CN1212275C - Method for preparing 3*3 tunnel structured manganese oxide octa hedral molecular sieve - Google Patents
Method for preparing 3*3 tunnel structured manganese oxide octa hedral molecular sieve Download PDFInfo
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- CN1212275C CN1212275C CNB021478392A CN02147839A CN1212275C CN 1212275 C CN1212275 C CN 1212275C CN B021478392 A CNB021478392 A CN B021478392A CN 02147839 A CN02147839 A CN 02147839A CN 1212275 C CN1212275 C CN 1212275C
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- manganese oxide
- birnessite
- molecular sieve
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Abstract
The present invention discloses a method for preparing manganese oxide octahedron molecular sieves with 3*3 tunnel structure, which specifically comprises: single phase manganese oxide mineral which has 3*3 tunnels and is well crystallized is synthesized under the reflux condition by heating under normal pressure, so that a large number of manganese oxide octahedron molecular sieves with 3*3 tunnel structure can be synthesized in one step. The method is characterized in that firstly, birnessite is synthesized in an alkaline medium, and the obtained birnessite is washed by water or purified by electric dialysis repeatedly until the birnessite approaches to neutrality; secondly, the birnessite is mixed with salt solution of elements in the IIA group or the IIIA group or transition metal elements in the periodic table, exchange reaction is kept for 3 to 24 hours at normal temperature and under a stirring condition, and products are centrifugally washed by water to prepare 1 nm of buserite; thirdly, the buserite is dispersed in water and is heated for reflux while stirred until the generated manganese oxide octahedron molecular sieve with 3*3 tunnel structure reaches the required thermal stability and crystallization degree; and finally, the chemical composition formula of the generated molecular sieve is MxMnOyH2Oz. The molecular sieve can be used for preparing catalysts of petrochemical engineering and cathode material of lithium ion secondary batteries.
Description
Technical field
The present invention relates to the preparation method of 3 * 3 tunnel construction manganese oxide octahedron molecular screens.The present invention be more particularly directed to good single-phase 3 * 3 tunnel oxidation manganese minerals of synthetic crystallization under normal pressure reflux condition, thereby can once synthesize 3 * 3 a large amount of tunnel construction manganese oxide octahedron molecular screens.
Background technology
The manganese oxide octahedron molecular screen is the manganese oxide mineral that a class has tunnel construction and vesicular structure.Its tunnel construction is arranged along equidirectional, is connected to form on the summit altogether with common rib and interchain in the chain by the MnO6 octahedron, according to MnO
6The length of octahedra chain can form 1 * 1,1 * 2,2 * 2,2 * 3,3 * 3 with the manganese oxide octahedron molecular screen of different tunnels size such as 3 * n.
At nature, the tunnel oxidation manganese mineral that this class has molecular sieve structure often is present in manganese ore deposit, contains in manganese atmospheric disintegration of rocks thing, soil and settling and the marine manganese nodule.Wherein, todorokite (todorokite) also claims todorokite, is the manganese oxide mineral that natural formation has 3 * 3 tunnel constructions, and since 1934 found in Japanese Todoroki mine, extremely people paid close attention to.The aperture, tunnel of todorokite is 0.69nm (seeing accompanying drawing 1), cation exchange property and zeolites seemingly, spacious tunnel size is to Li
+In its lattice, embed-deviate to have electrochemical reversibility and cyclical stability preferably, the surface has Lewis acid and Bronsted acid isoreactivity point position, except the catalyzer that is used for oxidative dehydrogenation, can also be used for acid catalyzed reactions such as polymerization, isomerization.Fields such as said structure characteristics and character make that todorokite is synthetic at molecular sieve, secondary battery electrode material and catalyst development can be widely used.
