CN108698849A - Pass through the production of the graphene-based composite nanostructure of non-loading type graphene nano on piece growing zinc oxide nanorod or the micron bar acquisition in suspension - Google Patents
Pass through the production of the graphene-based composite nanostructure of non-loading type graphene nano on piece growing zinc oxide nanorod or the micron bar acquisition in suspension Download PDFInfo
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- CN108698849A CN108698849A CN201680082279.XA CN201680082279A CN108698849A CN 108698849 A CN108698849 A CN 108698849A CN 201680082279 A CN201680082279 A CN 201680082279A CN 108698849 A CN108698849 A CN 108698849A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Abstract
A kind of innovative approach can control the form of ZnO nano-structure and the coating density of graphene platelet, electrical property modified with production zinc oxide micron rods or nanometer rods (may be doped with metal), with enhancing, Electronic Performance and mechanical performance graphene nanometer sheet.This method carries out in aqueous or water alcohol suspension, and causes to produce such nano material:It can be used as the filler in polymer substrate, to obtain the nanocomposite with specific electrical property, electromagnetic performance and electromechanical properties.The appropriate of process conditions limits and the use of the deposition of the seed layer on the surfaces GNP and suspension continuously mix in the appropriate case growing technology enables control over the form of nanostructure, and allows to obtain the height on the surfaces GNP and uniformly coat density.
Description
The present invention relates to field of nanometer technology, the nanometer rods or micron bar for production zinc oxide are more particularly related to
The innovative approach of the graphene nanometer sheet of (may be doped with metal) modification, the graphene nanometer sheet have improved electrical
Energy, Electronic Performance and mechanical performance.Graphene nanometer sheet (GNP) has been evenly coated with (in the both sides of piece) over its entire surface
The nanometer rods (NR) or micron bar (MR) (may be doped with metal) of zinc oxide (ZnO).ZnO can be controlled in growth course to receive
The rice morphological character of structure and the coating density on the surfaces GNP.
This method carries out in aqueous or water alcohol suspension, and leads to the production of such nano material:The nano material
It can be used as the filler in polymer substrate, to obtain the nano combined material with specific electrical property, electromagnetic performance and electromechanical properties
Material.
The method used in the present invention is simple, economically favorably, can amplify for mass producing, need not use urge
Agent, and final product is free from foreign meter.
Technical field
The present invention is to be intended to provide the novel nano structure stone with controlled electrical property, electromagnetic performance and electromechanical properties
It is developed in the research framework of mertenyl material.
There is great application value in multiple fields with the GNP of ZnO nano/micron bar modification, be either used as compound
Machinery enhancing in material, or possibly also with its piezoelectricity or electroactive performance, there is required electrical property and/or electricity for producing
The composite material of magnetic property, such as radar absorbing material, and catalysis or collection of energy application.
Invention content
According to the present invention, ZnO-GNP hybridized nanometers/micrometer structure is produced in the presence of seed layer, the seed layer has
Conducive to ZnO structures nucleation and obtain the uniform highdensity coating of GNP.Exist by various technologies as described below
While stirring the lower density and uniformity for keeping the suspension of GNP to control coating, the deposition of seed layer is carried out.
The fundamental novel features of the present invention are the simplicity of proposed method and cheapness, by described in deposition
Operating condition is suitably limited during the step of seed layer and growth ZnO micrometer/nanometer structures, enabling production has controlled
The GNP of the ZnO modifications of morphological feature.
Some are not studies have shown that previously in the case of deposited seed layer on GNP, from aqueous solution present in document
In on GNP growing ZnO nanorod be feasible.However, as can be seen that in this way to being produced from these researchs
The quality and form of ZnO micrometer/nanometer structures do not control satisfactorily, and it was found that the coating density contrast on the surfaces GNP, companion
With the limited uniformity of micrometer/nanometer structure distribution thereon.
In other researchs, show how the presence of seed layer allows to obtain GO (graphene oxide) or rGO (reduction
Graphene oxide) or support type graphene thin slice high coating density.
According to document, the hydrothermal growth of ZnO nano-structure is usually carried out in a static condition.
