CN107324393A - Metal hydroxides intercalation 1-dimention nano metal oxide, preparation method and detach method - Google Patents
Metal hydroxides intercalation 1-dimention nano metal oxide, preparation method and detach method Download PDFInfo
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- CN107324393A CN107324393A CN201710541795.0A CN201710541795A CN107324393A CN 107324393 A CN107324393 A CN 107324393A CN 201710541795 A CN201710541795 A CN 201710541795A CN 107324393 A CN107324393 A CN 107324393A
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Abstract
The invention discloses the preparation method of a kind of one-dimensional Mn oxide of structure reversible transformation and its intercalation metal hydroxides, belong to technical field of nanometer material preparation.The present invention utilizes the one-dimentional structure stability characteristic of metal oxide, prepare one-dimensional nano structure metal oxide, intercalation material is prepared by inserting the method for metal hydroxides in one-dimensional nano structure metal oxide again, is cemented out metal hydroxides finally by ammoniacal liquor so that 1-dimention nano metal oxide is recovered.The present invention is developed first extracts the method that metal hydroxides enables 1-dimention nano metal oxide to restore with ammoniacal liquor.This method technique is simple, with low cost, it is possible to achieve industrialization large-scale production.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, more particularly to a kind of gold with structure reversible transition property
Belong to hydroxide intercalation 1-dimention nano metal oxide materials, preparation method and detach method.
Background technology
1-dimention nano metal oxide has the chemistry of uniqueness in terms of ion exchange, intercalation reaction, catalysis and absorption
Performance, and also have in magnetic and conductibility special physical property.Such material is by two kinds or two or more
Cellular construction layer is alternately formed by accumulation.Nowadays the research about 1-dimention nano metal oxide is concentrated mainly on metallic cobalt
On oxide, relevant other kinds of 1-dimention nano metal oxide structures report is considerably less, and 1-dimention nano metal oxide
Structure there is the property and its collective effect of two kinds or two or more metal oxides in itself and produce other derive it is special
Property cause 1-dimention nano metal oxide structures to have special physics, chemical structure characteristic, the generations of these characteristics again can shadow
Answering in Dian Chi electrode material, sorbing material and catalytic field is rung to 1-dimention nano metal oxide structures composite oxides
With.
There is special architectural characteristic, physics and chemical property and pyroelectric effect due to 1-dimention nano metal oxide and
Receive significant attention.Root is it is reported that nowadays most famous, most study 1-dimention nano metal oxide materials are main with cobalt oxide
Based on compound material.Isobe, Klimczuk, Shizuya, Miyazaki et al. have successfully synthesized with Ca-Co 1-dimention nanos
Metal oxide structures composite oxides, main body is with CdI in these composite oxides2Type triangle (triangular)
Structure C oO2, object is the calcium oxide of layer structure, based on CaOH and CaO.Isobe et al. is thought in 1-dimention nano metal
Oxide structure (CaOH)1.14CoO2In, surrounded around each Co ions by six oxonium ions, and Co-O keys have 0.191nm
With two kinds of bond distances of 0.195nm, Co is approximately equal to3+(r1=0.0545nm) and O2-(r2=0.140nm) ionic radius sum.Octahedral
Body CoO6Thickness be about 0.207nm, wherein Co valence state is close to+trivalent, by octahedra CoO6It is mingled between the laminate of composition
CaOH laminates.Klimczuk et al. thinks that molecular formula is Ca25Co22O56(OH)28Ca-Co composite oxides there is 1-dimention nano
Metal oxide structures, laminate is respectively by the CoO with hexagonal structure2With the calcium oxidhydroxide with square structure
Composition, in CoO2It is mingled with double-deck calcium oxidhydroxide between laminate.Shizuya et al. has shown that octahedral body phase by research
(CaOH)1.14CoO2With (the Ca of monoclinic system0.85OH)1.16CoO2With identical chemical composition, the difference is that two kinds of compounds
With different structure cells, CoO of two kinds of compounds along c- axles2It is different with CaOH arrangement mode.Miyazaki et al. is also in nothing
Synthesize between meaning with [Ca2CoO3]pCoO2The 1-dimention nano metal oxide structures of chemical general formula, wherein parameter p are along b-
Axle bCoO2(RS is rock-salt accumulation type (rock-salt type) [Ca to/bRS ratio2CoO3]), CdI in compound2- type
CoO2With three layers of rock-salt accumulation type [Ca2CoO3] form Ca-Co 1-dimention nano metal oxide composite oxygens along the alternating accumulation of c- axles
Compound.It is additionally, since the special nature that 1-dimention nano metal oxide materials have, 1-dimention nano metal oxide materials gold
Category oxide has very big application potential in semiconductor, magnetic material, ferroelectric (Ferroelectric) and catalytic field.
