CN109133193A - A method of metal hydroxides multilevel structure is prepared using the derivative bimetallic oxide template of MOF - Google Patents
A method of metal hydroxides multilevel structure is prepared using the derivative bimetallic oxide template of MOF Download PDFInfo
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Abstract
The present invention relates to technical field of nano material more particularly to a kind of methods for preparing metal hydroxides multilevel structure using the derivative bimetallic oxide template of MOF, and the derivative bimetallic oxide template of MOF is obtained metal hydroxides multilevel structure by alkali process；M is set as the metal in the metal hydroxides multilevel structure, the derivative bimetallic oxide template of the MOF is MMoO4- MOF derives bimetallic oxide, and the metal hydroxides multilevel structure is M (OH)x.Preparation process of the present invention is simple, mild, pervasive, to equipment without particular/special requirement, does not use surfactant, can large-scale industrialized production；The metal hydroxides multilevel structure size uniformity prepared using this method, stable structure, composite distribution is uniform, shows excellent OER performance and constant current stability.
Description
Technical field
The present invention relates to technical field of nano material more particularly to a kind of derivative bimetallic oxide template systems of utilization MOF
The method of standby metal hydroxides multilevel structure.
Background technique
The nano material of multilevel structure studies this concern since its excellent physicochemical properties has caused extensively.
It can be the whole knot of material since nanoscale basic unit provides high surface area, high surface volume ratio, surface functional group
Structure provides ideal mechanical performance and chemical property.Multilevel structure is to be formed from molecule to macro-scale by stringent organizational principle
Structure, and the multilevel structure that forms can produce functional material more in any level.
Metal hydroxides nano material has obtained extensive research as a kind of important functional material.Multilevel structure
Controlled morphologies, orientation and dimension, become one of the hot spot of material science research.Due to its have it is some special physico
Learn property, it will have extensive potential application in terms of electromagnetism, electronics, catalysis, water process and the energy.Therefore, had
There is the Nano material of hydrate of multilevel structure of specific dimensions, pattern, dimension, polymolecularity to be of great significance.However, mesh
The Nano material of hydrate synthetic method of preceding multilevel structure mostly uses surfactant, toxic organic solvent, prepares work
Skill is complicated, and can not largely prepare.
Summary of the invention
The present invention is complicated in order to overcome the hydroxide preparation process of conventional multi-level structure, dependent on surfactant, no
The problem of conducive to industrialization, provides and a kind of prepares metal hydroxides multistage knot using the derivative bimetallic oxide template of MOF
The method of structure, preparation process is simple, mild, pervasive and can largely prepare, and does not use surfactant, is suitable for extensive industry
Metaplasia produces.
To achieve the goals above, the invention adopts the following technical scheme:
A method of metal hydroxides multilevel structure being prepared using the derivative bimetallic oxide template of MOF, MOF is derivative double
Metal oxide template obtains metal hydroxides multilevel structure by alkali process；It is multistage as the metal hydroxides to set M
Metal in structure, the derivative bimetallic oxide template of the MOF is MMoO4- MOF derives bimetallic oxide, the metal
Hydroxide multilevel structure is M (OH)2。
Metal-organic framework materials (Metal-organic frameworks, MOF) are metal ion and organic ligand knot
With the crystal of porous network structure made of conjunction, the cellular structure with high-sequential, bigger specific surface area is more connect
Touch active site.The present invention is with the derivative bimetallic oxide MMoO of MOF4- MOF is template, wherein M is metal target hydroxide
Metal in object multilevel structure, after alkali process, obtained MoO4 2-Lye is dissolved in, in target metal ions M and lye
OH-In conjunction with hydroxide is generated, the metal hydroxides multilevel structure M of the monodimension nano stick of two-dimensional nano piece composition is obtained
(OH)x, gained metal hydroxides multilevel structure size uniformity, stable structure, composite distribution is uniform.Preparation method of the invention
Easy to operate, independent of surfactant, mild condition can largely prepare metal hydroxides multilevel structure.
Preferably, the MMoO4The preparation method of-MOF material, comprising the following steps:
(1) by MoO3With 2-methylimidazole aqueous dissolution in deionized water, the water-soluble salt solution of M is added, is heated to 80
It~180 DEG C DEG C, is stirred to react 6h or more and M/Mo-MOF material is made after cooling, washing, drying；
(2) by M/Mo-MOF material high-temperature calcination under air atmosphere made from step (1), MMoO is obtained4- MOF is derivative double
Metal oxide.