On the contrary, according to the present invention, the life for the ZnO micrometer/nanometers stick (may be doped with metal) with required form
It is long, it is proposed that three kinds of different growing technologies are (that is, static hydrothermal-HT- growths, dynamic HT grow and pass through probe sonication PS's
Growth) so as to control the morphological feature (i.e. diameter and length) of produced structure.
It is being economically advantageous according to the production technology developed of the present invention and be suitable for mass producing.
Background technology
Composite material based on graphene and zinc oxide (ZnO) nanostructure is since it is with improved electrical property and machine
The novel and multifunctional material of tool performance and become for the potential application in the production of electronics and the new device of optical field
The Zhu Ti [ of many researchs;1,2].In document it has been shown that when for example zinc oxide is combined inorganic material with graphene, their electricity
Sub-feature get Dao Xianzhugaishan [3].ZnO nano-structure is usually expressed as n-type semiconductor, and therefore having can be on graphene
Carry out electron adulterated ability.Therefore, pass through the grapheme modified novel stone that can be produced with supplementary features of ZnO nano-structure
Black alkene nano material, the supplementary features are, for example, higher conductivity, improve when as filler in polymer substrate
With the relevant energy absorption capability of electromagnetic field, higher electron emission and Jian Cenengli [4,5,6]With better electrochemical properties
[7,8].Previous [ previous;9]In, produced by graphene nanometer sheet by using suspend mixing and vacuum filter
(GNP) and ZnO nano-wire composition composite material.Thus what is produced composite porous has shown that beneficial electrical property.It is special
It is not to have highlighted that, the optimum weight concentration there are ZnO nano-wire relative to GNP, this corresponds to the conductance of composite material
The maximum of rate improves, it was confirmed that ZnO nano-structure can induce the hypothesis of the electron adulterated effect on graphene.
Therefore, the present invention is within the scope of the research framework, and proposes a kind of innovative technology for producing graphene, institute
The nano/micron structure of the graphene ZnO or ZnO doped with metal is stated (in appropriate circumstances for controlled form
The nanometer rods or micron bar of characteristic) modification.Graphene nanometer sheet according to the present invention constitutes the growth of ZnO nano/micrometer structure
Matrix, therefore the effect of the interaction between Nano ZnO and graphene can be maximized.The growth of ZnO nano-structure
Occur in aqueous solution, wherein graphene nanometer sheet is dispersed in suspension.The appropriate restriction of process conditions, especially GNP tables
The use of the deposition of seed layer and growing technology on face includes the continuous mixing of suspension, enabling control nanostructure
The height on form and the surfaces GNP to be obtained and uniformly coat density.
Various researchs in scientific literature and patent document all have been directed to usually be received by graphene oxide (GO) and ZnO
The Sheng Chan [ for the mixing composite material that rice/micrometer structure is constituted;10,12].However, most of use in these researchs aoxidizes stone
Black alkene is as Qi Shicailiao [7,10], graphene oxide is not it is known that be good electric conductor.Therefore, in these researchs,
Always it is related to dedicated for restoring the processing step of obtained GO-ZnO mixing materials, especially in such an application:Its
Purpose (as described above) is the electricity using the final material generated by the repercussion effect between ZnO nano-structure and graphene
The effect of performance/Electronic Performance enhancing, such as in capacitor, photodetector and sensor.
Specifically, Junwei Ding Deng Rens [10]Pass through the water on the graphene oxide of reduction in aqueous solution
Thermal synthesis and it grown the mixed oxidization zinc structure being made of nano particle and micrometer spindle without using seed layer.By changing
Into Hummer methods obtain GO, then pass through glucose and ammonia and restore GO.However, ZnO micrometer spindles show to be less than root
Density is coated according to the rGO thin slices for coating density obtained by this patent.
In another study, Chien-Te Hsieh Deng Rens [11]It reports and ZnO nano crystalline substance is grown by microwave heating
Body.Under shearing force mixing, the GO obtained by improved Hummer methods coats the ZnO nano crystal produced.
In this case also without using seed layer.
And all it is from GO anyway using non-oxidized graphite alkene as a few studies of the growth substrate of ZnO nano-structure
The step of starting and implementing GO being reduced to rGO before nanostructure growth, this, which is usually directed to, uses toxic and dangerous examination
Agent.