Prior art is primarily present following 3 major defects：
1st, the irreversible conversion of 1-dimention nano metal oxide materials structure.Although being related to 1-dimention nano metal oxide
The report of intercalated metal oxide/metal hydroxides/organic constitution materials synthesis, but its synthetic product is respectively provided with stabilization
One-dimensional or two-dimensional space structure, with irreversible denaturation.
2nd, it can not realize that 1-dimention nano metal oxide structures separate preparation with intercalation compound.It is existing on 1-dimention nano
The report of metal oxide intercalated metal oxide/metal hydroxides/organic constitution materials synthesis belongs to synchronized compound
Method, i.e., simultaneously 1-dimention nano metal oxide starting material is mixed with intercalation compound raw material, synthesize under certain condition
Object construction compound, such as king pass through the intercalation configuration that is mixed with out divalent transition metal and benzoate.
3rd, intercalation compound is extracted or changing condition is harsh and speed is slower.The extraction of intercalation compound is more difficult key
Problem, in this process require i.e. can not destroy 1-dimention nano metal oxide structures, also to realize intercalation compound detach or
Transformation.Conventional method needs just intercalation compound can be made slowly to discharge in vacuum, high/low temperature or weak acid alkaline environment.
The content of the invention
For problems of the prior art, the present invention utilizes the one-dimentional structure stability characteristic of metal oxide, system
It is standby go out one-dimensional nano structure metal oxide, then pass through metal hydroxides inserted in one-dimensional nano structure metal oxide
Method prepares intercalation material, pulls out metal hydroxides come so that 1-dimention nano metal oxide is obtained finally by ammoniacal liquor
To recover.
Specifically, the invention provides a kind of preparation method of metal hydroxides intercalation 1-dimention nano metal oxide,
Specifically implement in accordance with the following steps：
S1：The preparation of 1-dimention nano Mn oxide
S11：Prepare 0.05~0.5mol/L manganese salt solutions and 3~10mol/L aqueous slkalis respectively, and by the manganese salt solution
5 DEG C are cooled to aqueous slkali；
S12：Manganese salt solution and aqueous slkali after cooling is poured into three-necked flask, Mn2+：OH-Mixing mol ratio be
0.004~0.135：1, quick stirring, and 2~8L/min purity oxygen is passed through, 10~60min is reacted, stops being passed through oxygen afterwards
Gas is further continued for 3~4h of reaction aging；
S13：Reacted sediment is washed with deionized to washing lotion in neutrality, gained moist press cake after filtering, is
1-dimention nano Mn oxide；
S2：The preparation of intercalation material
0.01~1.0M metal salt solution is prepared, the 1-dimention nano Mn oxide prepared at room temperature with S1 is mixed
Close, the molal quantity and 1-dimention nano Mn oxide mass ratio of metal ion are 0.003~1mol in metal salt solution：10g, regulation
The pH of mixed liquor to 8.0~10.5, continues to stir constant to pH value, after deionized water washing, is placed in crystallizing kettle in 0~200
DEG C 0~24h of crystallization, produces intercalation material.
It is preferred that in S11, the manganese salt solution is Manganous sulfate monohydrate, manganese nitrate, chloride hydrate manganese or its mixture；
The aqueous slkali is sodium hydroxide solution.
It is preferred that in S2, the pH of mixed liquor is adjusted by 0.1~1.0mol/L alkali lye, the alkali lye is that sodium hydroxide is molten
The mixture of one or both of liquid, potassium hydroxide solution.