The derivative bimetallic oxide of MOF of the present invention is to prepare resulting bimetallic MOF by being simply condensed back,
High-temperature calcination oxidation through the air is made.It is condensed back gained MOF stable structure, size uniformity, gained metal oxygen after calcining
Compound size uniformity, stable structure.The water-soluble salt solution of M such as Co (NO3)2·6H2O and Ni (NO3)2·6H2O and other sulphur
Hydrochlorate etc..
Preferably, the temperature of high-temperature calcination is 300~900 DEG C in step (2)；Calcination time be 1~for 24 hours；Heating speed
Rate is 1~20 DEG C/min.
Preferably, concentration is used to carry out alkali process for the KOH solution of 0.01~10mol/L.
Preferably, concentration is used to carry out alkali process for the KOH solution of 0.1mol/L.
Preferably, the MMoO4The derivative bimetallic oxide of-MOF and OH-The ratio between the amount of substance be 1:(1~100).
Preferably, the MMoO4The derivative bimetallic oxide of-MOF and OH-The ratio between the amount of substance be 1:25.
Preferably, by MMoO4The derivative bimetallic oxide of-MOF stands 0.5~8h in KOH solution, obtains metal
Hydroxide multilevel structure M (OH)x。
Preferably, MMoO4The derivative bimetallic oxide of-MOF time of repose in KOH solution is 6h.
Preferably, the M is selected from Cu, Zn, Fe, Mg, Al, one of Co and Ni.
Therefore, the invention has the following beneficial effects:
(1) preparation process is simple, mild, pervasive, to equipment without particular/special requirement, does not use surfactant, can extensive industry
Metaplasia produces；
(2) using the metal hydroxides multilevel structure size uniformity of this method preparation, stable structure, composite distribution is uniform, exhibition
Reveal excellent OER performance and constant current stability.
Detailed description of the invention
Fig. 1 is the appearance structure figure of product prepared by embodiment 1:
Co/Mo-MOF(a,b,c)；CoMoO4-MOF(d,e,f)；Co(OH)2Multilevel structure (g, h, i).
Fig. 2 is the XRD spectra of Co/Mo-MOF prepared by embodiment 1.
Fig. 3 is CoMoO prepared by embodiment 14The XRD spectra of-MOF.
Fig. 4 is Co (OH) prepared by embodiment 12The XRD spectra of multilevel structure.
Fig. 5 is Co (OH) prepared by embodiment 12The OER performance test figure of multilevel structure.
Fig. 6 is Co (OH) prepared by embodiment 12The constant current stability test figure of multilevel structure.
Fig. 7 is the appearance structure figure of product prepared by embodiment 2:
Ni/Mo-MOF(a,b,b1,b2)；NiMoO4-MOF(c,d,d1,d2)；Ni(OH)2Multilevel structure (e, f).
Fig. 8 is the XRD spectra of Ni/Mo-MOF prepared by embodiment 2.
Fig. 9 is NiMoO prepared by embodiment 24The XRD spectra of-MOF.
Figure 10 is Ni (OH) prepared by embodiment 22The XRD spectra of multilevel structure.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, the technical solutions of the present invention will be further described.
In the present invention, if not refering in particular to, all devices and raw material is commercially available or the industry is common are following
Method in embodiment is unless otherwise instructed conventional method in that art.
Embodiment 1
(1) clean beaker is taken, 25ml deionized water is added, weighs 0.5g MoO3It pours into deionized water, weighs 0.475g
2-methylimidazole pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs 0.3g
Co(NO3)2·6H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in cobalt nitrate solution3In solution.Oil bath heating is to 120
DEG C, it is stirred to react 12h, reaction is down to room temperature after stopping naturally.Deionized water centrifuge washing, in triplicate, and it is true at 60 DEG C
The dry 12h of sky, is made Co/Mo-MOF；
(2) it takes appropriate Co/Mo-MOF to place in ship type crucible, crucible is placed among quartz ampoule, in air atmosphere in tube furnace
Lower 500 DEG C of high-temperature oxydation 3h are enclosed, heating rate is 10 DEG C/min, and CoMoO is made4- MOF crystal powder；
(3) 10mg CoMoO is taken4MOF crystal powder is placed in a clean container, and it is molten that the KOH that 10ml concentration is 0.1mol/L is added
Liquid, CoMoO4- MOF and OH-The ratio between the amount of substance be 1:25, stand 6h at room temperature, after reaction, by product be transferred to from
In heart pipe, with deionized water centrifuge washing, be repeated 3 times, be placed at 60 DEG C of vacuum drying oven dry 12h, obtain Co (OH)2
Multilevel structure.
