CN107324393B - 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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- CN107324393B CN107324393B CN201710541795.0A CN201710541795A CN107324393B CN 107324393 B CN107324393 B CN 107324393B CN 201710541795 A CN201710541795 A CN 201710541795A CN 107324393 B CN107324393 B CN 107324393B
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Abstract
The invention discloses the preparation methods 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 the method for being inserted into metal hydroxides in one-dimensional nano structure metal oxide again, cements out metal hydroxides so that 1-dimention nano metal oxide is restored finally by ammonium hydroxide.The present invention develops for the first time extracts the method that metal hydroxides enables 1-dimention nano metal oxide to restore with ammonium hydroxide.This method simple process and low cost, may be implemented 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 detaches method.
Background technique
1-dimention nano metal oxide has unique chemistry in terms of ion exchange, intercalation reaction, catalysis and absorption
Performance, and also have special physical property in magnetic and conductibility.Substance of this kind is by two or more
Cellular construction layer alternately accumulate and formed.Nowadays the research in relation to 1-dimention nano metal oxide is concentrated mainly on metallic cobalt
On oxide, related other kinds of 1-dimention nano metal oxide structures report is considerably less, and 1-dimention nano metal oxide
Structure itself have two or more metal oxide property and its collective effect and generate other derive it is special
Property make 1-dimention nano metal oxide structures have special physics, chemical structure characteristic, the generation of these characteristics again can shadow
Answering in Dian Chi electrode material, adsorbent material and catalytic field is rung to 1-dimention nano metal oxide structures composite oxides
With.
Since 1-dimention nano metal oxide has special architectural characteristic, physics and chemical property and a pyroelectric effect
It receives significant attention.According to reports, nowadays most famous, most study 1-dimention nano metal oxide materials are mainly with cobalt oxide
Based on compound material.Isobe, Klimczuk, Shizuya, Miyazaki et al., which have successfully synthesized, has Ca-Co 1-dimention nano
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. thinks in 1-dimention nano metal
Oxide structure (CaOH)1.14CoO2In, it is surrounded around each Co ion by six oxonium ions, and Co-O key has 0.191nm
With two kinds of bond distances of 0.195nm, it is approximately equal to Co3+(r1=0.0545nm) and O2-(r2The sum of=0.140nm) ionic radius.Octahedral
Body CoO6Thickness be about 0.207nm, wherein the valence state of Co is close to+trivalent, by octahedra CoO6It is mingled between the laminate of composition
CaOH laminate.Klimczuk et al. thinks that molecular formula is Ca25Co22O56(OH)28Ca-Co composite oxides have 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 the double-deck calcium oxidhydroxide between laminate.Shizuya et al. proves octahedra phase after study
(CaOH)1.14CoO2With (the Ca of monoclinic system0.85OH)1.16CoO2Chemical composition having the same, the difference is that two kinds of compounds
With different structure cells, CoO of two kinds of compounds along c- axis2It is different with the arrangement mode of CaOH.Miyazaki et al. is also in nothing
Having synthesized between meaning has [Ca2CoO3]pCoO2The 1-dimention nano metal oxide structures of chemical general formula, wherein parameter p is along b-
Axis bCoO2(RS is rock-salt accumulation type (rock-salt type) [Ca to the ratio of/bRS2CoO3]), CdI in compound2Type
CoO2With three layers of rock-salt accumulation type [Ca2CoO3] along c- axis, alternately accumulation forms Ca-Co 1-dimention nano metal oxide composite oxygen
Compound.Moreover, because special nature possessed by 1-dimention nano metal oxide materials, 1-dimention nano metal oxide materials gold
Belonging to oxide has very big application potential in semiconductor, magnetic material, ferroelectric (Ferroelectric) and catalytic field.
The prior art is primarily present following 3 major defects:
1, the irreversible conversion of 1-dimention nano metal oxide materials structure.Although about 1-dimention nano metal oxide
Intercalated metal oxide/metal hydroxides/organic constitution materials synthesis report, but its synthetic product all has stabilization
One-dimensional or two-dimensional space structure, have irreversible denaturation.
2, it can not realize that 1-dimention nano metal oxide structures separate preparation with intercalation compound.It is existing about 1-dimention nano
Metal oxide intercalated metal oxide/metal hydroxides/organic constitution materials synthesis report 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 chemical combination object, such as king pass through the intercalation configuration that is mixed with out divalent transition metal and benzoate.