Under any circumstance, in the studies above, the poor quality of the nanostructure of growth.The representative configuration noticed is
Nano particle or nanometer rods form with low-down aspect ratio, with quite non-uniform characteristic and graphene surface
Rather low coating density.In addition, there is no growths doped with the possibility of the ZnO nano-structure of metal.
Other are research shows that growth of the ZnO nano-structure on support type graphene film, the passing through of graphene film
Learn vapor deposition (CVD) Ji Shu [11]Growth obtains [ by the mechanical stripping of graphite;12].Ren-JelChung Deng Rens [11]
ZnO nanorod is synthesized on support type graphene using hydrothermal technique, the graphene is by CVD and uses 100nm seeds
Layer growth, the seed layer are obtained by the evaporation activated by electron beam.Other than of high cost, used method is not easy to put
Greatly.Yong-Jin Kim Deng Rens [12]ZnO micron bars are reported in the multilayer for being by mechanically pulling off and being obtained without using seed layer
Growth on graphene.The structure of growth has 230 to 800nm diameter.The method that uses is laborious, expensive and be not easy to amplify.
However, it should be noted that there is no a kind of unsupported graphene being suitable for mass producing ZnO modifications thin in above-mentioned technology
Piece, for production new material and multifunction device.
The patent document of hereinafter brief analysis is not provided to the program of innovation yet so that for example can be unsupported
Realize that the high-density growth of ZnO nano/micrometer structure, the growth will be uniform in the whole surface of GNP and will on GNP
With economic feasibility and it is suitble to large-scale production.
Patent KR20140037518 (A) " ZnO nano-structure for including graphene " is related to by CVD growth and by base
ZnO nano-structure layer is deposited on the graphene film of matter load, for the application in the device for light detection.The patent
KR20140037518 is related to using carrier next life long graphene, has high cost, is not easy to amplify, and can make ZnO nano knot
Structure is only grown on graphene planes face.
Patent CN102157315 (A) " emitting cathode based on graphene/zinc oxide nanowire composite material and its preparation "
It is related to the production of the electron field emission cathode for FED (Field Emission Display), by being coated with graphene and being covered with ZnO nano
The conductive electrode of linear array is constituted.Using various technologies such as spraying or electrophoresis from the aqueous suspension use being ultrasonically treated in advance
Graphene layer coating conductive electrode (being usually made of the glass for being coated with metal layer by PVD).Then, ZnO nano-wire can be with
It is grown by hydrothermal technique or CVD or PVD, preferably CVD.As the previous case, patent CN102157315 is directed to
Using growth substrate and use expensive device.In addition, nanostructure is only grown on graphene planes face.
Patent US20130099196A1 " using solution growth formed semiconductor-graphene hybrid " be related to by
By (without using seed layer) the aqueous solution growth next life for carrying out ZnO on CVD growth and the graphene that is loaded on PMMA layers
The composite material by graphene and ZnO nano-micron bar construction is produced, to obtain UV detectors.One novel aspects of the patent
It is seed layer to be not present, and can be grown in the case where there:Graphene matrix placed face down is in reaction beaker
On Free Surface, or it is placed on the bottom of beaker up, and is loaded in this case through Si or glass substrate.
However, the United States Patent (USP) cannot all grow ZnO micrometer/nanometer structures on two faces of graphene film, and it is related to
Use matrix and expensive device.
Patent CN103734188 (A) " preparation method and application of zinc oxide-graphene oxide composite nanomaterial " is related to
From suspension production graphene oxide-zinc oxide composites and its as the purposes of antiseptic of the GO in alcohol, especially
It is as the preservative for Biomedical Instruments and equipment.The patent is related to the life of the composite material of GO and ZnO nano particle
Production, production needs to obtain GO first, using the improved form of well known Hummer methods, and therefore uses hazardous agents.
Patent CN104007236 (A) " preparation method and application of graphene/zinc oxide nanometer composite material " is related to using
The production for the hybridized nano composite material based on graphene/ZnO that ultrasonic wave obtains in aqueous suspension.The patent is related to nitre
Then the ultrasonic dissolution of sour zinc in aqueous solution is added GO and carries out in-situ reducing again by ultrasonic wave by using hydrazine.Specially
Sharp CN104007236 is directed to both production stages for GO and uses aggressivity reagent also for its subsequent reduction.In addition, each
Kind production stage includes a large amount of flows, this makes it implement long and technology and require height.