To Co/Mo-MOF crystal powder, CoMoO made from embodiment 14- MOF crystal powder and Co (OH)2Multilevel structure into
The following characterization of row:
(1) morphology analysis:
Sem analysis:
SEM test carries out in HITACHI S-4700 scanning electron microscope, and sample used is the preparation method is as follows: take on a small amount of
State gained Co/Mo-MOF crystal powder, CoMoO4Crystal powder, Co (OH)2Multilevel structure powder is placed in the support for posting conducting resinl
Platform surface then puts it into SEM chamber and is tested.
High-resolution tem analysis:
TEM test carried out on JEOL 2010F type transmission electron microscope, sample used the preparation method is as follows: taking above-mentioned reality
Apply the preparation gained Co/Mo-MOF of example 1 crystal powder, CoMoO4- MOF crystal powder, Co (OH)2Multilevel structure powder is micro, respectively
About 1ml deionized water is added dropwise, ultrasonic disperse 10min takes a small amount of dispersion liquid to be added dropwise using drip method in band micro-grid to being uniformly dispersed
Film (is supported containing microporous carbon) in copper mesh surface, is placed in and spontaneously dries at room temperature.
Co/Mo-MOF crystal powder, CoMoO obtained in embodiment 14- MOF crystal powder, Co (OH)2Multilevel structure
The SEM figure of powder is with TEM figure as shown in Figure 1, the whole pattern that Fig. 1 (a, b) illustrates Co/Mo-MOF material is that surface is smooth
Club shaped structure.Cross-sectional diameter about 1um, is about 5um.And it can largely prepare.It is good that Fig. 1 (c) shows that Co/Mo-MOF has
Crystallinity, stable structure, component are uniform.Fig. 1 (d, e) illustrates CoMoO4The whole pattern of-MOF material is the smooth stick in surface
Shape structure.Cross-sectional diameter about 1um is about 5um, and can largely prepare.Fig. 1 (f) shows CoMoO4- MOF has good
Crystallinity, stable structure, component are uniform.Fig. 1 (g, h) illustrates Co (OH)2The whole pattern of multilevel structure material is Co (OH)2
Nanometer sheet intersects the club shaped structure to be formed.Club shaped structure overall dimensions cross-sectional diameter about 1um, is about 5um.And it can be big
Amount preparation.Fig. 1 (i) shows Co (OH)2Multilevel structure has good crystallinity, and stable structure, component is uniform.
(2) wide-angle XRD analysis:
XRD test carries out on X'Pert Pro type X-ray diffractometer, and sample to be tested preparation is as follows: Co/Mo- in Example 1
MOF crystal powder, CoMoO4- MOF crystal powder, Co (OH)2It is recessed to be laid on rectangular frosted on quartz plate respectively for multilevel structure powder
In slot, and is flattened and tested with glass slide compacting.
Co/Mo-MOF crystal powder, the CoMoO prepared in embodiment 1 is set forth in Fig. 2-Fig. 44- MOF crystal powder,
Co(OH)2The wide-angle XRD spectra of multilevel structure powder shows that gained Co/Mo-MOF crystalline material has good crystallization in Fig. 2
Property, it shows that result is consistent with Fig. 1 (c), illustrates successfully to synthesize Co/Mo-MOF material, Fig. 3 is by obtained by high-temperature oxydation
CoMoO4The XRD spectrum of-MOF crystal powder, diffraction maximum and CoMoO in figure4Standard card (PDF#21-0868) is consistent, it was demonstrated that at
Function synthesizes CoMoO4- MOF material.Fig. 4 is by Co (OH) obtained by dipping by lye2The XRD spectrum of multilevel structure powder is spread out in figure
Penetrate peak and Co (OH)2Standard card (PDF#45-0031) is consistent, it was demonstrated that successfully synthesizes Co (OH)2Multilevel structure material.