It is preferred that in S2, the metal salt is CuSO4·xH2O、Cu(NO3)2·xH2O、CuCl2·xH2O、ZnCl2、
ZnSO4·xH2O、Ni(NO3)2·6H2O、NiCl2·xH2O、NiSO4·xH2O、Co(NO3)2·6H2O、CoSO4·7H2O、
CoCl2·xH2O、AgNO3In one or more of mixtures, but AgNO3Except the mixed solution of chlorine-containing compound.
Present invention also offers a kind of metal hydroxides intercalation 1-dimention nano metal oxide, by any of the above-described method system
Standby to obtain, the metal hydroxides intercalation 1-dimention nano metal oxide has structure reversible transition property.
Metal hydroxides intercalation 1-dimention nano metal oxide that the present invention is provided detaches method, and detailed process is such as
Under：
The metal hydroxides intercalation 1-dimention nano metal oxide is added into 2~14.8mol/L to detach in solution,
0.5~2h is stirred at room temperature, you can metal hydroxides intercalation is cemented out from 1-dimention nano Mn oxide, makes a wiener
Rice Mn oxide structure is recovered.
It is preferred that described detach the ammoniacal liquor that solution is 5~12mol/L.
The metal hydroxides intercalation 1-dimention nano metal oxide that the present invention is provided, metal target is carried in sewage disposal
The application or the application in terms of special sensor material is prepared taken.
Compared with prior art, the technical solution adopted in the present invention has the advantages that：
The present invention has synthesized the 1-dimention nano metal oxide with structure reversible transformation using manganese salt solution, realizes first
1-dimention nano Mn oxide and the separable two-dimensional structure system prepared of intercalation metal hydroxides, and develop use ammonia first
Water, which extracts metal hydroxides, enables the method that 1-dimention nano metal oxide restores.This method technique is simple, with low cost,
Industrialization large-scale production can be realized, 1-dimention nano metal oxide is reused, and temperature and pressure is applied widely；
1-dimention nano Mn oxide can be readily synthesized out in room temperature, normal pressure and oxidation environment, the 1-dimention nano Mn oxide can be
Room temperature, normal pressure into middle temperature, the alkaline environment of middle pressure by metal hydroxides stably intercalation in 1-dimention nano manganese oxide layer
Between plate, the 1-dimention nano Mn oxide intercalation metal hydroxides at room temperature and atmospheric pressure just can be by metallic hydrogen by ammoniacal liquor dipping
Oxide pulls out laminate, realizes the simple recovery detached with 1-dimention nano metal oxide structures of intercalation compound.Should
This special nature of intercalation material, intercalation preparation method and detach method can be extracted as metal target in sewage disposal or
Preparing has extensive use in terms of special sensor material.
Brief description of the drawings
Fig. 1 is 1-dimention nano Mn oxide preparation technology flow chart in the embodiment of the present invention 1；
Fig. 2 is 1-dimention nano Mn oxide intercalation metal hydroxides preparation technology flow chart in the embodiment of the present invention 1；
Fig. 3 is 1-dimention nano Mn oxide intercalation metal hydroxides reversible transformation technological process in the embodiment of the present invention 1
Figure；
Fig. 4 is 1-dimention nano Mn oxide SEM figures in the embodiment of the present invention 1；
Fig. 5 is 1-dimention nano Mn oxide XRD spectra in the embodiment of the present invention 1；
Fig. 6 is the SEM figures of 1-dimention nano Mn oxide intercalation Kocide SD in the embodiment of the present invention 1；
Fig. 7 is the XRD spectra of 1-dimention nano Mn oxide intercalation Kocide SD in the embodiment of the present invention 1；
Fig. 8 schemes for SEM after 1-dimention nano Mn oxide intercalation Kocide SD reversible transformation in the embodiment of the present invention 1；
Fig. 9 is XRD spectra after 1-dimention nano Mn oxide intercalation Kocide SD reversible transformation in the embodiment of the present invention 1；
Figure 10 is 1-dimention nano Mn oxide intercalation cobalt hydroxide XRD spectra in the embodiment of the present invention 4；
Figure 11 is 1-dimention nano Mn oxide intercalation silver hydroxide XRD spectra in the embodiment of the present invention 5.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description, it is to be understood that the protection of the present invention
Scope is not limited by embodiment.The test method of unreceipted actual conditions in the following example, generally according to normal
Conditional operation is advised, unreceipted experiment material source is commercially available, due to not being related to inventive point, therefore its step is not carried out detailed
Description.
