps are as follows:
Step one, Manganous chloride tetrahydrate is dissolved in deionized water, form the Manganous chloride tetrahydrate aqueous solution, the concentration of the Manganous chloride tetrahydrate in regulator solution is 0.2 ~ 4.0mol/L;
Step 2, Seignette salt is dissolved in deionized water, form aqueous sodium potassium tartrate, the concentration of the Seignette salt in regulator solution is 0.2 ~ 4.0mol/L;
Step 3, salt of wormwood is dissolved in deionized water, form wet chemical, the concentration of the salt of wormwood in regulator solution is 0.2 ~ 4.0mol/L;
The potassium sodium tartrate solution that step 4, manganese chloride solution step one obtained and step 2 obtain mixes mutually, and blending ratio is 1:1, obtains manganous tartrate precipitation as reaction precursor;
The manganous tartrate precipitation solution that step 5, the solution of potassium carbonate and the step 4 that step 3 are obtained obtain mixes mutually, blending ratio is 1:1, then join in reactor inner bag, regulate the reaction mass volume in reactor inner bag to reach 70% ~ 90% of reactor inner bag volume with distilled water;
Step 6, reactor inner bag step 5 being equipped with reaction mass are placed in reactor, and sealing, 50 ~ 200 ounder C, insulation carries out hydrothermal treatment consists in 3 ~ 10 hours, then allows reactor naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, filters, 50 oafter drying at C temperature, obtain manganous carbonate nanofiber ball.
Use manganous tartrate precipitation as reaction precursor in the present invention, if without manganous tartrate precipitation, just can not get this manganous carbonate nanofiber ball.This is because: under normal conditions, can pass through external force, the mode of namely adding tensio-active agent has orientation to make the growth of crystal, namely obtains the crystal of one-dimensional square to growth.When adding tensio-active agent in reaction system, because SURFACTANT ADSORPTION is in manganous carbonate growth unit surface, guide effect is served to the growth of manganous carbonate crystal, manganous carbonate crystal therefore can be made to occur oriented growth, one dimension manganous carbonate crystal can be obtained, as manganese carbonate nanorod.But tensio-active agent has huge pollution to environment.
And in the present invention, do not use any tensio-active agent.Reaction precursor is changed in the present invention, do not use conventional mn ion, and be the use of manganous tartrate precipitation as reaction precursor, this is because manganous tartrate is in the process of growth of manganous carbonate crystal, not only itself there is extraordinary orientation, and can make manganous carbonate crystal in the process of growth, there is self-assembly, thus make the total energy of manganous carbonate crystal reach minimum, therefore the present invention under the condition not using tensio-active agent, can obtain the nanofiber ball of one dimension manganous carbonate nanofiber composition.In the present invention, using manganous tartrate precipitation as reaction precursor, otherwise manganous carbonate nanofiber ball must be can not get.
The purity of described salt of wormwood, Manganous chloride tetrahydrate, Seignette salt and dehydrated alcohol is all not less than chemical pure.
Regulate the reaction mass volume in reactor inner bag to reach 70% ~ 90% of reactor inner bag volume with distilled water wherein in step 5, this is to make hydro-thermal reaction system be in boiling state, is beneficial to crystallization and the growth of manganous carbonate crystal.
Use distilled water repetitive scrubbing reaction product wherein in step 6, filters, 50 odry at C temperature, this is to obtain drying and the higher manganous carbonate crystal of purity.
Beneficial effect of the present invention is:
The present invention has prepared the manganous carbonate nanofiber ball that good crystallinity, purity are high, have unique texture, especially the manganous carbonate nanofiber ball obtained is formed by the self-assembly of manganous carbonate fiber, the diameter of manganous carbonate fiber is about 10-15nm, and the length of manganous carbonate fiber is about 400-500 nanometer.So-called self-assembly refers to basic structural unit (molecule, nano material, the material of micron or more big scale) the spontaneous a kind of technology being formed with sequence structure.In the process of self-assembly, basic structural unit spontaneous tissue or gathering under based on the interaction of non covalent bond are a structure stablizing, have certain regular geometric outward appearance.Self-assembly is the important means created novel substance and produce New function, and the special supramolecular structure utilizing self-assembly to be formed, conventional chemical can be prepared and synthesize the functional materials that cannot realize, be considered to solve the hope place that the current mankind such as material, the energy, health and environment develop the significant challenge faced.
