CN106865625A - A kind of nanometer sheet being made up of transition metal oxide nano-particles and preparation method thereof - Google Patents
A kind of nanometer sheet being made up of transition metal oxide nano-particles and preparation method thereof Download PDFInfo
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Abstract
A kind of nanometer sheet being made up of transition metal oxide nano-particles and preparation method thereof, it belongs to the technical field of transition metal oxide nano-material.The invention solves the problems that the existing method for preparing transition metal oxide nano-slice exist narrow application range, complex process, particle is larger, size is uneven and the problem that cannot synthesize on a large scale.Nanometer sheet of the present invention is using transition metal phthalocyanine as source metal, using graphene oxide as template, using hydrazine hydrate as reducing agent, using distilled water as medium, eventually through obtained in calcining；Specific method：First, add graphene oxide into distilled water, ultrasonic vibration is subsequently adding transition metal phthalocyanine, continues ultrasonic vibration；2nd, hydrazine hydrate is added, stirring is dried after centrifugation；3rd, calcining at constant temperature, naturally cools to room temperature.Product of the present invention is unique 2D folds nanometer chip architecture, and particle arrangement is uniform and size is smaller, with excellent catalytic performance and preferable stability.
Description
Technical field
The invention belongs to the technical field of transition metal oxide nano-material；Specifically related to one kind is by transiting metal oxidation
Nanometer sheet that thing nano-particle is constituted and preparation method thereof.
Background technology
Because ultra-thin two-dimension (2D) nanostructured has the huge specific surface area, flexibility of machinery, optical clear, special
Band structure and stabilization physicochemical property the features such as so that it has turned near in the field such as catalysis, sensing, photovoltaic and electrochemistry
Fall over each other the focus of research over year both at home and abroad.Today of whole world common recognition, non-noble gold are had become in Green Chemistry and sustainable development
Metal catalyst, especially transition metal oxide base catalyst, are increasingly paid attention to by academia and industrial circle, such material
Earth's crust rich reserves, it is cheap and catalytic performance is preferable, it is a kind of preferable alternative to conventional metals base catalyst.To the greatest extent
Managing research work for a long time on transition metal oxide functional material has a lot, but up to the present, and its is main to obtain
The form of obtaining still for the nano dot and thin nano-particle, one-dimensional nano wire and nanotube of zero dimension and the meso-hole structure of three-dimensional and is received
Rice cluster.By contrast, two-dimentional transition metal nano material, particularly that there is ultrathin, large area, independent support knot
The material of structure, is but extremely rare.The method for preparing two-dimentional transition metal nano material at present is mainly by will be with layer
Shape structural transition metal oxide or hydroxide body phase material are carried out obtained from mechanical stripping.It is unfortunately only few
Several transition metal oxides or hydroxide three-dimensional body phase material are to act on stacked structure with two-dimensional layer is weak, and can
To prepare two-dimentional transition metal oxide by peeling off.Additionally, stripping method efficiency is very low, the difficult control of product thickness, it is clear that nothing
Method is used for realizing preparing high-quality two-dimentional transition metal oxide nano-slice on a large scale.Therefore new preparation plan must be explored
Slightly, scope of application method wide is set up to realize the controlledly synthesis of transition metal oxide nano-slice, with meet sensing, catalysis,
The association area such as the energy storage and electronic equipment demand growing to two-dimensional metallic oxide.As people are to transition metal
What oxide material was studied deepens continuously, and the preparation method of existing some transition metal oxide nano-slices is reported out, example
Such as Ziqi Sun are assembled to cobalt ions in the solution using pluronic P123 and methenamine, after standing 24h, will be anti-