The todorokite of natural formation often is stored in the environment with the nanoparticle and the taxes such as other multiple manganese oxide, ferric oxide and clay mineral of weak crystalloid, content is low, the isolation identification difficulty, the synthetic todorokite of old friend worker is the main method that people prepare 3 * 3 tunnel construction manganese oxide octahedron molecular screens.Now disclosed todorokite preparation method has: adopt logical O in alkaline medium
2Oxidation Mn (OH)
2The preparation birnessite is then at 155 ℃ of following hydrothermal process Mg
2+The birnessite of exchange, preparation todorokite (Golden D C, ChenC C, Dixon J B.Science, 1986,231:717～719).Or with Mg (MnO in the alkaline medium
4)
2Oxidation Mn (OH)
2Make birnessite, again with the Mg-birnessite 10 to 40 hours synthetic todorokites of 155 ℃ to 170 ℃ following hydrothermal solutions reactions (ShenY F, Zerger R P, Suib S L, et al.Science, 1993,260:511-515).Also have report to select the synthetic birnessite of other different methods one-step synthesis todorokite of going forward side by side for use, perhaps adopt different type of heating, but under the High Temperature High Pressure hydrothermal solution synthetic be unique route of synthesis (United States Patent (USP) 5,635,155) of todorokite always.Because the synthetic todorokite of hydrothermal solution needs to carry out in the less autoclave of volume, one time the synthetic sample has only tens to the hundreds of milligram, and reaction easily generates other ore deposit phases such as manganite.These are difficult to satisfy the needs to its widespread use.
Summary of the invention
The present invention aims to provide a kind of new preparation method of 3 * 3 tunnel construction manganese oxide octahedron molecular screens.
Method of the present invention relates to the step of synthetic birnessite in alkaline medium earlier.The synthetic birnessite washed repeatedly or electrodialysis is purified near neutral, again with the periodic table of elements in the salt solution mix of IIA family, IIIA family or transition metal, at normal temperature and under stirring permutoid reaction 3-24 hour, make 1nm-Bu Saier ore deposit after the centrifugal washing.Then 1nm-Bu Saier ore deposit is dispersed in the water, under agitation reflux reaches required thermostability and degree of crystallinity until 3 * 3 tunnel construction manganese oxide octahedron molecular screens that generate.The chemical constitution of the molecular sieve that generates is M
xMnO
y(H
2O)
z, 0.1＜x＜0.9,1.5＜y＜2.5,0.4＜z＜2.0 wherein; Described M is IIA family, IIIA family or transition metal.
Said birnessite can be logical O in alkaline medium
2Oxidation Mn (OH)
2Synthetic, synthesize in enough alkalescence and oxygen flow condition, under the condition of accelerating the reaction solution flow rate, carry out simultaneously; Also can be MnO in alkaline medium
4 -Oxidation Mn (OH)
2Synthesize, and wore out 1 day at 40 ℃ to 60 ℃.
Said IIA family, IIIA family or transition metal can be Mg
2+, Ca
2+, Ba
2+, Al
3+, Cu
2+, Co
2+, Ni
2+Deng soluble salt or their several mixtures, for example muriate, vitriol, nitrate, acetate etc.These metal ions enter in the lattice of molecular sieve or the space, tunnel in the reaction rear section becomes structural cation or tunnel ion, thereby gives the different pattern of molecular sieve, thermostability and catalytic property etc.
Said reflux is to carry out in the open system of normal pressure, and temperature of reaction can be 50 ℃ to 100 ℃, and the reaction times can be 2 hours to 7 days.Make 3 * 3 tunnel construction manganese oxide octahedron molecular screens of generation reach required thermostability and degree of crystallinity.
Using this method can be at synthetic next time 3 * 3 tunnel construction manganese oxide octahedron molecular screen that mass crystallization is good, thermostability is high of the condition of normal pressure and reflux.It has the acidic site that comprises Lewis acid and Bronsted acid, pretends to the catalyzer of acid catalyzed reactions such as polymerization, isomerization and can be used widely in petrochemical complex.3 * 3 tunnel construction manganese oxide octahedron molecular screens that contain different transition metal also have advantages of high catalytic activity and selectivity to organic oxidative dehydrogenations such as ethanol, ethylbenzene.In addition, as the cathode material of lithium-ion secondary cell, 3 * 3 tunnel construction manganese oxide octahedron molecular screens can improve the fast charging and discharging ability and the cyclical stability of electrode, and cheap, and toxicity is little, has commercialized development prospect preferably.
Fig. 1, Fig. 2 are the synoptic diagram of 3 * 3 tunnel construction manganese oxide octahedron molecular screens of the present invention.