(3) OER performance test:
As seen from Figure 5, OER performance test is carried out in 1M KOH, reaches 10mA/cm in current density2When, commercial IrO2
Overpotential be 1.625V, and Co obtained in embodiment 1 (OH)2The overpotential of multilevel structure is 1.521V, than commercial IrO2
Low 104mV shows excellent OER performance.
(4) constant current stability test:
From fig. 6, it can be seen that being 10mA/cm in current density2When, after 12h, the overpotential of catalyst is almost without upper
It rises, illustrates Co obtained in embodiment 1 (OH)2Multilevel structure shows excellent constant current stability.
Embodiment 2
(1) clean beaker is taken, 25ml deionized water is added, weighs 0.5g MoO3It pours into deionized water, weighs 0.475g
2-methylimidazole pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs 0.3g
Ni(NO3)2·6H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in nickel nitrate solution3In solution.Oil bath heating is to 80
DEG C, it is stirred to react 18h, reaction is down to room temperature after stopping naturally.Deionized water centrifuge washing, in triplicate.And it is true at 60 DEG C
The dry 12h of sky, is made Ni/Mo-MOF crystal powder；
(2) it takes appropriate Ni/Mo-MOF to place in ship type crucible, crucible is placed among quartz ampoule, in air atmosphere in tube furnace
Lower 900 DEG C of high-temperature oxydation 1h are enclosed, heating rate is 20 DEG C/min, obtains NiMoO4- MOF crystal powder；
(3) NiMoO for taking 10mg to be prepared by step (2)4- MOF crystal powder is placed in a clean container, and 10ml concentration is added and is
The KOH solution of 10mol/L, NiMoO4The ratio between amount of substance of-MOF and OH- is 1:1,60 DEG C of oil bath heatings reflux 6h, reaction knot
Product is transferred in centrifuge tube by Shu Hou, with deionized water centrifuge washing, is repeated 3 times, be placed at 60 DEG C of vacuum drying oven do
Dry 12h obtains Ni (OH)2Multilevel structure.
To Ni/Mo-MOF crystal powder, NiMoO made from embodiment 24- MOF crystal powder and Ni (OH)2Multilevel structure into
The following characterization of row:
(1) morphology analysis:
Sem analysis:
SEM test carries out in HITACHI S-4700 scanning electron microscope, and sample used is the preparation method is as follows: take on a small amount of
State gained Ni/Mo-MOF crystal powder, NiMoO4Crystal powder, Ni (OH)2Multilevel structure powder is placed in the support for posting conducting resinl
Platform surface then puts it into SEM chamber and is tested.
High-resolution tem analysis:
TEM test carried out on JEOL 2010F type transmission electron microscope, sample used the preparation method is as follows: taking above-mentioned reality
Apply the preparation gained Ni/Mo-MOF of example 2 crystal powder, NiMoO4Crystal powder, Ni (OH)2Multilevel structure powder is micro, is added dropwise respectively
About 1ml deionized water, ultrasonic disperse 10min take a small amount of dispersion liquid to be added dropwise using drip method in band micro-grid copper mesh to being uniformly dispersed
Film (is supported containing microporous carbon) in surface, is placed in and spontaneously dries at room temperature.
Ni/Mo-MOF crystal powder, NiMoO obtained in embodiment 24Crystal powder, Ni (0H)2Multilevel structure powder
SEM figure with TEM figure as shown in fig. 7, the whole pattern that Fig. 7 (a, b) illustrates Ni/Mo-MOF material is smooth rodlike in surface
Structure.Cross-sectional diameter about 1um, is about 5um.Fig. 7 (b1, b2) shows that Ni/Mo-MOF has good crystallinity, and structure is steady
Fixed, component is uniform.Fig. 7 (c, d) illustrates NiMoO4The whole pattern of-MOF material is the smooth club shaped structure in surface.Cross section
Diameter about 1um, is about 5um.Fig. 7 (d1, d2) shows NiMoO4- MOF has good crystallinity, and stable structure, component is uniform.
Fig. 7 (e, f) illustrates Ni (OH)2The whole pattern of multilevel structure material is Ni (OH)2Nanometer sheet intersects the rodlike knot to be formed
Structure.Club shaped structure overall dimensions cross-sectional diameter about 1um, is about 5um.