When embodiment provides number range, it should be appreciated that except non-invention is otherwise noted, two ends of each number range
Any one numerical value can select between point and two end points.Unless otherwise defined, in the present invention all technologies for using and
Scientific terminology is identical with the meaning that those skilled in the art of the present technique are generally understood that.Except the specific method used in embodiment, equipment,
Outside material, according to those skilled in the art to the grasp of prior art and the record of the present invention, it can also use and this
Any method, equipment and the material of the similar or equivalent prior art of method, equipment described in inventive embodiments, material come real
The existing present invention.
Embodiment 1
The present embodiment 1-dimention nano Mn oxide intercalation Kocide SD material, its preparation process is specific as follows：
Weigh 11.0g MnSO4·H2O is added in 130ml deionized waters and is configured to manganese sulfate solution, weighs 36.7g's
NaOH, which is added in 167ml deionized waters, is configured to NaOH solution, and the manganese sulfate solution and NaOH solution of preparation are dropped respectively
Temperature is to 5 DEG C.Manganese sulfate solution and NaOH solution are poured into three-necked flask, quick stirring (500r/min), and are passed through 5L/min
Purity oxygen, react 30min, stop being passed through oxygen being further continued for reaction aging 4h afterwards.With distillation water washing precipitate to neutrality,
Gained moist press cake is the 1-dimention nano Mn oxide material with structure reversible transition property, specific preparation technology after filtering
Flow chart is as shown in Figure 1.
Weigh 15.0g CuSO4·5H2O, which is added in 300ml deionized waters, is configured to manganese sulfate solution, at room temperature with
1-dimention nano Mn oxide mixing obtained above 10.0g, then mixed liquor is titrated to pH with 0.5mol/L sodium hydroxide solution
=10.0, continue to stir constant to pH value, deionized water, which is washed to sulfate radical-free, to be placed in crystallizing kettle in 150 DEG C of crystallization 10h,
1-dimention nano Mn oxide intercalation Kocide SD material is produced, specific preparation technology flow chart is as shown in Figure 2.
Above-mentioned 1-dimention nano Mn oxide intercalation Kocide SD is added in 8mol/L ammonia spirits, stirred at room temperature
1h, you can Kocide SD will be pulled out from 1-dimention nano Mn oxide and, and enable 1-dimention nano Mn oxide structure extensive
Multiple, the reversible transformation process chart is as shown in Figure 3.
We are tested above-mentioned 1-dimention nano Mn oxide material, its SEM spectrogram as shown in figure 4, its XRD spectra such as
Shown in Fig. 5；We are tested above-mentioned 1-dimention nano Mn oxide intercalation Kocide SD material, obtained 1-dimention nano manganese
The SEM spectrograms of oxide intercalation Kocide SD material are as shown in fig. 6, XRD spectra is as shown in Figure 7；Comparison chart 4 and Fig. 6 can be seen
Go out, after intercalation processing, one-dimensional Mn oxide remains in that thin plates pattern, and intercalation process is not to one-dimensional Mn oxide shape
Looks are damaged.Comparison chart 5 and Fig. 7 can be seen that metal hydroxides does enter into one-dimensional Mn oxide laminate after intercalation
Between, 2 θ=9.3 correspond to Mn oxide laminate diffraction maximum in XRD spectra, and 2 θ=18.7 correspond to Mn oxide laminate and metal
Hydroxide laminate diffraction maximum.SEM spectrums after obtained 1-dimention nano Mn oxide intercalation Kocide SD material reversible transformation
Figure is as shown in figure 8, XRD spectra is as shown in figure 9, as seen from Figure 8, detaching process and one-dimensional Mn oxide pattern not being caused
Destruction and change, further relate to the structure reusable.As seen from Figure 9, after detaching, 1-dimention nano Mn oxide X is penetrated
Line diffraction maximum has recovered diffraction maximum shown in Fig. 5, illustrates that 1-dimention nano Mn oxide structure can be recovered.
