It is a kind of to prepare metal hydroxides multistage using the derivative bimetallic oxide template of MOFThe method of structureTechnical field
The present invention relates to technical field of nano material more particularly to a kind of derivative bimetallic oxide template systems of utilization MOFThe 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 groupStructure provides ideal mechanical performance and chemical property.Multilevel structure is to be formed from molecule to macro-scale by stringent organizational principleStructure, 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 structureControlled morphologies, orientation and dimension, become one of the hot spot of material science research.Due to its have it is some special physicoLearn property, it will have extensive potential application in terms of electromagnetism, electronics, catalysis, water process and the energy.Therefore, hadThere is the Nano material of hydrate of multilevel structure of specific dimensions, pattern, dimension, polymolecularity to be of great significance.However, meshThe Nano material of hydrate synthetic method of preceding multilevel structure mostly uses surfactant, toxic organic solvent, prepares workSkill 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, noThe problem of conducive to industrialization, provides and a kind of prepares metal hydroxides multistage knot using the derivative bimetallic oxide template of MOFThe method of structure, preparation process is simple, mild, pervasive and can largely prepare, and does not use surfactant, is suitable for extensive industryMetaplasia 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 doubleMetal oxide template obtains metal hydroxides multilevel structure by alkali process；It is multistage as the metal hydroxides to set MMetal in structure, the derivative bimetallic oxide template of the MOF is MMoO4- MOF derives bimetallic oxide, the metalHydroxide multilevel structure is M (OH)2。
Metal-organic framework materials (Metal-organic frameworks, MOF) are metal ion and organic ligand knotWith the crystal of porous network structure made of conjunction, the cellular structure with high-sequential, bigger specific surface area is more connectTouch active site.The present invention is with the derivative bimetallic oxide MMoO of MOF4- MOF is template, wherein M is metal target hydroxideMetal in object multilevel structure, after alkali process, obtained MoO42-Lye is dissolved in, in target metal ions M and lyeOH-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 inventionEasy 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 80It~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 doubleMetal 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 calciningCompound size uniformity, stable structure.The water-soluble salt solution of M such as Co (NO3)2·6H2O and Ni (NO3)2·6H2O and other sulphurHydrochlorate etc..
Preferably, the temperature of high-temperature calcination is 300~900 DEG C in step (2)；Calcination time be 1~for 24 hours；Heating speedRate 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 metalHydroxide 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 industryMetaplasia produces；
(2) using the metal hydroxides multilevel structure size uniformity of this method preparation, stable structure, composite distribution is uniform, exhibitionReveal 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 followingMethod 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 0.475g2-methylimidazole pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs 0.3gCo(NO3)2·6H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in cobalt nitrate solution3In solution.Oil bath heating is to 120DEG 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 CThe 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 furnaceLower 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 addedLiquid, 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 fromIn 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)2Multilevel structure.
To Co/Mo-MOF crystal powder, CoMoO made from embodiment 14- MOF crystal powder and Co (OH)2Multilevel structure intoThe 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 ofState gained Co/Mo-MOF crystal powder, CoMoO4Crystal powder, Co (OH)2Multilevel structure powder is placed in the support for posting conducting resinlPlatform 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 realityApply the preparation gained Co/Mo-MOF of example 1 crystal powder, CoMoO4- MOF crystal powder, Co (OH)2Multilevel structure powder is micro, respectivelyAbout 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 dispersedFilm (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 structureThe 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 smoothClub 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 hasCrystallinity, stable structure, component are uniform.Fig. 1 (d, e) illustrates CoMoO4The whole pattern of-MOF material is the smooth stick in surfaceShape structure.Cross-sectional diameter about 1um is about 5um, and can largely prepare.Fig. 1 (f) shows CoMoO4- MOF has goodCrystallinity, stable structure, component are uniform.Fig. 1 (g, h) illustrates Co (OH)2The whole pattern of multilevel structure material is Co (OH)2Nanometer 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 bigAmount 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 1MOF crystal powder, CoMoO4- MOF crystal powder, Co (OH)2It is recessed to be laid on rectangular frosted on quartz plate respectively for multilevel structure powderIn 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. 2Property, 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 oxydationCoMoO4The XRD spectrum of-MOF crystal powder, diffraction maximum and CoMoO in figure4Standard card (PDF#21-0868) is consistent, it was demonstrated that atFunction 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 figurePenetrate 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 IrO2Overpotential be 1.625V, and Co obtained in embodiment 1 (OH)2The overpotential of multilevel structure is 1.521V, than commercial IrO2Low 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 upperIt 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 0.475g2-methylimidazole pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs 0.3gNi(NO3)2·6H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in nickel nitrate solution3In solution.Oil bath heating is to 80DEG 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 CThe 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 furnaceLower 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 isThe 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 knotProduct 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 doDry 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 intoThe 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 ofState gained Ni/Mo-MOF crystal powder, NiMoO4Crystal powder, Ni (OH)2Multilevel structure powder is placed in the support for posting conducting resinlPlatform 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 realityApply the preparation gained Ni/Mo-MOF of example 2 crystal powder, NiMoO4Crystal powder, Ni (OH)2Multilevel structure powder is micro, is added dropwise respectivelyAbout 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 dispersedFilm (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 powderSEM 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 surfaceStructure.Cross-sectional diameter about 1um, is about 5um.Fig. 7 (b1, b2) shows that Ni/Mo-MOF has good crystallinity, and structure is steadyFixed, component is uniform.Fig. 7 (c, d) illustrates NiMoO4The whole pattern of-MOF material is the smooth club shaped structure in surface.Cross sectionDiameter 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 formedStructure.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 2MOF 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)2The wide-angle XRD spectra of multilevel structure powder shows that gained Ni/Mo-MOF crystalline material has good crystallinity in Fig. 8, with figure7 (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 synthesizesNiMoO4Material.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- firstBase 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 180DEG 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 CThe 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 furnaceEnclose 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 addedSolution, CoMoO4- MOF and OH-The ratio between the amount of substance be 1:100, stand 6h at room temperature, after reaction, product be transferred toIn 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 0.475g2-methylimidazole pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs0.304g Cu(NO3)2·6H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in copper nitrate solution3In solution.Oil bath addsHeat 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 60It 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 furnaceLower 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 isThe 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 knotProduct 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 doDry 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 0.475g2-methylimidazole pours into deionized water, ultrasonic dissolution.A clean beaker is separately taken, is added in 25ml deionized water, weighs0.264g Mg(NO3)2·9H2O is poured into deionized water, ultrasonic dissolution, and MoO is added in magnesium nitrate solution3In solution.Oil bath addsHeat 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 60It 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 furnaceLower 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 addedSolution, MgMoO4- MOF and OH-The ratio between the amount of substance be 1:30, stand 4h at room temperature, after reaction, product be transferred toIn 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 surpassingThere are also other variations and modifications under the premise of technical solution documented by claim out.