CN100558644C - Layered mesoporous birnessite manganese dioxide cellular nanometer ball and its production and use - Google Patents
Layered mesoporous birnessite manganese dioxide cellular nanometer ball and its production and use Download PDFInfo
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- CN100558644C CN100558644C CNB2006101134210A CN200610113421A CN100558644C CN 100558644 C CN100558644 C CN 100558644C CN B2006101134210 A CNB2006101134210 A CN B2006101134210A CN 200610113421 A CN200610113421 A CN 200610113421A CN 100558644 C CN100558644 C CN 100558644C
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Abstract
The invention belongs to the nano material preparation technical field, particularly a kind of layered mesoporous birnessite type MnO
2Cellular nano-sphere and hollow nano-sphere and preparation method thereof.The present invention is to be reactant with the potassium permanganate of cheapness and oleic acid, need not be through peracid or alkaline purification, redox reaction takes place in neutral aqueous solution, by control potassium permanganate/oleic mol ratio, can obtain monodispersed layered mesoporous birnessite type MnO respectively
2Cellular nano-sphere and hollow nano-sphere.Method of the present invention need not tensio-active agent, and preparation technology is simple, and cost is low, the reaction conditions gentleness.The layered mesoporous birnessite type MnO that the present invention makes
2Cellular nano-sphere and hollow nano-sphere have abundant mesoporous, and bigger specific surface area and pore capacities have good structural stability, can be used as the carrier of catalyzer or sorbent material; And as parting material, magneticsubstance, the electrode materials of battery, oxidative degradation material, desulfurization or material for air purification etc.
Description
Technical field
The invention belongs to the nano material preparation technical field, particularly a kind of layered mesoporous birnessite type MnO
2Cellular nano-sphere and its production and use.
Background technology
Birnessite (below write a Chinese character in simplified form Bir) type Mn oxide (also claims birnessite, Na
4Mn
14O
279H
2O), being widespread in nature in soil and settling, is a class two-dimensional stratiform Mn oxide, the about 0.7nm of interlamellar spacing (Y.Ma, J.Luo, S.L.Suib, Chem.Mater.1999,11,1972; Q.Feng, H.Kanoh, K.Ooi, J.Mater.Chem.1999,9,319; Z.H.Liu, K.Ooi, H.Kanoh, W.P.Tang, T.Tomoda, Langmuir 2000,16, and 4154).Its lamella is by manganese oxygen octahedra MnO
6The limit constitutes altogether, and interlayer occupies filling by water molecules, metal ion.The layer structure on every 6 manganese oxygen octahedra MnO
6A room is just arranged, make that whole octahedral layer is electronegative, the positively charged ion between embeding layer keeps the stable of laminate structure by electrostatic interaction.Because the special laminate structure that Bir type Mn oxide has, in a lot of fields important use is arranged, as molecular sieve, ion-exchanger, effective catalyst, magneticsubstance, secondary battery electrode material, electrochemistry, selective adsorbent, nano composite material and sulfidizing agent etc.Therefore, correlative study has caused numerous scientific workers' concern.