Fig. 3 is the X-ray diffracting spectrum of 3 * 3 tunnel construction manganese oxide octahedron molecular screens of the present invention.
Fig. 4 is the pattern electromicroscopic photograph of 3 * 3 tunnel construction manganese oxide octahedron molecular screens of the present invention.
Fig. 5 is the high power electromicroscopic photograph of 3 * 3 tunnel construction manganese oxide octahedron molecular screens of the present invention.
Fig. 6 is the electron-diffraction diagram of 3 * 3 tunnel construction manganese oxide octahedron molecular screens of the present invention.
Embodiment
Embodiment 1: contain the synthetic of magnesium 3 * 3 tunnel construction manganese oxide octahedron molecular screens.
At first synthetic birnessite in alkaline medium is taken the new 0.5M MnCl for preparing of distillation deionized water
2Solution 200ml and 5.5M NaOH solution 250ml.NaOH solution is added MnCl fast
2In the solution, feed 2Lmin immediately
-1The oxygen of flow, oxidation is 5 hours under mechanical stirring.Reaction solution is through high speed centrifugation (centrifugal force 2.54 * 10
4G) back is with distilling deionized water washing sediment, and re-treatment repeatedly obtains manganese oxide mineral.Birnessite washed repeatedly or electrodialysis is purified near neutral.Get the 1M MgCl that the clean birnessite of 10g is scattered in 1L then
2In the solution, the vibration exchange is after 12 hours, and 1nm-Bu Saier ore deposit is made in centrifugal washing, the 1nm-Bu Saier ore deposit of cleaning is dispersed in the 400mL water again, and reflux is 24 hours while stirring.Reflux and finish postcooling, the mineral water that generates is washed till electricity leads less than 2 μ Scm
-1Obtain containing magnesium 3 * 3 tunnel construction manganese oxide octahedron molecular screens after the reaction product lyophilize.
Fig. 3 is for containing magnesium 3 * 3 tunnel construction manganese oxide octahedron molecular screens at the X-ray diffracting spectrum of 140 ℃ of heating after 12 hours.At this moment, 0.952 and the 0.475nm diffraction peak be the characteristic diffraction peak of todorokite (100) and (200) face, its tunnel width is 1nm as can be seen.Fig. 4 is for containing the pattern electromicroscopic photograph of magnesium 3 * 3 tunnel construction manganese oxide octahedron molecular screens, and it is different in size fibrous that todorokite is, and this is the fibrous todorokite broken result that fractures easily under the ultrasonic wave effect when electron microscopyc sample preparation.Fig. 5 is for containing the high power electromicroscopic photograph of magnesium 3 * 3 tunnel construction manganese oxide octahedron molecular screens.The fibrous crystal of todorokite is stretched out by the parent that profile is similar to birnessite, and long several microns to tens microns, wide about tens nanometers.Under the high power transmission electron microscope, these parents are actually by the trilling adhesion and form as can be seen, and this is the typical shape characteristic that todorokite is different from birnessite.Fig. 6 is for containing the electron-diffraction diagram of magnesium 3 * 3 tunnel construction manganese oxide octahedron molecular screen trilling parents, and unit cell parameters is: rhombic system, a=0.975nm, b=0.284, c=0.959nm.It is symmetrical to be false six sides along the electron-diffraction diagram of the trilling parent of three directions growth.
Embodiment 2: cupric 3 * 3 tunnel construction manganese oxide octahedron molecular screens synthetic.
The synthesis step of birnessite is got the 1M CuCl that the clean birnessite of 10g is scattered in 1L with embodiment 1
2In the solution, the vibration exchange is after 12 hours, and 1nm-Bu Saier ore deposit is made in centrifugal washing, the 1nm-Bu Saier ore deposit of cleaning is dispersed in the 400mL water again, and reflux is 48 hours while stirring.Reflux and finish postcooling, the mineral water that generates is washed till electricity leads less than 2 μ Scm
-1Obtain cupric 3 * 3 tunnel construction manganese oxide octahedron molecular screens after the reaction product lyophilize.
Embodiment 3: nickeliferous 3 * 3 tunnel construction manganese oxide octahedron molecular screens synthetic.