Liquid is answered to be transferred in reactor the reaction under high pressure 2h under the conditions of 170 DEG C, product is washed through washing, ethanol, take off under the conditions of 150~400 DEG C
Water process 2h, is finally obtained TiO2, ZnO and Co3O4Deng metal oxide nano-sheet (Nature Communications, 2014,
5,3812), gained nanometer chip size is small, and without obvious particle structure, but the method needs multistep reaction, is related to HTHP solvent
Heat etc. is operated, and is related to medicine and reagent many, high cost, the low yield and reaction time is long, it is difficult to mass produced；Sakae
Takenaka et al. in anhydrous conditions by graphite oxide respectively with several metal alkoxides (Ti (OC4H9)4,Zr(OC4H9)4,Nb
(OC4H9)5,Sn(OC4H9)4With Ta ((OC4H9)5) be added in hexamethylene, (graphite oxide is difficult to be dispersed within more than several days for stirring
In non-polar solven), then 180 DEG C of reaction under high pressure 6h in a kettle., after centrifugal drying, then calcine 2h under the conditions of 450 DEG C,
Metal oxide nano-sheet (J.Phys.Chem.C 2015,119,12445) is obtained.The method uses the metal alcohol of facile hydrolysis
Salt is raw material (only a few transition metal can generate relatively stable metal alkoxide), and narrow application range is needed also exist for many
Step reaction, is related to the waterless operation of complexity and the process such as HTHP solvent heat, high cost, the low yield and reaction time is long, difficult
To mass produce.
Although the preparation method of transition metal oxide nano-slice has been obtained certain journey by the strong driving of demand in recent years
The development of degree, and many significant results are achieved, but current technology of preparing still suffers from problems, such as preparation method
Limited by raw material sources, narrow application range, preparation process step is various, be related to complex operations such as HTHP solvent heat etc., produced
Rate is low and the reaction time is long, it is difficult to mass produce, additionally, obtained transition metal oxide nano-slice form, thickness are difficult
Control, some are not particle compositions, and some particles are larger and skewness.Therefore, easy, efficient and controllable transition gold is sought
The preparation method of category oxide nano-slice (nanometer sheet being especially made up of transition metal oxide nano-particles) is still current
Major issue urgently to be resolved hurrily.
The content of the invention
The invention solves the problems that the narrow application range of the existing method presence for preparing transition metal oxide nano-slice, technique are multiple
The technical problem that miscellaneous, particle is larger, size is uneven and cannot synthesize on a large scale, there is provided one kind is received by transition metal oxide
Nanometer sheet that rice corpuscles is constituted and preparation method thereof.
In order to solve the above technical problems, the nanometer sheet that transition metal oxide nano-particles of the present invention are constituted be with
Transition metal phthalocyanine as source metal, using graphene oxide as template, using hydrazine hydrate as reducing agent, using distilled water as Jie
Matter, it is obtained eventually through calcining；By weight percentage, the proportioning of raw material is as follows：0.22%~0.46% graphite oxide
Alkene, 0.90%~1.94% transition metal phthalocyanine, 8.99%~10.43% hydrazine hydrate and 87.17%~89.89% steaming
Distilled water；Wherein, each raw material dosage sum is 100%；Specific preparation method is carried out in the steps below：Step one, will oxidation
Graphene is added in distilled water, 30~50min of ultrasonic vibration, adds transition metal phthalocyanine, continues 1~4h of ultrasonic vibration；Step
Rapid two, hydrazine hydrate is subsequently adding, 1~2h is stirred under the conditions of 10~50 DEG C, dried under the conditions of 80 DEG C after centrifugation；Step
3rd, 1~3h of calcining at constant temperature under 300~600 DEG C, air or oxygen atmospheric condition again, naturally cools to room temperature, that is, obtain by mistake
Cross the nanometer sheet of metal oxide nanoparticles composition.
Transition metal in the transition metal phthalocyanine is cobalt, iron, nickel, molybdenum, manganese or copper；The water content of the hydrazine hydrate is
20%.
The frequency of ultrasound described in step one is 40kHz；Calcining at constant temperature is carried out using Muffle furnace in step 3.