Embodiment 2
The present embodiment 1-dimention nano Mn oxide intercalation zinc hydroxide material, its preparation process is specific as follows：
Weigh 23.2ml 50wt% Mn (NO3)2Solution is added in 276.8ml deionized waters that to be configured to manganese nitrate molten
Liquid, the NaOH for weighing 50.0g is added in 150.0ml deionized waters and is configured to NaOH solution, and by manganese nitrate solution and NaOH
Solution is cooled to 5 DEG C.Manganese nitrate solution and NaOH solution after cooling is poured into three-necked flask, quick stirring (500r/
Min), and 6L/min purity oxygen is passed through, reacts 50min, stop being passed through oxygen being further continued for reaction aging 4h afterwards.Use distilled water
Washing precipitate is to neutrality, and gained moist press cake is the 1-dimention nano Mn oxide with structure reversible transition property after filtering
Material.
Weigh 10.0g ZnSO4It is added in 300ml deionized waters and is configured to solution of zinc sulfate, at room temperature with 10.0g
Above-mentioned 1-dimention nano Mn oxide mixing, then pH=9.5 is titrated to 0.5mol/L sodium hydroxide solutions, continue to stir to pH value
Constant, deionized water is washed to sulfate radical-free, produces 1-dimention nano Mn oxide intercalation zinc hydroxide material.
Above-mentioned 1-dimention nano Mn oxide intercalation zinc hydroxide is added in 5mol/L ammonia spirits, stirred at room temperature
1h, you can zinc hydroxide will be pulled out from 1-dimention nano Mn oxide and, and enable 1-dimention nano Mn oxide structure extensive
It is multiple.
Embodiment 3
The present embodiment 1-dimention nano Mn oxide intercalation nickel hydroxide material, its preparation process is specific as follows：
Weigh 10.0g MnCl2·4H2O is added in 150.0ml deionized waters and is configured to manganese chloride solution, weighs
50.0g NaOH, which is added in 150.0ml deionized waters, is configured to NaOH solution, and manganese chloride solution and NaOH solution are cooled
To 5 DEG C.Manganese chloride solution and NaOH solution after cooling is poured into three-necked flask, quick stirring (500r/min), and be passed through
8L/min purity oxygen, reacts 40min, and stopping afterwards being passed through oxygen and is further continued for reaction aging 4h.With distillation water washing precipitate
To neutral, gained moist press cake as the 1-dimention nano Mn oxide material with structure reversible transition property, gained after filtering
The XRD spectra of 1-dimention nano Mn oxide material is as shown in Figure 9.
Weigh 5.0g NiSO4·6H2O, which is added in 300ml deionized waters, is configured to nickel sulfate liquid, at room temperature with
10.0g 1-dimention nanos Mn oxide is mixed, then is titrated to pH=8.0 with 0.5mol/L sodium hydroxide solutions, continues to stir to pH
Value is constant, and deionized water, which is washed to sulfate radical-free, to be placed in crystallizing kettle in 200 DEG C of crystallization 10h, produces the oxidation of 1-dimention nano manganese
Thing intercalation nickel hydroxide material.
Above-mentioned 1-dimention nano Mn oxide intercalation nickel hydroxide material is added in 12mol/L ammonia spirits, at room temperature
Stir 1h, you can nickel hydroxide will be pulled out from 1-dimention nano Mn oxide and, and obtain 1-dimention nano Mn oxide structure
To recover.
Embodiment 4
In the present embodiment 1-dimention nano Mn oxide intercalation cobalt hydroxide material, its preparation process, the oxidation of 1-dimention nano manganese
It is identical in the preparation process and embodiment 1 of thing material.1-dimention nano Mn oxide intercalation cobalt hydroxide materials process is：Weigh
10.0g CoSO4·7H2O, which is added in 300ml deionized waters, is configured to metal salt solution, at room temperature with 10.0g above-mentioned one
Tie up nano manganese oxide mixing, then be titrated to 1mol/L sodium hydroxide solutions pH=9, continue to stir constant to pH value, go from
It is placed in after sub- water washing to sulfate radical-free in crystallizing kettle in 70 DEG C of room temperature crystallization, produces 1-dimention nano Mn oxide intercalation hydroxide
Cobalt material.