The common synthetic method of Bir type Mn oxide has hydrothermal method, sol-gel method, circumfluence method and high temperature solid-state chemical reaction method etc.Hydrothermal method is generally finished reaction under the mild conditions between 100～300 ℃.This method is dissolved in the water inorganic manganese salt, adds a certain amount of alkali or acid, is made into certain density mixing solutions, after stirring, transfers in the autoclave, controls certain hydrothermal temperature and time.For example Xu etc. (Y.H.Xu, Q.Feng, K.Kajiyoshi and K.Yanagisawa, Chem.Mater., 2002,14,697.) adopts hydrothermal method to synthesize multiple stratiform Bir oxide compound.With respect to other method, can obtain the high Bir oxide compound of purity.Difficulty is to control reaction pressure, and reactant feed proportioning and purity are also had certain requirement.The synthetic basic process of Bir oxide compound of sol-gel method such as Fig. 4.This method principle is simple, but influenced by solvent, pH, amount of water, digestion time and calcining temperature etc., thereby synthetic reaction condition is had relatively high expectations.High temperature solid state reaction prepares stratiform Na
xMnO
2, obtain product Li through ion-exchange
xMnO
2Utilize Li
xMnO
2The stratiform secondary lithium battery of preparation, compare with common lithium-manganese cell, have advantages such as specific storage height, cycle performance be better, and laminate structure has bigger reversible lithium embedding ability than other any structure, these good electrochemical properties have caused the very big interest of people (H Kanoh, W P Tang, Y Makitaet al.Langmuir, 1997,13:6845.).But up to now, also do not find to prepare the controlled Bir type Mn oxide of pattern by redox under the property condition at room temperature.The present invention develops the novel process of simple, the with low cost preparation of a kind of method Bir type Mn oxide.Ratio by the control reactant can obtain monodispersed cellular nano-sphere and hollow nano-sphere respectively.The Bir type Mn oxide specific surface area that makes through test shows is big, pore size distribution mesoporous scope (2～50nm), have higher structural stability, through 120W, the ultrasonication of 40KHz 30 minutes, pattern remains unchanged.
Summary of the invention
One of purpose of the present invention provides a kind of purity height, and the good layered mesoporous birnessite type MnO of structural stability
2Cellular nano-sphere.
Two of purpose of the present invention provides a kind of purity height, and the good layered mesoporous birnessite type MnO of structural stability
2Cellular hollow nano-sphere.
Three of purpose of the present invention provides a kind of brand-new layered mesoporous birnessite type MnO
2The preparation method of cellular nano-sphere and hollow nano-sphere, this preparation method's technology is simple, cost is low.
Four of purpose of the present invention provides layered mesoporous birnessite type MnO
2The purposes of cellular nano-sphere and hollow nano-sphere.
The present invention is to be reactant with the potassium permanganate of cheapness and oleic acid, need not redox reaction take place through peracid or alkaline purification in neutral aqueous solution, by the control potassium permanganate/oleic mol ratio (MnO of the amount of potassium permanganate to generating
2Pattern influence bigger), can obtain monodispersed birnessite type MnO respectively
2Cellular nano-sphere and hollow nano-sphere.The birnessite type MnO that the present invention makes
2Have abundant mesoporous, bigger specific surface area and pore capacities and good structural stability.
Layered mesoporous birnessite type MnO of the present invention
2Cellular nano-sphere is characterised in that the MnO that is made of polynuclear plane
2Nanometer ball, the aperture of its honeycomb are mesoporous size 3～15nm, and the stratified pieces between the honeycomb is by 5～9 layers of MnO
6The octahedra individual layer that constitutes is formed, and wherein the thickness of every stratified pieces is 7～10 nanometers; This MnO
2The specific surface area of cellular nano-sphere is 60～80m
2/ g, pore capacities is 0.1～0.3cm
3/ g, MnO
2The cellular nano-sphere particle diameter is in 70～100 nanometers.This MnO
2Cellular nano-sphere has higher structural stability, and through 120W ultrasonication 30～40 minutes, pattern remained unchanged.
Layered mesoporous birnessite type MnO of the present invention
2Cellular nano-sphere comprises the MnO that polynuclear plane constitutes
2Hollow nano-sphere, the aperture of its honeycomb are mesoporous size 3～15nm, and the stratified pieces between the honeycomb is by MnO
6Octahedra formation, thickness is 1～6 nanometer; This MnO
2The specific surface area of cellular hollow nano-sphere is 30～50m
2/ g, pore capacities is 0.05～0.2cm
3/ g, MnO
2Cellular hollow nano-sphere particle diameter is in 50～150 nanometers.This MnO
2Cellular hollow nano-sphere has higher structural stability, and through 120W ultrasonication 30～40 minutes, pattern remained unchanged.