The synthetic method of manganous carbonate nanofiber ball provided by the invention, have simple to operate, do not use the advantages such as any organic surface active agent, pollution-free, with low cost, morphology controllable, be easy to suitability for industrialized production.The manganous carbonate nanofiber ball that the present invention prepares first, has unique fibrous texture, thus in electronics, pottery, catalyzer, medicine, coating, enamel etc., will have more excellent performance, and have application prospect more widely.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the manganous carbonate nanofiber ball that the present invention synthesizes.
Fig. 2 is transmission electron microscope (TEM) photo of the manganous carbonate nanofiber ball that the present invention synthesizes.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Step one, Manganous chloride tetrahydrate is dissolved in deionized water, form the Manganous chloride tetrahydrate aqueous solution, the concentration of the Manganous chloride tetrahydrate in regulator solution is 0.2mol/L;
Step 2, Seignette salt is dissolved in deionized water, form aqueous sodium potassium tartrate, the concentration of the Seignette salt in regulator solution is 0.2mol/L;
Step 3, salt of wormwood is dissolved in deionized water, form wet chemical, the concentration of the salt of wormwood in regulator solution is 0.2mol/L;
The potassium sodium tartrate solution that step 4, manganese chloride solution step one obtained and step 2 obtain mixes mutually, and blending ratio is 1:1, obtains manganous tartrate precipitation as reaction precursor;
The manganous tartrate precipitation solution that step 5, the solution of potassium carbonate and the step 4 that step 3 are obtained obtain mixes mutually, blending ratio is 1:1, then join in reactor inner bag, regulate the reaction mass volume in reactor inner bag to reach 90% of reactor inner bag volume with distilled water;
Step 6, reactor inner bag step 5 being equipped with reaction mass are placed in reactor, and sealing, 60 ounder C, insulation carries out hydrothermal treatment consists in 10 hours, then allows reactor naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, filters, 50 oafter drying at C temperature, obtain manganous carbonate nanofiber ball.Manganous carbonate nanofiber ball is formed by the self-assembly of manganous carbonate fiber, and the diameter of manganous carbonate fiber is about 10nm, and the length of manganous carbonate fiber is about 400 nanometers, and its XRD figure spectrum is shown in Fig. 1; Transmission electron microscope picture is shown in Fig. 2.
Embodiment 2
Step one, Manganous chloride tetrahydrate is dissolved in deionized water, form the Manganous chloride tetrahydrate aqueous solution, the concentration of the Manganous chloride tetrahydrate in regulator solution is 1.8mol/L;
Step 2, Seignette salt is dissolved in deionized water, form aqueous sodium potassium tartrate, the concentration of the Seignette salt in regulator solution is 1.8mol/L;
Step 3, salt of wormwood is dissolved in deionized water, form wet chemical, the concentration of the salt of wormwood in regulator solution is 1.8mol/L;
The potassium sodium tartrate solution that step 4, manganese chloride solution step one obtained and step 2 obtain mixes mutually, and blending ratio is 1:1, obtains manganous tartrate precipitation as reaction precursor;
The manganous tartrate precipitation solution that step 5, the solution of potassium carbonate and the step 4 that step 3 are obtained obtain mixes mutually, blending ratio is 1:1, then join in reactor inner bag, regulate the reaction mass volume in reactor inner bag to reach 80% of reactor inner bag volume with distilled water;
Step 6, reactor inner bag step 5 being equipped with reaction mass are placed in reactor, and sealing, 120 ounder C, insulation carries out hydrothermal treatment consists in 6 hours, then allows reactor naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, filters, 50 oafter drying at C temperature, obtain manganous carbonate nanofiber ball.
Embodiment 3
Step one, Manganous chloride tetrahydrate is dissolved in deionized water, form the Manganous chloride tetrahydrate aqueous solution, the concentration of the Manganous chloride tetrahydrate in regulator solution is 3.3mol/L;
Step 2, Seignette salt is dissolved in deionized water, form aqueous sodium potassium tartrate, the concentration of the Seignette salt in regulator solution is 3.3mol/L;
Step 3, salt of wormwood is dissolved in deionized water, form wet chemical, the concentration of the salt of wormwood in regulator solution is 3.3mol/L;
The potassium sodium tartrate solution that step 4, manganese chloride solution step one obtained and step 2 obtain mixes mutually, and blending ratio is 1:1, obtains manganous tartrate precipitation as reaction precursor;
The manganous tartrate precipitation solution that step 5, the solution of potassium carbonate and the step 4 that step 3 are obtained obtain mixes mutually, blending ratio is 1:1, then join in reactor inner bag, regulate the reaction mass volume in reactor inner bag to reach 70% of reactor inner bag volume with distilled water;
Step 6, reactor inner bag step 5 being equipped with reaction mass are placed in reactor, and sealing, 200 ounder C, insulation carries out hydrothermal treatment consists in 3 hours, then allows reactor naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, filters, 50 oafter drying at C temperature, obtain manganous carbonate nanofiber ball.