Above-mentioned 1-dimention nano Mn oxide intercalation cobalt hydroxide is added in 10mol/L ammonia spirits, 1h is stirred at room temperature,
Cobalt hydroxide will can be pulled out from 1-dimention nano Mn oxide, 1-dimention nano Mn oxide structure is recovered.
We are tested above-mentioned 1-dimention nano Mn oxide intercalation cobalt hydroxide material, obtained 1-dimention nano manganese
As shown in Figure 10, as seen from Figure 10, Co salt can also realize intercalation knot to the XRD spectra of oxide intercalation cobalt hydroxide material
Between metal cobalt hydroxide enters one-dimensional Mn oxide laminate after the preparation of structure, intercalation, 2 θ=9.2 correspond to manganese in XRD spectra
Oxide laminate diffraction maximum, 2 θ=18.5 correspond to Mn oxide laminate and metal cobaltous hydroxide layer plate diffraction maximum.
Embodiment 5
In the present embodiment 1-dimention nano Mn oxide intercalation silver hydroxide material, its preparation process, the oxidation of 1-dimention nano manganese
It is identical in the preparation process and embodiment 1 of thing material.1-dimention nano Mn oxide intercalation silver hydroxide materials process is：Weigh
1.0g AgNO3It is added in 300ml deionized waters and is configured to metal salt solution, at 5 DEG C with the above-mentioned 1-dimention nano manganese of 10.0g
Oxide is mixed, then is titrated to 0.2mol/L sodium hydroxide solutions pH=8.5, and deionized water is washed to after without nitrate anion, i.e.,
Obtain 1-dimention nano Mn oxide intercalation silver hydroxide material.
Above-mentioned 1-dimention nano Mn oxide intercalation silver hydroxide is added in 8mol/L ammonia spirits, stirred at room temperature
1h, you can silver hydroxide will be pulled out from 1-dimention nano Mn oxide and, and enable 1-dimention nano Mn oxide structure extensive
It is multiple.
We are tested above-mentioned 1-dimention nano Mn oxide intercalation cobalt hydroxide ag material, obtained 1-dimention nano
As shown in figure 11, as seen from Figure 11, silver salt can also be realized slotting the XRD spectra of Mn oxide intercalation cobalt hydroxide ag material
Metal silver hydroxide is entered between one-dimensional Mn oxide laminate after the preparation of Rotating fields, intercalation, the correspondence of 2 θ in XRD spectra=9.2
In Mn oxide laminate diffraction maximum, 2 θ=18.5 correspond to Mn oxide laminate and metallic hydrogen silver oxide laminate diffraction maximum, it is necessary to
Illustrate, the one-dimensional Mn oxide of silver hydroxide intercalation is unstable, can occur silver hydroxide oxidation in air for a long time
Decompose, note preserving.
The elementary analysis of the intercalation material prepared in above-described embodiment 1- embodiments 5 is as shown in table 1 below：
The 1-dimention nano Mn oxide of table 1 and its element analysis of intercalation metal hydroxide per
As can be seen from Table 1, there is no the presence of other metals in 1-dimention nano Mn oxide prepared by embodiment 1；We
Other metal salts can be intercalation between one-dimensional Mn oxide laminate by the preparation of intercalation configuration, and then can be by by ammoniacal liquor
Metal hydroxides intercalation all pulls out 1-dimention nano Mn oxide structure, therefore, and this is that a class has structure reversible transition
The material of property.
Embodiment described above is only the preferred embodiment to absolutely prove the present invention and being lifted, and its protection domain is not limited
In this.Equivalent substitute or conversion that those skilled in the art are made on the basis of the present invention, the protection in the present invention
Within the scope of, protection scope of the present invention is defined by claims.