The synthesis step of birnessite is got the 1M Ni (NO that the clean birnessite of 10g is scattered in 1L with embodiment 1
3)
2In the solution, the vibration exchange is after 12 hours, and 1nm-Bu Saier ore deposit is made in centrifugal washing, the 1nm-Bu Saier ore deposit of cleaning is dispersed in the 400mL water again, and reflux is 72 hours while stirring.Reflux and finish postcooling, the mineral water that generates is washed till electricity leads less than 2 μ Scm
-1Obtain nickeliferous 3 * 3 tunnel construction manganese oxide octahedron molecular screens after the reaction product lyophilize.
Claims (7)
1, a kind of method of preparation 3 * 3 tunnel construction manganese oxide octahedron molecular screens is characterized in that: described molecular sieve is that its preparation process comprises at open normal pressure and a large amount of next time synthetic of reflux condition:
1) elder generation's synthetic birnessite in alkaline medium is washed the birnessite that obtains repeatedly or electrodialysis is purified near neutral;
2) again with the periodic table of elements in the salt solution mix of IIA family, IIIA family or transition metal, at normal temperature and under stirring permutoid reaction 3-24 hour, make 1nm-Bu Saier ore deposit after the centrifugal washing;
3) then 1nm-Bu Saier ore deposit is dispersed in the water, under agitation reflux reaches required thermostability and degree of crystallinity until 3 * 3 tunnel construction manganese oxide octahedron molecular screens that generate; The chemical constitution of the molecular sieve that generates is M
xMnO
y(H
2O)
z, 0.1＜x＜0.9,1.5＜y＜2.5,0.4＜z＜2.0 wherein; Described M is IIA family, IIIA family or transition metal.
2, the described preparation method of claim 1 is characterized in that: described birnessite is logical O in alkaline medium
2Oxidation Mn (OH)
2Synthetic, synthesize in enough alkalescence and oxygen flow condition, under the condition of accelerating the reaction solution flow rate, carry out simultaneously.
3, the described method of claim 1 is characterized in that, described birnessite is MnO in alkaline medium
4 -Oxidation Mn (OH)
2Synthesize, and wore out 1 day at 40 ℃ to 60 ℃.
4, the described preparation method of claim 1 is characterized in that: the salt of said IIA family, IIIA family or transition metal is Mg
2+, Ca
2+, Ba
2+, Al
3+, Gu
2+, Co
2+, Ni
2+Soluble salt or their several mixtures.
5, the described preparation method of claim 1 is characterized in that: the salt of said IIA family, IIIA family or transition metal is selected from muriate, vitriol, nitrate or acetate.
6, the described method of claim 5, it is characterized in that, described metal ion enters in the lattice of molecular sieve or the space, tunnel in the reaction rear section becomes structural cation or tunnel ion, thereby gives the different pattern of molecular sieve, thermostability and catalytic property.
7, the described preparation method of claim 1 is characterized in that: said reflux is to carry out in the open system of normal pressure, and temperature of reaction is 50 ℃ to 100 ℃, and the reaction times can be 2 hours to 7 days; Make 3 * 3 tunnel construction manganese oxide octahedron molecular screens of generation reach required thermostability and degree of crystallinity.
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| JP5450057B2 (en) * | 2006-05-04 | 2014-03-26 | エルジー・ケム・リミテッド | Electrode active material with improved safety and electrochemical device using the same |
| CN101428151B (en) * | 2008-12-17 | 2013-08-28 | 清远博大生化机械工程有限公司 | Ionic-exchange manganese oxygen octahedron molecular sieve hemostatic material and preparation method thereof |
| CN102049194B (en) * | 2009-10-30 | 2013-06-05 | 中国石油化工股份有限公司 | Method for performing ion exchange on molecular sieve containing exchangeable ions |
| CN101791559B (en) * | 2010-02-09 | 2012-07-18 | 广东工业大学 | Metal ion doped manganese oxide catalyst, preparation method and use thereof |
| CN103112868B (en) * | 2013-03-05 | 2015-06-24 | 广东工业大学 | Preparation method and application of sulfur-doped manganese oxide octahedral molecular sieve |
| CN110038556B (en) * | 2019-05-06 | 2020-07-28 | 中国科学院兰州化学物理研究所 | OMS-2 type composite material with mixed crystal phase, preparation method and application thereof |
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