Layered mesoporous birnessite type MnO of the present invention
2The preparation method of cellular nano-sphere may further comprise the steps:
(1). at room temperature get 0.1～1.0 gram potassium permanganate and be dissolved in 40～60mL distilled water, stir and formed uniform solution in 15～30 minutes;
(2). oleic acid is joined in the solution that step (1) obtains, and wherein, potassium permanganate and oleic molar ratio are 1/10～3/10, and stirring reaction 5～20 hours obtains the chocolate solid sediment;
(3). the chocolate solid sediment that step (2) obtains is centrifugal, washing;
(4). the product that step (3) is obtained is not less than 10 hours 50～70 degrees centigrade of vacuum-dryings, can obtain pattern layered mesoporous birnessite type MnO preferably
2Cellular nano-sphere.
Potassium permanganate consumption in increasing reaction system, making potassium permanganate and oleic molar ratio is 〉=1 o'clock, can obtain pattern layered mesoporous birnessite type MnO preferably
2Cellular hollow nano-sphere.
Described potassium permanganate purity is not less than 99.5%.
Described oleic acid density is 0.891～0.899g/mL, and saponification value is not less than 3, and acid number is 190～200.
Layered mesoporous birnessite type MnO of the present invention
2Cellular nano-sphere, or layered mesoporous birnessite type MnO
2Cellular hollow nano-sphere can be as the carrier of catalyzer or sorbent material; And as parting material, magneticsubstance, the electrode materials of battery, oxidative degradation material, desulfurization or material for air purification.
Birnessite type MnO provided by the invention
2Material and preparation method thereof and mechanism: get potassium permanganate and be dissolved in the distilled water, stir, purpose is to make potassium permanganate dissolve and form the solution of homogeneous fully.Dropwise add oleic acid then, purpose is to make the oleic acid can uniform distribution in solution, and it is too high to be unlikely to partial concn.Keep reaction to carry out more than 5 hours, can obtain layered mesoporous birnessite type MnO respectively
2Cellular nano-sphere, and layered mesoporous birnessite type MnO
2Cellular hollow nano-sphere is at last with sample separation, washing, in vacuum-drying under 50～70 degrees celsius more than 10 hours.Use 120W at normal temperatures, the ultrasonication of 40KHz, observation structure stability, through 120W ultrasonication 30～40 minutes, pattern remained unchanged.
Preparation method of the present invention need not tensio-active agent, and preparation technology is simple, and cost is low, the birnessite type MnO that the present invention makes
2Have abundant mesoporous, good structural stability, higher specific surface area can be in catalysis, absorption, parting material, and magneticsubstance, the electrode materials of battery, the oxidative degradation material, aspects such as desulfurization and material for air purification have important use and are worth.
Description of drawings
Fig. 1. the layered mesoporous birnessite type MnO of the embodiment of the invention 1 and 2 preparations
2The scanning electron microscope of cellular nano-sphere and hollow nano-sphere and transmission electron microscope photo.Wherein:
Fig. 1 a and 1b are respectively embodiment 1 layered mesoporous birnessite type MnO
2The scanning electron microscope of cellular nano-sphere and transmission electron microscope photo;
Fig. 1 c and 1d are respectively embodiment 2 layered mesoporous birnessite type MnO
2The scanning electron microscope of hollow nano-sphere and transmission electron microscope photo.
Fig. 2. the layered mesoporous birnessite type MnO that the embodiment of the invention 1 makes
2The cellular nano-sphere last X-ray diffractogram of pulverizing.
Fig. 3. the layered mesoporous birnessite type MnO of the embodiment of the invention 3
2Nitrogen adsorption-the desorption isotherm of cellular nano-sphere and cellular hollow nano-sphere reaches the mesoporous pore size distribution curve that is calculated by this nitrogen adsorption-desorption isotherm.Wherein:
Fig. 3 a is layered mesoporous birnessite type MnO
2Nitrogen adsorption-the desorption isotherm of cellular nano-sphere, branch is adsorbed in real triangle curve representative, and empty four angular curves are represented desorption branch;
Fig. 3 b is layered mesoporous birnessite type MnO
2Nitrogen adsorption-the desorption isotherm of hollow nano-sphere, branch is adsorbed in real triangle curve representative, and empty four angular curves are represented desorption branch.
Fig. 4 sol-gel method is synthesized the basic process of Bir oxide compound.
Embodiment
Embodiment 1.