The present invention using graphene oxide as template, using transition metal phthalocyanine cheap and easy to get as source metal, by
Strong between metal phthalocyanine and graphene oxide π-π effects, first by transition metal phthalocyanine is in situ in order, equably induction group
Surface of graphene oxide is attached to, the synthesis of catalyst precursor is realized, the transition metal on graphene oxide and surface in precursor
Phthalocyanine is closely linked to form complex；Calcined under oxygen or air conditionses, complex meeting very exothermic can be by oxygen
Graphite alkene and transition metal phthalocyanine are decomposed simultaneously, and formation is entirely free of the transition metal oxide nano-slice of graphene oxide.
The present invention is acted on by π-π strong between metal phthalocyanine and graphene oxide, and metal phthalocyanine is assembled into oxidation
Graphenic surface, realizes the controlledly synthesis of transition metal oxide nano-slice, and obtained nanometer sheet is by transition metal oxide
What nano-particle was constituted, with unique 2D folds nanometer chip architecture, the big I of nanometer sheet with selected graphene oxide chi
Little progress row regulates and controls, and the thickness of nanometer sheet can be controlled by the ratio of metal phthalocyanine and graphene oxide.
The inventive method controls metal oxide and receives by π-π effects strong between metal phthalocyanine and graphene oxide
The growth of rice corpuscles, obtains size smaller (a diameter of 4~10nm) and the particle being evenly distributed, and this structure is catalyzed in increase
While agent material specific surface area, it can be made to expose more active sites.
The present invention it is simple to operate, with low cost, suitable for large-scale production.Transition metal oxide prepared by the present invention is received
Rice piece is demonstrated by excellent electro-catalysis water dispersible can be had important with preferable stability in electro-catalysis water decomposition product oxygen field
Application value.
Brief description of the drawings
Fig. 1 is transmission electron microscope (TEM) figure of cobalt oxide nanometer sheet prepared by the methods described of specific embodiment one,
Enlargement ratio：8000 times；
Fig. 2 is transmission electron microscope (TEM) figure of cobalt oxide nanometer sheet prepared by the methods described of specific embodiment one,
Enlargement ratio：40000 times；
Fig. 3 is AFM (AFM) figure of cobalt oxide nanometer sheet prepared by the methods described of specific embodiment one,
(A) atomic force shape appearance figure, (B) cross-section analysis figure；
Fig. 4 is the thermal gravimetric analysis curve of cobalt oxide nanometer sheet prepared by the methods described of specific embodiment one；
Fig. 5 is the XRD spectrum of cobalt oxide nanometer sheet prepared by the methods described of specific embodiment one；
Fig. 6 is the full spectrograms of XPS of cobalt oxide nanometer sheet prepared by the methods described of specific embodiment one；
Fig. 7 is that the oxygen evolution reaction LSV curves of cobalt oxide nanometer sheet prepared by method described in specific embodiment one (sweep speed
It is 2mV s-1, solution is 1M KOH).
Fig. 8 is that the oxygen evolution reaction LSV curves of nickel oxide nano piece prepared by method described in specific embodiment one (sweep speed
It is 2mV s-1, solution is 1M KOH).
Specific embodiment
Specific embodiment one：The nanometer sheet being made up of cobaltosic oxide nanoparticles in present embodiment is with Cobalt Phthalocyanine
It is the hydrazine hydrate of 20% (quality) as reducing agent using water content, with distillation using graphene oxide as template as source metal
Water is obtained eventually through calcining as medium；By weight percentage, the proportioning of raw material is as follows：0.22% graphite oxide
Alkene, 0.90% Cobalt Phthalocyanine, 8.99% hydrazine hydrate and 89.89% distilled water；Specific preparation method is to enter in the steps below
Capable：Step one, add graphene oxide into distilled water, under the conditions of supersonic frequency is 40kHz ultrasonic vibration 30min,
Cobalt Phthalocyanine is added, continues the ultrasonic vibration 1h under the conditions of supersonic frequency is 40kHz；Step 2, hydrazine hydrate is subsequently adding, at 40 DEG C
Under the conditions of stir 1h, after centrifugation under the conditions of 80 DEG C dry；Step 3, it is placed in Muffle furnace again, in 400 DEG C, oxygen gas
Calcining at constant temperature 2h under the conditions of atmosphere, naturally cools to room temperature, that is, obtain the nanometer sheet being made up of cobaltosic oxide nanoparticles.