Claims (2)

1. a preparation method for manganous carbonate nanofiber ball, is characterized in that: step one, Manganous chloride tetrahydrate is dissolved in deionized water, and form the Manganous chloride tetrahydrate aqueous solution, the concentration of the Manganous chloride tetrahydrate in regulator solution is 0.2 ~ 4.0mol/L; Step 2, Seignette salt is dissolved in deionized water, form aqueous sodium potassium tartrate, the concentration of the Seignette salt in regulator solution is 0.2 ~ 4.0mol/L; Step 3, salt of wormwood is dissolved in deionized water, form wet chemical, the concentration of the salt of wormwood in regulator solution is 0.2 ~ 4.0mol/L; The potassium sodium tartrate solution that step 4, manganese chloride solution step one obtained and step 2 obtain mixes mutually, and blending ratio is 1:1, obtains manganous tartrate precipitation as reaction precursor; The manganous tartrate precipitation solution that step 5, the solution of potassium carbonate and the step 4 that step 3 are obtained obtain mixes mutually, and blending ratio is 1:1, then joins in reactor inner bag; Step 6, reactor inner bag step 5 being equipped with reaction mass are placed in reactor, and sealing, 50 ~ 200 ounder C, insulation carries out hydrothermal treatment consists in 3 ~ 10 hours, then allows reactor naturally cool to room temperature, after unloading still, by distilled water repetitive scrubbing reaction product, filters, 50 oafter drying at C temperature, obtain manganous carbonate nanofiber ball.
2. the preparation method of a kind of manganous carbonate nanofiber ball according to claim 1, it is characterized in that: the manganous tartrate precipitation solution that solution of potassium carbonate step 3 obtained obtains with step 4 mixes mutually, then join in reactor inner bag, regulate the reaction mass volume in reactor inner bag to reach 70% ~ 90% of reactor inner bag volume with distilled water.
CN201410191556.3A 2014-05-08 2014-05-08 A kind of preparation method of manganous carbonate nanofiber ball Expired - Fee Related CN103991907B (en)

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CN108530024A (en) * 2018-05-28 2018-09-14 钦州学院 It is a kind of can shock resistance Nixing pottery manufacture craft
CN111704169B (en) * 2020-07-01 2022-09-30 洛阳理工学院 Preparation method of manganese molybdate nanosheet crystal

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101269840A (en) * 2008-03-05 2008-09-24 广州融捷材料科技有限公司 Spherical manganese carbonate and preparing method thereof
CN101805024A (en) * 2010-04-27 2010-08-18 江苏大学 Preparation method of manganese carbonate nanorod
CN102120618A (en) * 2011-01-26 2011-07-13 江苏方舟新能源股份有限公司 Preparation method of high-tap density manganese carbonate
CN102531065A (en) * 2010-12-30 2012-07-04 河南科隆集团有限公司 Spherical manganese carbonate synthetic method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101269840A (en) * 2008-03-05 2008-09-24 广州融捷材料科技有限公司 Spherical manganese carbonate and preparing method thereof
CN101805024A (en) * 2010-04-27 2010-08-18 江苏大学 Preparation method of manganese carbonate nanorod
CN102531065A (en) * 2010-12-30 2012-07-04 河南科隆集团有限公司 Spherical manganese carbonate synthetic method
CN102120618A (en) * 2011-01-26 2011-07-13 江苏方舟新能源股份有限公司 Preparation method of high-tap density manganese carbonate

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Inventor after: Yang Linlin

Inventor after: Wang Yonggang

Inventor after: Wang Xiaofeng

Inventor after: Wang Yujiang

Inventor after: Xu Guohui

Inventor after: Lin Haiyan

Inventor after: Luo Wei

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Free format text: CORRECT: INVENTOR; FROM: WANG YONGGANG YANG LINLIN WANG XIAOFENG WANG YUJIANG XU GUOHUI LIN HAIYAN LUO WEI TO: YANG LINLIN WANG YONGGANG WANG XIAOFENG WANG YUJIANG XU GUOHUI LIN HAIYAN LUO WEI

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