Patent CN103435033 (A) " prepares the simplicity side of graphene-zinc-oxide nano rod composite material in ultrasonic wave
Method " is related to producing from fine grinding metal Zn powder ultrasonic processing in the presence of the expanded graphite in being suspended in ethanol water miscellaneous
Graphite alkene-ZnO nanorod composite material.
The production of hydridization graphene-ZnO nanorod composite material is obtained by lasting 6-10 hours of long ultrasonic procedure.
Patent CN102580716 (A) " for the method by solvent structure zinc oxide/graphene complex " report
By the production method of the GO of the ZnO modifications with the photocatalysis performance hybrid composite materials constituted.This method, which is included in, to be less than
At a temperature of 200 DEG C carry out solvent-thermal process (and partial reduction GO simultaneously), this on the mixture of GO and zinc acetylacetonate
It is carried out in solvent (being usually ethylene glycol or ethyl alcohol) appropriate.Patent CN102580716 is related to using using strong acid and oxidant
In the improved form production GO by known Hummer methods.
Patent CN101857222 (A) " preparation method of large area continuous graphite alkene/zinc oxide composite construction " is related to by stone
The preparation of setting out of the aqueous suspension of black alkene or GO or suspension in organic solvent is answered by what G/GO and ZnO nano-structure were formed
Condensation material.After G/GO is suspended in solvent by supersound process, according to the structure to be obtained from different reagent (nitre
Sour zinc and HMTA or zinc acetate) by hydrothermal growth come to produce ZnO nano-structure (include various geometries, including nano dot
With nano wire/nanometer rods).Then it is restored with hydrazine.The production that the patent is directed to both be used for GO using aggressivity reagent walks
Suddenly it is also used for its subsequent reduction.Different production stages further includes a large amount of process, this makes its implementation become tediously long and have
Problem.
Patent CN10342614 (A) " preparation method of graphene-ZnO nanoparticle composite material " is related to from simple Zn
Salt (nitrate, acetate, sulfate, chloride etc.), which sets out, prepares GO-ZnO nano particle composite materials.By water-soluble in GO
Salt is simply mixed in liquid and is then heat-treated between 150 DEG C and 1000 DEG C to obtain product (grain size 10nm).Specially
Sharp CN103482614 uses GO as the precursor for preparing GO-ZnO nano particle composite materials.In addition, used method includes
Using high temperature and even up to 10 hours long reaction time.
Hence it is evident that feeling to need a kind of receiving for growth ZnO on the non-loading type GNP in being scattered in aqueous suspension
The method of rice/micrometer structure (may be doped with metal), this method will coat the whole surface of GNP simultaneously (on both sides of the sheet)
It is mass produced realizing, wherein the coating density of the morphological character of ZnO nano-structure and the surfaces GNP can be grown entirely
It is controlled in journey.
Invention content
The experiment that the applicant carries out has revealed that grows ZnO on the both sides non-loading type GNP and in aqueous suspension
Micrometer/nanometer structure (may be doped with metal) possibility, there is coating evenly and with high density, without by means of
It is related to any reduction step using hazardous agents.In addition, further highlighting for the process conditions of growth and in non-loading type GNP
Existing correlation between the ZNO nanometer rods of upper growth and the form of micron bar, density and uniformity.
Therefore a kind of innovative approach being suitable for large-scale production has been developed, wherein producing ZnO- in the presence of seed layer
GNP hybridized nanometers/micrometer structure, the seed layer be conducive to ZnO structures nucleation and cause GNP on two sides it is uniform and high
The coating of density.In addition, making GNP keep suspending under stiring by using various technologies As described in detail below to be planted
The deposition of sublayer, to control the density and uniformity of the coating of graphene platelet, so as to control the final properties of material.This
Another character of innovation of invention is related to the metal-doped possibility of the ZnO micrometer/nanometers structure that will be grown on GNP.It should
Feature does not describe in the literature.The method developed includes the following steps:
Step 1:Produce the aqueous suspension of graphene nanometer sheet (GNP);
Step 2:Deposited seed layer on non-loading type GNP in aqueous suspension;
Step 3:Growing ZnO nanorod/micron bar on non-loading type GNP in aqueous suspension.