3, intercalation compound extracts or changing condition is harsh and rate is slower.The extraction of intercalation compound is the key that more difficult
Problem, in this process require i.e. cannot destroy 1-dimention nano metal oxide structures, also to realize intercalation compound detach or
Transformation.Conventional method needs can just make intercalation compound slow release in vacuum, high/low temperature or weak acid alkaline environment.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention utilizes the one-dimentional structure stability characteristic of metal oxide, system
Standby one-dimensional nano structure metal oxide out, then by being inserted into metal hydroxides in one-dimensional nano structure metal oxide
Method prepares intercalation material, pulls out metal hydroxides to come so that 1-dimention nano metal oxide obtains finally by ammonium hydroxide
To restore.
Specifically, the present 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: preparing 0.05~0.5mol/L manganese salt solution and 3~10mol/L aqueous slkali respectively, and by the manganese salt solution
5 DEG C are cooled to aqueous slkali；
S12: manganese salt solution after cooling and aqueous slkali are poured into three-necked flask, Mn2+: OH-Mixing molar ratio be
0.004~0.135:1 is quickly stirred, and is passed through the purity oxygen of 2~8L/min, reacts 10~60min, stops being passed through oxygen later
Gas is further continued for reaction 3~4h of aging；
S13: the sediment after reaction, which is washed with deionized to washing lotion, to be in neutrality, gained moist press cake after filtering, as
1-dimention nano Mn oxide；
S2: the preparation of intercalation material
The metal salt solution of 0.01~1.0M is prepared, the 1-dimention nano Mn oxide being prepared at room temperature with S1 is mixed
It closes, the molal quantity of metal ion and 1-dimention nano Mn oxide mass ratio are 0.003~1mol:10g in metal salt solution, are adjusted
The pH to 8.0~10.5 of mixed liquor, continue stirring it is constant to pH value, deionized water washing after, be placed in crystallizing kettle in 0~200
DEG C crystallization 0~for 24 hours to get intercalation material.
Preferably, the manganese salt solution is or mixtures thereof Manganous sulfate monohydrate, manganese nitrate, chloride hydrate manganese in S11；
The aqueous slkali is sodium hydroxide solution.
Preferably, adjusting the pH of mixed liquor by 0.1~1.0mol/L lye in S2, the lye is that sodium hydroxide is molten
The mixture of one or both of liquid, potassium hydroxide solution.
Preferably, the metal salt is CuSO in S24·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、AgNO3One or more of mixture, but AgNO3Except the mixed solution of chlorine-containing compound.
The present invention also provides a kind of metal hydroxides intercalation 1-dimention nano metal oxides, 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 provided by the invention detaches method, and detailed process is such as
Under:
The metal hydroxides intercalation 1-dimention nano metal oxide is added to 2~14.8mol/L to detach in solution,
0.5~2h is stirred at room temperature, metal hydroxides intercalation can be cemented out from 1-dimention nano Mn oxide, be made a wiener
Rice Mn oxide structure is restored.
Preferably, described detach the ammonium hydroxide that solution is 5~12mol/L.
Metal hydroxides intercalation 1-dimention nano metal oxide provided by the invention, metal target mentions in sewage treatment
The application taken or the application in terms of preparing special sensor material.
Compared with prior art, the technical solution adopted in the present invention has the following beneficial effects:
The present invention has synthesized the 1-dimention nano metal oxide with structure reversible transformation using manganese salt solution, realizes for the first time
The two-dimensional structure system of 1-dimention nano Mn oxide and the separable preparation of intercalation metal hydroxides, and develop use ammonia for the first time
Water extracts the method that metal hydroxides enables 1-dimention nano metal oxide to restore.This method simple process and low cost,
Industrialization large-scale production may be implemented, 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, which can be
Room temperature, normal pressure to medium temperature, middle pressure alkaline environment in by metal hydroxides steadily intercalation in 1-dimention nano manganese oxide layer
Between plate, which at room temperature and atmospheric pressure can be by metallic hydrogen by ammonium hydroxide dipping
Oxide pulls out laminate, realizes the recovery of intercalation compound simply detached with 1-dimention nano metal oxide structures.It should
This special nature of intercalation material, intercalation preparation method and detach method can be used as metal target in sewage treatment extract or
Preparing special sensor material etc. has extensive use.