The preparation method of the Cobalt Phthalocyanine used by present embodiment is as follows：First, 8.53% neighbour is weighed according to percentage by weight
Benzene dicarbonitrile, 3.02% waterless cobaltous chloride, 77.59% n-amyl alcohol and 10.86% 1,8- diazabicylos [5.4.0] ten
One carbon -7- alkene；, in 250mL round-bottomed flasks, add step one phthalonitrile, waterless cobaltous chloride, the n-amyl alcohol and 1 that weigh,
Carbon -7- the alkene of 8- diazabicylos [5.4.0] 11, is then heated to reflux and magnetic agitation reaction 12h, cooling under nitrogen protection
To room temperature, after filtering, products therefrom is successively with absolute methanol, hydrochloric acid (mass concentration 3%), distillation water washing, 100 DEG C of bakings
It is dry, that is, Cobalt Phthalocyanine crude product is obtained, further with concentrated sulfuric acid dissolution reprecipitation method purified product, that is, the preparation of Cobalt Phthalocyanine is completed,
Yield is 83%.
Gained cobalt oxide nanometer sheet in present embodiment, as illustrated in fig. 1 and 2, material is in its transmission electron micrograph
Uniform 2D folds nanometer chip architecture, and its laminated structure is assembled by uniform nano-particle of arranging, particle it is average straight
Footpath is 7~8nm.
Gained cobalt oxide nanometer sheet, its atomic force microscope images in present embodiment are as shown in figure 3, material is in uniformly to receive
Rice chip architecture, and its laminated structure thickness is 7~8nm.
The thermal gravimetric analysis curve of cobalt oxide nanometer sheet prepared in present embodiment is as shown in figure 4, as can be seen from Figure 4
The pyrolysis temperature of material is 400 DEG C, illustrates to be calcined under oxygen or air conditionses, and the metal phthalocyanine of surface of graphene oxide can be acute
Strong heat release, can burn graphene oxide, realize that phthalocyanine is synchronous with graphene oxide and decompose, and formation is entirely free of oxidation stone
The cobalt oxide nanometer sheet of black alkene.
The XRD spectrum of cobalt oxide nanometer sheet prepared in present embodiment is as shown in Figure 5.From fig. 5, it can be seen that made
Standby cobalt oxide nanometer sheet be pyrolyzed through 400 DEG C after the product that obtains at 19.93 °, 31.28 °, 36.79 °, 44.84 °, 59.37 ° and
There is sharp diffraction maximum at 65.38 °, correspond respectively to (111), (220), (311), (400), (511) of cobalt oxide crystalline phase
(440) crystal face (JCPDS No.42-1467), this result indicates the successful preparation of cobalt oxide nanometer sheet.
The full spectrograms of XPS of cobalt oxide nanometer sheet prepared in present embodiment are as shown in Figure 6.From fig. 6, it can be seen that having
Obvious Co, C, O characteristic peak is present on the spectral line of cobalt oxide nanometer sheet, and these results further demonstrate cobalt oxide nanometer sheet
Successful preparation.