Getting a certain amount of purity is not less than 99.5% potassium permanganate and is dissolved in 40～60mL distilled water, stirring at normal temperature 15～30 minutes, (oleic acid density is 0.891～0.899g/mL dropwise to add 1mL oleic acid, saponification value is not less than 3, acid number is 190～200), making potassium permanganate/oleic mol ratio is 1/10～3/10, continues stirring reaction and is not less than 5 hours.To the solid sediment appearance, under 4000 rev/mins of conditions, separated 10～15 minutes behind the reaction certain hour, use distilled water and washing with alcohol sample then, repeat 3～5 times.The sample that makes at last is in vacuum-drying under 50～70 degrees celsius more than 10 hours, the layered mesoporous birnessite type MnO of the chocolate that obtains
2Cellular nano-sphere is shown in Fig. 1 a and 1b.The dried sample that takes a morsel is dispersed in the ethanol again, at 120W, ultra-sonic dispersion is 30～40 minutes under the ultrasonic wave condition of 40KHz, point sample is in the copper mesh that is used for transmission electron microscope, use transmission electron microscope and scanning electron microscopic observation afterwards, observation structure shows that it is spherical that nanostructure keeps, do not observe the fragment that nanostructure is broken and produced, show that structure has advantages of higher stability.Shown in Fig. 1 a and 1b.
Fig. 1 a and 1b are respectively layered mesoporous birnessite type MnO
2The electron scanning micrograph of cellular nano-sphere and transmission electron microscope photo.Fig. 1 a shows, the birnessite type MnO that obtains
2The cellular nano-sphere median size is in 85 nanometers, and each nanometer ball is to connect and compose cellular nanometer ball by some stratified pieces, and (stratified pieces is by 7 layers of MnO in 8.1 nanometers for the thickness of every stratified pieces
6The octahedra individual layer that constitutes is formed), it is spherical that each particle all keeps, and proves absolutely its structural stability.Fig. 1 b shows, forms layered mesoporous birnessite type MnO
2The stratified pieces of cellular nano-sphere is radial arrangement around the centre of sphere, and when the black part branch showed electron microscopic observation, electron beam was parallel to stratified pieces; When the ash color part showed electron microscopic observation, electron beam was non-parallel in stratified pieces.
Fig. 2 is the layered mesoporous birnessite type MnO that makes
2The cellular nano-sphere last X-ray diffractogram of pulverizing.In 2 θ=12.29 °, 18.68 °, 36.84 °, 54.98 °, 65.76 ° of diffraction peaks of locating correspond respectively to birnessite type MnO
2(002) of cellular nano-sphere, (101), (006), (301) and (119) crystal face.Halfwidth by (002) crystal face diffraction peak calculates MnO
2The interlamellar spacing of stratified pieces is 0.72 nanometer, about 8.1 nanometers of the thickness of every stratified pieces.
Embodiment 2.
Method according to embodiment 1 prepares layered mesoporous birnessite type MnO
2Cellular hollow Nano spherical structure.Getting a certain amount of purity is not less than 99.5% potassium permanganate and is dissolved in 40～60mL distilled water, stirring at normal temperature 15～30 minutes, (oleic acid density is 0.891～0.899g/mL dropwise to add 1mL oleic acid, saponification value is not less than 3, acid number is 190～200), making potassium permanganate/oleic mol ratio is 1～2, continues stirring reaction and is not less than 5 hours.Behind the reaction certain hour, under 4000 rev/mins of conditions, separated 10～15 minutes, use distilled water and washing with alcohol sample then, repeat 3～5 times.The sample dispersion that makes at last is in vacuum-drying under 50～70 degrees celsius more than 10 hours, the layered mesoporous birnessite type MnO of the chocolate that obtains
2Cellular hollow nano-sphere is shown in Fig. 1 c and 1d.The dried sample that takes a morsel is dispersed in the ethanol again, at 120W, ultra-sonic dispersion is 30～40 minutes under the ultrasonic wave condition of 40KHz, point sample is in the copper mesh that is used for transmission electron microscope, use transmission electron microscope and scanning electron microscopic observation afterwards, observation structure shows that it is spherical that nanostructure keeps, do not observe the fragment that nanostructure is broken and produced, show that structure has advantages of higher stability.Shown in Fig. 1 c and 1d.