Claims (7)
1. a kind of preparation method of metal hydroxides intercalation 1-dimention nano metal oxide materials, it is characterised in that specifically press
Implement according to following steps：
S1：The preparation of 1-dimention nano Mn oxide
S11：Prepare 0.05~0.5mol/L manganese salt solutions and 3~10mol/L aqueous slkalis respectively, and by the manganese salt solution and alkali
Solution is cooled to 5 DEG C；
S12：Manganese salt solution and aqueous slkali after cooling is poured into three-necked flask, Mn2+：OH-Mixing mol ratio for 0.004~
0.135：1, quick stirring, and 2~8L/min purity oxygen is passed through, 10~60min is reacted, stopping afterwards being passed through oxygen and is further continued for
React 3~4h of aging；
S13：The sediment obtained after reaction is washed with deionized to washing lotion in neutrality, gained moist press cake after filtering, is
1-dimention nano Mn oxide；
S2：The preparation of intercalation material
0.01~1.0mol/L metal salt solution is prepared, the 1-dimention nano Mn oxide prepared at room temperature with S1 is mixed
Close, the molal quantity and 1-dimention nano Mn oxide mass ratio of metal ion are 0.003~1mol in metal salt solution：10g, regulation
The pH of mixed liquor to 8.0~10.5, continues to stir constant to pH value, after deionized water washing, is placed in crystallizing kettle in 0~200
DEG C 0~24h of crystallization, produces intercalation material.
2. the preparation method of metal hydroxides intercalation 1-dimention nano metal oxide according to claim 1, its feature
It is, in S11, the manganese salt solution is Manganous sulfate monohydrate, manganese nitrate, chloride hydrate manganese or its mixture；The aqueous slkali
For sodium hydroxide solution.
3. the preparation method of metal hydroxides intercalation 1-dimention nano metal oxide according to claim 1, its feature
It is, in S2, the pH of mixed liquor is adjusted by 0.1~1.0mol/L alkali lye, the alkali lye is sodium hydroxide solution, potassium hydroxide
The mixture of one or both of solution.
4. the preparation method of metal hydroxides intercalation 1-dimention nano metal oxide according to claim 1, its feature
It is, in S2, the metal salt is CuSO4·xH2O、Cu(NO3)2·xH2O、CuCl2·xH2O、ZnCl2、ZnSO4·xH2O、
Ni(NO3)2·6H2O、NiCl2·xH2O、NiSO4·xH2O、Co(NO3)2·6H2O、CoSO4·7H2O、CoCl2·xH2O、
AgNO3In one or more of mixtures, but AgNO3Except the mixed solution of chlorine-containing compound.
5. a kind of metal hydroxides intercalation 1-dimention nano metal oxide, it is characterised in that by any institute of Claims 1 to 4
The method of stating is prepared, and the metal hydroxides intercalation 1-dimention nano metal oxide has structure reversible transition property.
6. metal hydroxides intercalation 1-dimention nano metal oxide according to claim 5 detaches method, its feature
It is, detailed process is as follows：
The metal hydroxides intercalation 1-dimention nano metal oxide is added into 2~14.8mol/L to detach in solution, room temperature
0.5~2h of lower stirring, you can metal hydroxides intercalation is cemented out from 1-dimention nano Mn oxide, makes 1-dimention nano manganese
Oxide structure is recovered.
7. metal hydroxides intercalation 1-dimention nano metal oxide according to claim 6 detaches method, its feature
It is, it is described to detach the ammoniacal liquor that solution is 5~12mol/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1080506A1 (en) * | 1998-04-30 | 2001-03-07 | Massachusetts Institute Of Technology | Intercalation compounds and electrodes for batteries |
| CN102921408A (en) * | 2012-11-27 | 2013-02-13 | 广东工业大学 | Preparation method and application of layered manganese oxide porous material catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1080506A1 (en) * | 1998-04-30 | 2001-03-07 | Massachusetts Institute Of Technology | Intercalation compounds and electrodes for batteries |
| CN102921408A (en) * | 2012-11-27 | 2013-02-13 | 广东工业大学 | Preparation method and application of layered manganese oxide porous material catalyst |
Non-Patent Citations (2)
| Title |
|---|
| CHENLIANG ZHOU ET AL.: ""synthesis of Misfit-Layered copper-manganese oxides"", 《ADVANCED MATERIALS RESEARCH》 * |
| 周晨亮等: ""层状氧化锰的制备及其表征"", 《内蒙古工业大学学报》 * |
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