(2) wide-angle XRD analysis
XRD test carries out on X'Pert Pro type X-ray diffractometer, and sample to be tested preparation is as follows: Ni/Mo- in Example 2
MOF crystal powder, NiMoO4Crystal powder, Ni (0H)2Multilevel structure powder is laid on respectively on quartz plate in rectangular frosted groove,
And it is flattened and is tested with glass slide compacting.
Fig. 8-Figure 10 gives Ni/Mo-MOF crystal powder, the NiMoO prepared in embodiment 24Crystal powder, Ni (OH)2
The wide-angle XRD spectra of multilevel structure powder shows that gained Ni/Mo-MOF crystalline material has good crystallinity in Fig. 8, with figure
7 (b1, b2) show that result is consistent, illustrate successfully to synthesize Ni/Mo-MOF material, and Fig. 9 is by NiMoO obtained by high-temperature oxydation4-
The XRD spectrum of MOF crystal powder, diffraction maximum and NiMoO in figure4Standard card (PDF#33-0948) is consistent, it was demonstrated that successfully synthesizes
NiMoO4Material.Figure 10 is by Ni (OH) obtained by dipping by lye2The XRD spectrum of multilevel structure powder, diffraction maximum and Ni in figure
(OH)2Standard card (PDF#14-0117) is consistent, it was demonstrated that successfully synthesizes Ni (OH)2Multilevel structure material.
Embodiment 3
A clean beaker is taken, 25ml deionized water is added, weighs 0.5g MoO3It pours into deionized water, weighs 0.475g 2- first
Base imidazoles pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs 0.3g Co
(NO3)2·6H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in cobalt nitrate solution3In solution.Oil bath heating is to 180
DEG C, it is stirred to react 10h, reaction is down to room temperature after stopping naturally.Deionized water centrifuge washing, is repeated four times, and true at 60 DEG C
The dry 12h of sky, is made Co/Mo-MOF；
(2) it takes appropriate Co/Mo-MOF to place in ship type crucible, crucible is placed among quartz ampoule, in air atmosphere in tube furnace
Enclose lower 300 DEG C of high-temperature oxydations for 24 hours, heating rate is 1 DEG C/min, and CoMoO is made4- MOF crystal powder；
(3) 10mg CoMoO is taken4- MOF crystal powder is placed in a clean container, and the KOH that 10ml concentration is 0.01mol/L is added
Solution, CoMoO4- MOF and OH-The ratio between the amount of substance be 1:100, stand 6h at room temperature, after reaction, product be transferred to
In centrifuge tube, with deionized water centrifuge washing, be repeated 3 times, be placed at 60 DEG C of vacuum drying oven dry 12h, obtain Co
(OH)2Multilevel structure.
Embodiment 4
(1) clean beaker is taken, 25ml deionized water is added, weighs 0.5g MoO3It pours into deionized water, weighs 0.475g
2-methylimidazole pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs
0.304g Cu(NO3)2·6H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in copper nitrate solution3In solution.Oil bath adds
Heat is stirred to react 15h to 150 DEG C, and reaction is down to room temperature after stopping naturally.Deionized water centrifuge washing, in triplicate.And in 60
It is dried in vacuo 12h at DEG C, Cu/Mo-MOF crystal powder is made；
(2) it takes appropriate Cu/Mo-MOF to place in ship type crucible, crucible is placed among quartz ampoule, in air atmosphere in tube furnace
Lower 600 DEG C of high-temperature oxydation 2.5h are enclosed, heating rate is 10 DEG C/min, obtains CuMoO4- MOF crystal powder；
(3) CuMoO for taking 10mg to be prepared by step (2)4- MOF crystal powder is placed in a clean container, and 10ml concentration is added and is
The KOH solution of 2mol/L, CuMoO4The ratio between amount of substance of-MOF and OH- is 1:1,60 DEG C of oil bath heatings reflux 5h, reaction knot
Product is transferred in centrifuge tube by Shu Hou, with deionized water centrifuge washing, is repeated 3 times, be placed at 60 DEG C of vacuum drying oven do
Dry 12h obtains Cu (OH)2Multilevel structure.