Detailed description of the invention
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 process flow in the embodiment of the present invention 1
Figure；
Fig. 4 is 1-dimention nano Mn oxide SEM figure 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 figure 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 is that SEM schemes 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.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments, it is to be understood that protection of the invention
Range is not limited by the specific implementation.The test method of actual conditions is not specified in the following example, usually according to normal
Advise conditional operation, the experimental material source being not specified be it is commercially available, due to not being related to inventive point, therefore its step is not carried out detailed
Description.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
Scientific term is identical as the normally understood meaning of those skilled in the art of the present technique.Except specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to the prior art can also be used and this
Any method, equipment and the material of the similar or equivalent prior art of method described in inventive embodiments, equipment, material come real
The existing present invention.
Embodiment 1
The present embodiment 1-dimention nano Mn oxide intercalation Kocide SD material, preparation process are specific as follows:
Weigh the MnSO of 11.0g4·H2O is added in 130ml deionized water and is configured to manganese sulfate solution, weighs 36.7g's
NaOH, which is added in 167ml deionized water, is configured to NaOH solution, and the manganese sulfate solution of preparation and NaOH solution are dropped respectively
Temperature is to 5 DEG C.Manganese sulfate solution and NaOH solution are poured into three-necked flask, quickly stir (500r/min), and be passed through 5L/min
Purity oxygen, react 30min, later stop be passed through oxygen be further continued for reaction aging 4h.Sediment is washed with distilled water to neutrality,
Gained moist press cake is the 1-dimention nano Mn oxide material with structure reversible transition property, specific preparation process after filtering
Flow chart is as shown in Figure 1.
Weigh the CuSO of 15.0g4·5H2O, which is added in 300ml deionized water, is configured to manganese sulfate solution, at room temperature with
1-dimention nano Mn oxide mixing 10.0g obtained above, then mixed liquor is titrated to pH with the sodium hydroxide solution of 0.5mol/L
=10.0, continue stirring it is constant to pH value, deionized water is washed to sulfate radical-free and is placed in crystallizing kettle in 150 DEG C of crystallization 10h,
Up to 1-dimention nano Mn oxide intercalation Kocide SD material, 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 spirit, is stirred at room temperature
Kocide SD can will be pulled out from 1-dimention nano Mn oxide and, and keep 1-dimention nano Mn oxide structure extensive by 1h
Multiple, the reversible transformation process flow chart is as shown in Figure 3.
We test above-mentioned 1-dimention nano Mn oxide material, SEM spectrogram as shown in figure 4, its XRD spectra such as
Shown in Fig. 5；We test above-mentioned 1-dimention nano Mn oxide intercalation Kocide SD material, obtained 1-dimention nano manganese
The SEM spectrogram of oxide intercalation Kocide SD material is as shown in fig. 6, XRD spectra is as shown in Figure 7；Comparison chart 4 and Fig. 6 can be seen
Out, after intercalation processing, one-dimensional Mn oxide still maintains thin plates pattern, and intercalation process is not to one-dimensional Mn oxide shape
Looks damage.Metal hydroxides does enter into one-dimensional Mn oxide laminate after comparison chart 5 and Fig. 7 can be seen that 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 spectrum after obtained 1-dimention nano Mn oxide intercalation Kocide SD material reversible transformation
Scheme as shown in figure 8, XRD spectra is as shown in figure 9, as seen from Figure 8, detaching process and not causing to one-dimensional Mn oxide pattern
It destroys and changes, it is reusable to further relate to the structure.As seen from Figure 9, after detaching, 1-dimention nano Mn oxide X is penetrated
Line diffraction maximum has restored diffraction maximum shown in Fig. 5, illustrates that 1-dimention nano Mn oxide structure can be restored.