Cobalt oxide nanometer sheet prepared by the present embodiment method of 10.0mg is added in the middle of the absolute ethyl alcohol of 2ml,
Ultrasonic vibration 30min, is made uniform dispersion liquid, is added dropwise after the 30 μ L catalyst with micro-sampling pin and on glass-carbon electrode and dried
It is dry, test electrode is obtained.As can be seen from Figure 7 the cobalt oxide nanometer sheet prepared by present embodiment method is in 1M KOH solutions
In have good electro-catalysis analysis oxygen performance, its analysis oxygen take-off potential is 1.53V, reaches 10mAcm-2Current density need
The overpotential of 1.56V, compared with same type of material, has a clear superiority, and illustrates that the cobalt oxide in present embodiment prepared by method is received
Rice piece can be expected to be applied to electro-catalysis water decomposition product oxygen.
Using following verification experimental verification invention effects：
Tested using the method for specific embodiment one.Except the weight of metal phthalocyanine and graphene oxide is than different
Outward, other reaction conditions and parameter are identical with specific embodiment one.The flat of nanometer sheet is surveyed using AFM (AFM)
Equal thickness, the results are shown in Table 1：
Table 1：Average thickness table of the weight of different metal phthalocyanine and graphene oxide than acquisition nanometer sheet
| The weight ratio of metal phthalocyanine and graphene oxide | The average thickness of nanometer sheet |
| 2:1 | About 5nm |
| 4:1 | 7~8nm |
| 6:1 | 9~10nm |
| 8:1 | 10~13nm |
As shown in Table 1, the average thickness of nanometer sheet can be controlled by adjusting the ratio of metal phthalocyanine and graphene oxide.
Specific embodiment two：The nanometer sheet being made up of ferric oxide nanoparticles in present embodiment is with FePC
It is the hydrazine hydrate of 20% (quality) as reducing agent using water content, with distillation using graphene oxide as template as source metal
Water is obtained eventually through calcining as medium；By weight percentage, the proportioning of raw material is as follows：0.46% graphite oxide
Alkene, 1.94% FePC, 10.43% hydrazine hydrate and 87.17% distilled water；Specific preparation method is to enter in the steps below
Capable：Step one, add graphene oxide into distilled water, under the conditions of supersonic frequency is 40kHz ultrasonic vibration 50min,
FePC is added, continues the ultrasonic vibration 4h under the conditions of supersonic frequency is 40kHz；Step 2, hydrazine hydrate is subsequently adding, at 20 DEG C
Under the conditions of stir 2h, after centrifugation under the conditions of 80 DEG C dry；Step 3, it is placed in Muffle furnace again, in 500 DEG C, oxygen gas
Calcining at constant temperature 2h under the conditions of atmosphere, naturally cools to room temperature, that is, obtain the nanometer sheet being made up of ferric oxide nanoparticles.
The preparation method of the FePC used by present embodiment is as follows：First, 8.43% neighbour is weighed according to percentage by weight
Benzene dicarbonitrile, 3.15% anhydrous frerrous chloride, 76.56% n-amyl alcohol and 11.86% 1,8- diazabicylos [5.4.0]
11 carbon -7- alkene；2nd, in 250mL round-bottomed flasks, phthalonitrile, anhydrous frerrous chloride, positive penta for adding step one to weigh
Alcohol and the carbon -7- alkene of 1,8- diazabicylo [5.4.0] 11, are then heated to reflux and magnetic agitation reaction under nitrogen protection
12h, is cooled to room temperature, and after filtering, products therefrom uses absolute methanol, hydrochloric acid (mass concentration 3%), distillation water washing successively,
100 DEG C of drying, that is, obtain FePC crude product, further with concentrated sulfuric acid dissolution reprecipitation method purified product, that is, completes FePC
Preparation, yield is 70%.
In uniform 2D folds nanometer chip architecture, thickness is 6 to di-iron trioxide nanometer sheet material prepared by present embodiment
~7nm, and its laminated structure is assembled by uniform nano-particle of arranging, the average diameter of particle is 5~6nm.
Di-iron trioxide nanometer sheet prepared by present embodiment can be used for electro-catalysis water decomposition and produce oxygen.