Fig. 1 c and 1d are respectively layered mesoporous birnessite type MnO
2Cellular hollow nano-sphere electron scanning micrograph and transmission electron microscope photo.Fig. 1 c shows, the birnessite type MnO that obtains
2Cellular hollow nano-sphere particle diameter is in 50～150 nanometers, and each nanometer ball is to connect and compose cellular hollow nano-sphere by some stratified pieces, and (stratified pieces is by MnO in 1～6 nanometer for the thickness of every stratified pieces
6Octahedra formation).Fig. 1 d shows, the birnessite type MnO that obtains
2There are a lot of spinules on cellular hollow nano-sphere surface, and the dark part of spheroid is the shell of hollow ball, and grey color part is a hollow parts.It is spherical that each particle all keeps, and proves absolutely its structural stability.
Embodiment 3.
Get the layered mesoporous birnessite type MnO that makes in embodiment 1 and 2
2Cellular nano-sphere and cellular hollow nano-sphere, after handling through the degassing under 150 degrees centigrade respectively, at nitrogen adsorption-desorption analyser (Quantachrome NOVA 4200e, U.S. Kang Ta) goes up its nitrogen adsorption characteristic under-196 degrees centigrade of measurement, experimental result is seen curve among Fig. 3, and this curve shows the layered mesoporous birnessite type MnO that makes
2Cellular nano-sphere and cellular hollow nano-sphere have good gas adsorption characteristic.Fig. 3 a is layered mesoporous birnessite type MnO
2Nitrogen adsorption-the desorption isotherm of cellular nano-sphere and pore size distribution curve; Fig. 3 b is layered mesoporous birnessite type MnO
2Nitrogen adsorption-the desorption isotherm of cellular hollow nano-sphere and pore size distribution curve.This thermoisopleth has hysteresis loop, shows the layered mesoporous birnessite type MnO that makes
2Contain abundant mesoporous in the structure.Cut line among Fig. 3 a and the 3b, the mesoporous distribution that these materials had is not single, the mesoporous 3～15nm that is of a size of.Layered mesoporous birnessite type MnO
2The specific surface area of cellular nano-sphere and cellular hollow nano-sphere reaches 60～80m respectively
2/ g and 30～50m
2/ g, pore capacities reaches 0.1～0.3cm respectively
3/ g and 0.05～0.2cm
3/ g.
Claims (6)
1. layered mesoporous birnessite type MnO
2Cellular nano-sphere is characterized in that: the MnO that is made of polynuclear plane
2Nanometer ball, the aperture of its honeycomb are 3～15nm, this MnO
2The specific surface area of cellular nano-sphere is 60～80m
2/ g, pore capacities is 0.1～0.3cm
3/ g; MnO
2The cellular nano-sphere particle diameter is in 70～100 nanometers;
Stratified pieces between the described honeycomb is by 5～9 layers of MnO
6The octahedra individual layer that constitutes is formed, and wherein the thickness of each stratified pieces is 7～10 nanometers.
2. layered mesoporous birnessite type MnO
2Cellular nano-sphere is characterized in that: described layered mesoporous birnessite type MnO
2Cellular nano-sphere comprises the MnO that polynuclear plane constitutes
2Hollow nano-sphere, MnO
2The aperture of the honeycomb of cellular hollow nano-sphere is 3～15nm, this MnO
2The specific surface area of cellular hollow nano-sphere is 30～50m
2/ g, pore capacities is 0.05～0.2cm
3/ g; MnO
2Cellular hollow nano-sphere particle diameter is in 50～150 nanometers;
Stratified pieces between the described honeycomb is by MnO
6Octahedra formation, thickness is 1～6 nanometer.