Embodiment 2
The present embodiment 1-dimention nano Mn oxide intercalation zinc hydroxide material, preparation process are specific as follows:
Weigh the Mn (NO of the 50wt% of 23.2ml3)2Solution is added in 276.8ml deionized water that be configured to manganese nitrate molten
Liquid, the NaOH for weighing 50.0g, which is added in 150.0ml deionized water, is configured to NaOH solution, and by manganese nitrate solution and NaOH
Solution is cooled to 5 DEG C.By after cooling manganese nitrate solution and NaOH solution pour into three-necked flask, quickly stir (500r/
Min), and it is passed through the purity oxygen of 6L/min, reacts 50min, stop being passed through oxygen being further continued for reaction aging 4h later.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 the ZnSO of 10.0g4Be added in 300ml deionized water and be configured to solution of zinc sulfate, at room temperature with 10.0g
Above-mentioned 1-dimention nano Mn oxide mixing, then it is titrated to pH=9.5 with 0.5mol/L sodium hydroxide solution, continue stirring to pH value
It is constant, deionized water wash to sulfate radical-free after to get 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 spirit, is stirred at room temperature
Zinc hydroxide can will be pulled out from 1-dimention nano Mn oxide and, and keep 1-dimention nano Mn oxide structure extensive by 1h
It is multiple.
Embodiment 3
The present embodiment 1-dimention nano Mn oxide intercalation nickel hydroxide material, preparation process are specific as follows:
Weigh the MnCl of 10.0g2·4H2O is added in 150.0ml deionized water and is configured to manganese chloride solution, weighs
The NaOH of 50.0g, which is added in 150.0ml deionized water, is configured to NaOH solution, and manganese chloride solution and NaOH solution are cooled down
To 5 DEG C.By after cooling manganese chloride solution and NaOH solution pour into three-necked flask, quickly stir (500r/min), and be passed through
The purity oxygen of 8L/min reacts 40min, and stopping later being passed through oxygen and is further continued for reaction aging 4h.It is washed with distilled water sediment
To neutrality, gained moist press cake is 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 the NiSO of 5.0g4·6H2O, which is added in 300ml deionized water, is configured to nickel sulfate liquid, at room temperature with
The mixing of 10.0g 1-dimention nano Mn oxide, then it is titrated to pH=8.0 with 0.5mol/L sodium hydroxide solution, continue stirring to pH
Be worth it is constant, deionized water wash to sulfate radical-free be placed in crystallizing kettle in 200 DEG C of crystallization 10h to get 1-dimention nano manganese oxidation
Object intercalation nickel hydroxide material.
Above-mentioned 1-dimention nano Mn oxide intercalation nickel hydroxide material is added in 12mol/L ammonia spirit, at room temperature
1h is stirred, nickel hydroxide will can be pulled out from 1-dimention nano Mn oxide and, and obtain 1-dimention nano Mn oxide structure
To restore.
Embodiment 4
The present embodiment 1-dimention nano Mn oxide intercalation cobalt hydroxide material, in preparation process, the oxidation of 1-dimention nano manganese
It is identical in the preparation process and embodiment 1 of object material.1-dimention nano Mn oxide intercalation cobalt hydroxide materials process are as follows: weigh
10.0g CoSO4·7H2O, which is added in 300ml deionized water, 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 pH=9 with 1mol/L sodium hydroxide solution, it is constant to pH value to continue stirring, go from
Sub- water washing to sulfate radical-free is placed in crystallizing kettle in 70 DEG C of room temperature crystallization to get 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 spirit, stirs 1h at room temperature,
Cobalt hydroxide will can be pulled out from 1-dimention nano Mn oxide and, 1-dimention nano Mn oxide structure is enable to restore.
We test above-mentioned 1-dimention nano Mn oxide intercalation cobalt hydroxide material, obtained 1-dimention nano manganese
The XRD spectra of oxide intercalation cobalt hydroxide material is as shown in Figure 10, and as seen from Figure 10, intercalation knot also may be implemented in Co salt
The preparation of structure, between metal cobalt hydroxide enters one-dimensional Mn oxide laminate after 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
The present embodiment 1-dimention nano Mn oxide intercalation silver hydroxide material, in preparation process, the oxidation of 1-dimention nano manganese
It is identical in the preparation process and embodiment 1 of object material.1-dimention nano Mn oxide intercalation silver hydroxide materials process are as follows: weigh
The AgNO of 1.0g3Be added in 300ml deionized water and be configured to metal salt solution, at 5 DEG C with the above-mentioned 1-dimention nano manganese of 10.0g
Oxide mixing, then it is titrated to pH=8.5 with 0.2mol/L sodium hydroxide solution, deionized water is washed to no 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 spirit, is stirred at room temperature
Silver hydroxide can will be pulled out from 1-dimention nano Mn oxide and, and keep 1-dimention nano Mn oxide structure extensive by 1h
It is multiple.