Specific embodiment three：The nanometer sheet being made up of NiO nanoparticle in present embodiment be using Nickel Phthalocyanine as
Source metal, is the hydrazine hydrate of 20% (quality) as reducing agent using water content using graphene oxide as template, with distilled water work
It is medium, it is obtained eventually through calcining；By weight percentage, the proportioning of raw material is as follows：0.36% graphene oxide,
1.64% Nickel Phthalocyanine, 9.43% hydrazine hydrate and 88.57% distilled water；Specific preparation method is to carry out in the steps below
's：Step one, by distilled water add graphene oxide in, supersonic frequency be 40kHz under the conditions of ultrasonic vibration 40min, add
Nickel Phthalocyanine, continues the ultrasonic vibration 2h under the conditions of supersonic frequency is 40kHz；Step 2, hydrazine hydrate is subsequently adding, in 30 DEG C of conditions
Lower stirring 1.5h, dries after centrifugation under the conditions of 80 DEG C；Step 3, it is placed in Muffle furnace again, in 500 DEG C, oxygen atmosphere
Under the conditions of calcining at constant temperature 2h, naturally cool to room temperature, that is, obtain the nanometer sheet being made up of NiO nanoparticle.
The preparation method of the Nickel Phthalocyanine used by present embodiment is as follows：
First, 8.53% phthalonitrile, 3.05% Dehydrated nickel chloride, 77.56% is weighed according to percentage by weight
N-amyl alcohol and the 10.86% carbon -7- alkene of 1,8- diazabicylos [5.4.0] 11；
2nd, in 250mL round-bottomed flasks, phthalonitrile, Dehydrated nickel chloride, the n-amyl alcohol and 1 for adding step one to weigh,
Carbon -7- the alkene of 8- diazabicylos [5.4.0] 11, is then heated to reflux and magnetic agitation reaction 12h, cooling under nitrogen protection
To room temperature, after filtering, products therefrom is successively with absolute methanol, hydrochloric acid (mass concentration 3%), distillation water washing, 100 DEG C of bakings
It is dry, that is, Nickel Phthalocyanine crude product is obtained, further with concentrated sulfuric acid dissolution reprecipitation method purified product, that is, the preparation of Nickel Phthalocyanine is completed,
Yield is 79%.
Nickel oxide nano sheet material prepared by present embodiment in uniform 2D folds nanometer chip architecture, thickness is 8~
9nm, and its laminated structure is assembled by uniform nano-particle of arranging, the average diameter of particle is 6~7nm.
Nickel oxide nano piece prepared by the present embodiment method of 10.0mg is added in the middle of the absolute ethyl alcohol of 2ml,
Ultrasonic vibration 30min, is made uniform dispersion liquid, is added dropwise after the 30 μ L catalyst with micro-sampling pin and on glass-carbon electrode and dried
It is dry, test electrode is obtained.As can be seen from Figure 8 the nickel oxide nano piece prepared by present embodiment method is in 1M KOH solutions
In have good electro-catalysis analysis oxygen performance, its analysis oxygen take-off potential is 1.55V, reaches 10mAcm-2Current density need
The overpotential of 1.67V, compared with same type of material, has a clear superiority, and illustrates that the cobalt oxide in present embodiment prepared by method is received
Rice piece can be applied to electro-catalysis water decomposition and produce oxygen.
Nickel oxide nano piece prepared by present embodiment can be used for electro-catalysis water decomposition and produce oxygen.