Embodiment 5
(1) clean beaker is taken, 25ml deionized water is added, weighs 0.5g MoO3It pours into deionized water, weighs 0.475g
2-methylimidazole pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs
0.264g Mg(NO3)2·9H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in magnesium nitrate solution3In solution.Oil bath adds
Heat is stirred to react 10h to 110 DEG C, and reaction is down to room temperature after stopping naturally.Deionized water centrifuge washing, in triplicate, and in 60
It is dried in vacuo 12h at DEG C, Mg/Mo-MOF is made；
(2) it takes appropriate Mg/Mo-MOF to place in ship type crucible, crucible is placed among quartz ampoule, in air atmosphere in tube furnace
Lower 450 DEG C of high-temperature oxydation 4h are enclosed, heating rate is 10 DEG C/min, and MgMoO is made4- MOF crystal powder；
(3) 10mg MgMoO is taken4- MOF crystal powder is placed in a clean container, and the KOH that 10ml concentration is 0.2mol/L is added
Solution, MgMoO4- MOF and OH-The ratio between the amount of substance be 1:30, stand 4h at room temperature, after reaction, product be transferred to
In centrifuge tube, with deionized water centrifuge washing, be repeated 3 times, be placed at 60 DEG C of vacuum drying oven dry 12h, obtain Mg
(OH)2Multilevel structure.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, and is not surpassing
There are also other variations and modifications under the premise of technical solution documented by claim out.
Claims (10)
1. a kind of method for preparing metal hydroxides multilevel structure using the derivative bimetallic oxide template of MOF, feature exist
In the derivative bimetallic oxide template of MOF is obtained metal hydroxides multilevel structure by alkali process；M is set as the gold
Belong to the metal in hydroxide multilevel structure, the derivative bimetallic oxide template of the MOF is MMoO4- MOF derives bimetallic oxygen
Compound, the metal hydroxides multilevel structure are M (OH)x。
2. a kind of derivative bimetallic oxide template of utilization MOF according to claim 1 prepares metal hydroxides multistage
The method of structure, which is characterized in that the MMoO4The preparation method of-MOF material, comprising the following steps:
(1) by MoO3With 2-methylimidazole aqueous dissolution in deionized water, the water-soluble salt solution of M is added, it is heated to 80~
It 180 DEG C, is stirred to react 6h or more and M/Mo-MOF material is made after cooling, washing, drying；
(2) by M/Mo-MOF material high-temperature calcination under air atmosphere made from step (1), MMoO is obtained4The derivative double gold of-MOF
Belong to oxide.
3. a kind of derivative bimetallic oxide template of utilization MOF according to claim 2 prepares metal hydroxides multistage
The method of structure, which is characterized in that in step (2), the temperature of high-temperature calcination is 300~900 DEG C；Calcination time be 1~for 24 hours；
Heating rate is 1~20 DEG C/min.
4. a kind of derivative bimetallic oxide template of utilization MOF according to claim 1 or 2 or 3 prepares metal hydroxide
The method of object multilevel structure, which is characterized in that concentration is used to carry out alkali process for the KOH solution of 0.01~10mol/L.
5. a kind of derivative bimetallic oxide template of utilization MOF according to claim 4 prepares metal hydroxides multistage
The method of structure, which is characterized in that concentration is used to carry out alkali process for the KOH solution of 0.1mol/L.
6. a kind of derivative bimetallic oxide template of utilization MOF according to claim 4 prepares metal hydroxides multistage
The method of structure, which is characterized in that the MMoO4The derivative bimetallic oxide of-MOF and OH-The ratio between the amount of substance for 1:(1~
100)。
7. a kind of derivative bimetallic oxide template of utilization MOF according to claim 6 prepares metal hydroxides multistage
The method of structure, which is characterized in that the MMoO4The derivative bimetallic oxide of-MOF and OH-The ratio between the amount of substance be 1:25.
8. a kind of described according to claim 1 or 5 or 6 or 7 prepare metal hydrogen-oxygen using the derivative bimetallic oxide template of MOF
The method of compound multilevel structure, which is characterized in that by MMoO4- the derivative bimetallic oxide of MOF stands 0.5 in KOH solution~
8h obtains metal hydroxides multilevel structure M (OH)x。
9. a kind of derivative bimetallic oxide template of utilization MOF according to claim 8 prepares metal hydroxides multistage
The method of structure, which is characterized in that MMoO4The derivative bimetallic oxide of-MOF time of repose in KOH solution is 6h.
10. a kind of described according to claim 1 or 2 or 3 or 9 prepare metallic hydrogen using the derivative bimetallic oxide template of MOF
The method of oxide multilevel structure, which is characterized in that the M is selected from Cu, Zn, Fe, Mg, Al, one of Co and Ni.
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