We test above-mentioned 1-dimention nano Mn oxide intercalation cobalt hydroxide ag material, obtained 1-dimention nano
The XRD spectra of Mn oxide intercalation cobalt hydroxide ag material is as shown in figure 11, and as seen from Figure 11, silver salt also may be implemented to insert
The preparation of layer structure, between metal silver hydroxide enters one-dimensional Mn oxide laminate after intercalation, 2 θ=9.2 are corresponding in XRD spectra
In Mn oxide laminate diffraction maximum, 2 θ=18.5 correspond to Mn oxide laminate and metallic hydrogen silver oxide laminate diffraction maximum, need
Illustrate, the one-dimensional Mn oxide of silver hydroxide intercalation is unstable, and silver hydroxide oxidation can be occurred by being exposed in air for a long time
It decomposes, pays attention to saving.
The elemental analysis for the intercalation material being prepared in above-described embodiment 1- embodiment 5 is as shown in table 1 below:
1 1-dimention nano Mn oxide of table and its analysis of intercalation metal hydroxide per element
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
Between other metal salts being intercalation into one-dimensional Mn oxide laminate by the preparation of intercalation configuration, and can then it be incited somebody to action by ammonium hydroxide
Metal hydroxides intercalation all pulls out 1-dimention nano Mn oxide structure, and therefore, this is a kind of with structure reversible transition
The material of property.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, and protection scope is unlimited
In this.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in protection of the invention
Within the scope of, protection scope of the present invention is subject to claims.
Claims (4)
1. a kind of metal hydroxides intercalation 1-dimention nano metal oxide materials detach method, which is characterized in that specifically press
Implement according to following steps:
S1: the preparation of 1-dimention nano Mn oxide
S11: preparing 0.05~0.5mol/L manganese salt solution and 3~10mol/L aqueous slkali respectively, and by the manganese salt solution and alkali
Solution is cooled to 5 DEG C；
S12: manganese salt solution after cooling and aqueous slkali are poured into three-necked flask, Mn2+: OH-Mixing molar ratio be 0.004~
0.135:1 is quickly stirred, and is passed through the purity oxygen of 2~8L/min, reacts 10~60min, and stopping is passed through oxygen and is further continued for later
React 3~4h of aging；
S13: the sediment obtained after reaction, which is washed with deionized to washing lotion, to be in neutrality, gained moist press cake after filtering, as
1-dimention nano Mn oxide；
S2: the preparation of intercalation material
The metal salt solution of 0.01~1.0mol/L is prepared, the 1-dimention nano Mn oxide being prepared at room temperature with S1 is mixed
It closes, the molal quantity of metal ion and 1-dimention nano Mn oxide mass ratio are 0.003~1mol:10g in metal salt solution, are adjusted
The pH to 8.0~10.5 of mixed liquor, continue stirring it is constant to pH value, deionized water washing after, be placed in crystallizing kettle in 0~200
DEG C crystallization 0~for 24 hours to get intercalation material；
S3: it detaches
The metal hydroxides intercalation 1-dimention nano metal oxide is added to 2~14.8mol/L to detach in solution, room temperature
Metal hydroxides intercalation can be cemented out from 1-dimention nano Mn oxide, make 1-dimention nano manganese by 0.5~2h of lower stirring
Oxide structure is restored, described to detach the ammonium hydroxide that solution is 5~12mol/L.
2. metal hydroxides intercalation 1-dimention nano metal oxide according to claim 1 detaches method, feature
It is, in S11, the manganese salt solution is or mixtures thereof Manganous sulfate monohydrate, manganese nitrate, chloride hydrate manganese；The aqueous slkali
For sodium hydroxide solution.
3. metal hydroxides intercalation 1-dimention nano metal oxide according to claim 1 detaches method, feature
It is, in S2, the pH of mixed liquor is adjusted by 0.1~1.0mol/L lye, the lye is sodium hydroxide solution, potassium hydroxide
The mixture of one or both of solution.
4. metal hydroxides intercalation 1-dimention nano metal oxide according to claim 1 detaches method, 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、
AgNO3One or more of mixture, but AgNO3Except the mixed solution of chlorine-containing compound.
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