Specific embodiment four：The nanometer sheet being made up of manganese dioxide nano particle in present embodiment is made with manganese phthalocyanine
It is source metal, using graphene oxide as template, using water content as the hydrazine hydrate of 20% (quality) as reducing agent, with distilled water
It is obtained eventually through calcining as medium；By weight percentage, the proportioning of raw material is as follows：0.41% graphene oxide,
1.84% manganese phthalocyanine, 9.79% hydrazine hydrate and 87.96% distilled water；Specific preparation method is to carry out in the steps below
's：Step one, by distilled water add graphene oxide in, supersonic frequency be 40kHz under the conditions of ultrasonic vibration 40min, add
Manganese phthalocyanine, continues the ultrasonic vibration 3h under the conditions of supersonic frequency is 40kHz；Step 2, hydrazine hydrate is subsequently adding, in 20 DEG C of conditions
Lower stirring 2h, dries after centrifugation under the conditions of 80 DEG C；Step 3, it is placed in Muffle furnace again, in 500 DEG C, oxygen atmosphere bar
Calcining at constant temperature 2h under part, naturally cools to room temperature, that is, obtain the nanometer sheet being made up of manganese dioxide nano particle.
The preparation method for stating manganese phthalocyanine used by present embodiment is as follows：
First, 8.47% phthalonitrile, 3.74% anhydrous Manganese chloride, 77.01% is weighed according to percentage by weight
N-amyl alcohol and the 10.78% carbon -7- alkene of 1,8- diazabicylos [5.4.0] 11；
2nd, in 250mL round-bottomed flasks, phthalonitrile, anhydrous Manganese chloride, the n-amyl alcohol and 1 for adding step one to weigh,
Carbon -7- the alkene of 8- diazabicylos [5.4.0] 11, is then heated to reflux and magnetic agitation reaction 12h, cooling under nitrogen protection
To room temperature, after filtering, products therefrom is successively with absolute methanol, hydrochloric acid (mass concentration 3%), distillation water washing, 100 DEG C of bakings
It is dry, that is, manganese phthalocyanine crude product is obtained, further with concentrated sulfuric acid dissolution reprecipitation method purified product, that is, the preparation of manganese phthalocyanine is completed,
Yield is 44%.
Manganese dioxide nano-plates material prepared by present embodiment in uniform 2D folds nanometer chip architecture, thickness is 8~
9nm, and its laminated structure is assembled by uniform nano-particle of arranging, the average diameter of particle is 5~6nm.
Manganese dioxide nano-plates prepared by present embodiment can be used for electro-catalysis water decomposition and produce oxygen.
Specific embodiment five：The nanometer sheet being made up of copper oxide nano particle in present embodiment be using CuPc as
Source metal, is the hydrazine hydrate of 20% (quality) as reducing agent using water content using graphene oxide as template, with distilled water work
It is medium, it is obtained eventually through calcining；By weight percentage, the proportioning of raw material is as follows：0.35% graphene oxide,
1.64% CuPc, 10.13% hydrazine hydrate and 87.88% distilled water；Specific preparation method is to carry out in the steps below
's：Step one, by distilled water add graphene oxide in, supersonic frequency be 40kHz under the conditions of ultrasonic vibration 50min, add
Manganese phthalocyanine, continues the ultrasonic vibration 3h under the conditions of supersonic frequency is 40kHz；Step 2, hydrazine hydrate is subsequently adding, in 30 DEG C of conditions
Lower stirring 2h, dries after centrifugation under the conditions of 80 DEG C；Step 3, it is placed in Muffle furnace again, in 400 DEG C, oxygen atmosphere bar
Calcining at constant temperature 3h under part, naturally cools to room temperature, that is, obtain the nanometer sheet being made up of copper oxide nano particle.
The preparation method of the CuPc used by present embodiment is as follows：
First, 8.52% phthalonitrile, 3.11% anhydrous cupric chloride, 77.52% is weighed according to percentage by weight
N-amyl alcohol and the 10.85% carbon -7- alkene of 1,8- diazabicylos [5.4.0] 11；
2nd, in 250mL round-bottomed flasks, phthalonitrile, anhydrous cupric chloride, the n-amyl alcohol and 1 for adding step one to weigh,
Carbon -7- the alkene of 8- diazabicylos [5.4.0] 11, is then heated to reflux and magnetic agitation reaction 12h, cooling under nitrogen protection
To room temperature, after filtering, products therefrom is successively with absolute methanol, hydrochloric acid (mass concentration 3%), distillation water washing, 100 DEG C of bakings
It is dry, that is, CuPc crude product is obtained, further with concentrated sulfuric acid dissolution reprecipitation method purified product, that is, the preparation of CuPc is completed,
Yield is 62%.