The novel aspects of the characterization present invention are related to the step 2 and 3 of the growth course of ZnO nano/micrometer structure, following institute
It states.
In step 2, during the embryo deposit on the GNP in seed layer (SL) in suspension, the nanometer of SL is constituted
The uniformity and size of grain control in the following manner:
(magnetic or mechanical type) hybrid technology or Probe Ultrasonic Searching is used to handle;With
The temperature for the step of then heating in an oven.
In step 3, it for the growth of the micrometer/nanometer stick of the ZnO with required form (may be doped with metal), carries
Three kinds of different growing technologies (static HT growths, dynamic HT grow and grown by PS) are gone out, so as to produced by controlling
Structure morphological feature (i.e. diameter and length).In particular, proposing following technology:
I) it is used to grow the hydrothermal growth of ZnO micron bars in a static condition (usually within the scope of 100nm to 300nm
Stick diameter and up to 1-2 μm of length are characterized);
Ii) the hydrothermal growth for (continuously stirring suspension) in a dynamic condition is received with obtaining the ZnO with high aspect ratio
Rice stick (usually characterized by the length of the stick diameter of about 20-40nm and up to 500-800nm);
Iii it) is grown by probe sonication, for producing the ZnO nanorod with the aspect ratio reduced (usually
Characterized by the length of the diameter of 20-40nm and usually more than 300nm).
Other features and advantages of the present invention will clearly be displayed from subsequent detailed description, the detailed description phase
After three steps for illustrating production process.
The production of the aqueous suspension of step 1-GNP
According to Xian Youjishu [13,14,15], using heat chemistry lift-off technology GNP is produced from intercalated graphite compounds.
However, the deposition method of seed layer and ZnO nano/micrometer structure is acted in a similar way by epitaxial growth, chemical gaseous phase
The graphene oxide (rGO) for the graphene and reduction that deposition, mechanical stripping obtain.Using GNP as starting grapheme material
Advantage is the better Dao electricity Xing [ of the GNP compared with rGO;14], and it is the production technology of GNP, the production technology is in economy
On be advantageous, be suitable for mass producing, and do not use noxious material.
Step 2- deposited seed layers on non-loading type GNP in aqueous solution
Seed layer for growing ZnO nano/micron bar is deposited on GNP in aqueous suspension, aqueous suspension by
The mixture of water and isopropanol is constituted, wherein being dissolved with zinc acetate dihydrate of suitable concentration within the scope of 1mM to 10mM
(Zn(CH3COO)22H2O)[16]。
The deposition process of seed layer includes sub-step described below.
I) by the aqueous solution of zinc acetate dihydrate (1mM to 10mM) and isopropanol by magnetic agitation with 400-600rpm
Speed mix 20-60 minutes.
Ii) GNP obtained in step 1 (or the graphene nanometer sheet of commercially available type or GO or rGO) is rinsed with isopropanol,
And solvent is removed by centrifugation.Then GNP is dispersed in containing zinc acetate dihydrate by being vigorously stirred in centrifuge tube
In aqueous solution.Then suspension is transferred in glass beaker and carries out one of two kinds of different disposals described below:
A) 10 minutes to 60 minutes time is stirred with the stirring of the speed mechanical of 100rpm to 500rpm or with magnetic bar;
B) 5 minutes to the 30 minutes time of probe sonication, by the oscillation amplitude of probe be fixed on 20% and 80% it
Between;
Iii) thus obtained suspension is further centrifuged to remove the growth solution of seed layer;
Iv) sediment of acquisition is heat-treated 10 minutes to 60 minutes at a temperature of 200 DEG C to 400 DEG C in an oven
Time, to obtain the GNP for being coated with the nano particle for being constituted seed layer, size and (on GNP) coating density can lead to
It crosses selection machinery/magnetic agitation technology or sonication techniques and suitably technique for fixing temperature and time is controlled.
Step 3- growing ZnO nanorod/micron bars on non-loading type GNP in aqueous suspension
Growth of the ZnO nanorod on the non-loading type GNP in being scattered in aqueous suspension uses Shui Refa [17]Low
It is carried out under the conditions of either statically or dynamically under temperature, or uses probe sonication Ji Shu [18]It carries out, it then follows following sub-steps.