3. layered mesoporous birnessite type MnO according to claim 1
2The preparation method of cellular nano-sphere is characterized in that, this method may further comprise the steps:
(1). at room temperature get potassium permanganate and be dissolved in the distilled water, stir and form uniform solution;
(2). oleic acid is joined in the solution that step (1) obtains, and wherein, potassium permanganate and oleic molar ratio are 1/10～3/10, and stirring reaction obtains solid sediment;
(3). the solid sediment that step (2) obtains is centrifugal, washing;
(4). the product that step (3) is obtained is not less than 10 hours 50～70 degrees centigrade of vacuum-dryings, obtains layered mesoporous birnessite type MnO
2Cellular nano-sphere.
4. layered mesoporous birnessite type MnO according to claim 2
2The preparation method of cellular nano-sphere is characterized in that, this method may further comprise the steps:
(1). at room temperature get potassium permanganate and be dissolved in the distilled water, stir and form uniform solution;
(2). oleic acid is joined in the solution that step (1) obtains, and wherein, potassium permanganate and oleic molar ratio are 〉=1, and stirring reaction obtains solid sediment;
(3). the solid sediment that step (2) obtains is centrifugal, washing;
(4). the product that step (3) is obtained is not less than 10 hours 50～70 degrees centigrade of vacuum-dryings, obtains layered mesoporous birnessite type MnO
2Cellular hollow nano-sphere.
5. according to claim 3 or 4 described methods, it is characterized in that: described potassium permanganate purity is not less than 99.5%; Described oleic acid density is 0.891～0.899g/mL, and saponification value is not less than 3, and acid number is 190～200.
6. layered mesoporous birnessite type MnO according to claim 1 and 2
2The purposes of cellular nano-sphere is characterized in that: described nanometer ball can be as the carrier of catalyzer or sorbent material; And as parting material, magneticsubstance, the electrode materials of battery, oxidative degradation material, desulfurization or material for air purification.
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| CN101993036B (en) * | 2009-08-30 | 2013-01-02 | 中国科学院合肥物质科学研究院 | Manganese oxide nano hollow tetrakaidecahedron and preparation method thereof |
| CN102145921B (en) * | 2010-05-28 | 2013-03-13 | 南京理工大学 | Preparation method of MnO2 nanoclusters by using graphene as template |
| WO2012167010A2 (en) * | 2011-06-02 | 2012-12-06 | Cornell University | Manganese oxide nanoparticles, methods and applications |
| CN102339996A (en) * | 2011-10-08 | 2012-02-01 | 广州市香港科大***研究院 | Synthesis and performance of spherical mesoporous anode materials MnO/Mn2O3 for lithium ion battery |
| CN102701284B (en) * | 2012-06-11 | 2013-11-13 | 华东理工大学 | Method for preparing surface appearance controllable hollow manganese dioxide nano spheres |
| CN102867655B (en) * | 2012-10-16 | 2015-08-05 | 桂林电子科技大学 | Ultracapacitor of tubulose meso-porous titanium dioxide manganese and preparation method thereof |
| CN103785345B (en) * | 2014-03-04 | 2016-03-02 | 武汉大学 | A kind of support type manganese dioxide adsorbent and utilize the method for its pretreatment aniline waste water |
| CN108479688A (en) * | 2018-03-27 | 2018-09-04 | 天津大学 | A kind of nano lamellar manganite adsorbent, preparation method and the usage |
| CN109395081B (en) * | 2018-11-30 | 2021-09-17 | 南京邮电大学 | Nano photodynamic reagent capable of near infrared light excitation and self oxygen supply and preparation and application thereof |
| CN110773130A (en) * | 2019-11-28 | 2020-02-11 | 福建工程学院 | Self-driven micro-nano motor with pine pollen as template and preparation method thereof |
| CN112268882B (en) * | 2020-09-29 | 2021-12-31 | 山西大学 | Preparation method and application of carbon dot-manganese dioxide nano fluorescent probe for high-selectivity detection of glutathione |
| CN113387389A (en) * | 2021-07-20 | 2021-09-14 | 云南农业大学 | Manganese oxide nanosheet with single-layer octahedral structure and preparation method thereof |
| CN114534717B (en) * | 2022-02-25 | 2023-05-30 | 中南大学 | Birnessite@hydrated calcium silicate composite material and preparation and application thereof |
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