Cupric oxide nano sheet material prepared by present embodiment in uniform 2D folds nanometer chip architecture, thickness is 7~
8nm, and its laminated structure is assembled by uniform nano-particle of arranging, the average diameter of particle is 5~6nm.
Cupric oxide nano piece prepared by present embodiment can be used for electro-catalysis water decomposition and produce oxygen.
Claims (10)
1. a kind of nanometer sheet being made up of transition metal oxide nano-particles, it is characterised in that the nanometer sheet is with transition gold
Category phthalocyanine as source metal, using graphene oxide as template, using hydrazine hydrate as reducing agent, using distilled water as medium, most
It is obtained by calcining eventually.
2. a kind of nanometer sheet being made up of transition metal oxide nano-particles according to claim 1, it is characterised in that with
Percentage by weight meter, the proportioning of raw material is as follows：0.22%~0.46% graphene oxide, 0.90%~1.94% transition gold
Category phthalocyanine, 8.99%~10.43% hydrazine hydrate and 87.17%~89.89% distilled water.
3. a kind of nanometer sheet being made up of transition metal oxide nano-particles according to claim 2, it is characterised in that institute
It is cobalt, iron, nickel, molybdenum, manganese or copper to state the transition metal in transition metal phthalocyanine.
4. a kind of nanometer sheet being made up of transition metal oxide nano-particles according to claim 2, it is characterised in that institute
The water content for stating hydrazine hydrate is 20%.
5. the preparation of a kind of nanometer sheet being made up of transition metal oxide nano-particles as described in claim 1,2,3 or 4
Method, it is characterised in that the preparation method of the nanometer sheet is carried out in the steps below：
Step one, add graphene oxide into distilled water, 30~50min of ultrasonic vibration adds transition metal phthalocyanine, continue
1~4h of ultrasonic vibration；
Step 2, be subsequently adding hydrazine hydrate, stir 1~2h under the conditions of 10~50 DEG C, products therefrom be centrifuged after 80
Dried under the conditions of DEG C；
Step 3, again 1~3h of calcining at constant temperature under 300~600 DEG C, air or oxygen atmospheric condition, naturally cool to room temperature, i.e.,
Obtain the nanometer sheet being made up of transition metal oxide nano-particles.
6. the preparation method of a kind of nanometer sheet being made up of transition metal oxide nano-particles according to claim 5,
It is characterized in that ultrasonic vibration is carried out in step one under the supersonic frequency of 40kHz.
7. the preparation method of a kind of nanometer sheet being made up of transition metal oxide nano-particles according to claim 5,
It is characterized in that being stirred under conditions of being 20 DEG C, 30 DEG C or 40 DEG C in temperature in step 2.
8. the preparation method of a kind of nanometer sheet being made up of transition metal oxide nano-particles according to claim 5,
It is characterized in that the temperature of calcining at constant temperature is 400 DEG C or 500 DEG C in step 3.
9. the preparation method of a kind of nanometer sheet being made up of transition metal oxide nano-particles according to claim 5,
It is characterized in that in step 3 calcining at constant temperature time be 2h.
10. the preparation method of a kind of nanometer sheet being made up of transition metal oxide nano-particles according to claim 5,
It is characterized in that carrying out calcining at constant temperature using Muffle furnace in step 3.
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| CN111068726A (en) * | 2019-11-26 | 2020-04-28 | 浙江大学 | Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material |
| CN112002908A (en) * | 2020-08-19 | 2020-11-27 | 嵊州市芝草科技有限公司 | Manganese dioxide modified nickel cobalt phthalocyanine oxygen reduction composite catalyst and preparation method thereof |
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