I) by by the zinc nitrate hexahydrate of equimolar amounts and hexa (HMTA) within the scope of 2mM to 0.5M
Concentration is dissolved in double steaming (DI) water, prepares the aqueous solution for growing ZnO nano/micron bar.It is metal-doped in order to produce
Six hydrated metal nitrate or anhydrous metal nitrate is further added in ZnO nano/micron bar in growth solution.Then will
Acquired solution at room temperature with 20 minutes to the 60 minutes time of speed magnetic agitation within the scope of 300rpm to 700rpm, to
It obtains without turbidity solution.
Ii DIH) is used2O rinses the GNP coated with seed layer again, and water is removed by centrifugation.
Iii) then by be vigorously stirred in centrifuge tube will from the GNP of recycling precipitate be evenly dispersed in growth it is water-soluble
In liquid.
Iv ZnO nano/micron bar then) is grown by one of technology described below:
A. the hydrothermal growth under static conditions:Suspension of the GNP in aqueous growth solution (is had been transferred into glass beaker
In) be placed in the baking oven preheated at a temperature of 70 DEG C -150 DEG C 1 hour to 10 hours.
B. hydrothermal growth in a dynamic condition:Suspension of the GNP in aqueous growth solution (is had been transferred to glass to burn
In cup) it is placed on the hot plate heated at 40 DEG C to 120 DEG C and is mixed by mechanical (or magnetic force) blender 1 hour to 10 small
When.During the reaction, the temperature of solution is kept constant between 30 DEG C and 80 DEG C.
C. probe sonication:Suspension (have been transferred in glass beaker) of the GNP in aqueous growth solution is carried out
The oscillation amplitude of probe is fixed on (its maximum value) 20% He by 5 minutes to the 60 minutes time of probe sonication
Between 100%.
Once v) growth step is completed, suspension is centrifuged to remove growth solution and be washed twice with distilled water.
Vi) that obtained sediment is 10 to 30 minutes dry at a temperature of 70 DEG C to 180 DEG C in an oven.Final products
It is made of the GNP coated with ZnO nano/micron bar.
Description of the drawings
Other features for illustrating the present invention by embodiment provided below, with reference to attached drawing with pure illustrative and non-limit
The mode of property processed illustrates each step of this method, wherein:
Fig. 1 a and 1b show two kinds of different amplifications of the GNP of the seed layer coating obtained by magnetic agitation
SEM image;
Fig. 2 a and 2b show two kinds of different amplifications of the GNP of the seed layer coating obtained by probe sonication
SEM image;
Fig. 3 a and 3b show by by mechanical agitation generate seed layer then in a static condition hydrothermal growth obtain
The SEM image of two kinds of different amplifications of the GNP of ZnO micrometer/nanometer bar coatings;
Fig. 4 a and 4b show by by mechanical agitation generate seed layer then in a dynamic condition hydrothermal growth obtain
The SEM image of two kinds of different amplifications of the GNP of ZnO nanorod coating;
Fig. 5 a and 5b are shown by generating seed layer and then hydrothermal growth obtains in a dynamic condition by probe sonication
The SEM image of two kinds of different amplifications of the GNP of the ZnO nanorod coating obtained;
Fig. 6 a and 6b are shown by being generated seed layer by probe sonication and then being given birth at room temperature by probe sonication
The SEM image of two kinds of different amplifications of the GNP of the long ZnO nanorod coating obtained;And
Fig. 7 a and 7b show SEM image of the ZnO micron bars doped with magnesium under two kinds of different amplifications.
Specific implementation mode
Embodiment
The preparation of embodiment 1-GNP
According to according to [13-15]The method of middle report produces GNP using graphite intercalation compound (GIC) as precursor.
In short, GIC is thermally expanded 5 seconds in Muffle furnace at 1150 DEG C.Then 20mg expanded graphites are immersed into ethyl alcohol (([13-
15]Described in acetone or acetone-DMF mixtures or acetone-NMP mixtures) in, and by 15 minutes under pulse condition
Probe sonication in 30 minutes total times is removed in the liquid phase, and the oscillation amplitude of probe is fixed on 70% and is passed through
The temperature of suspension is controlled at 15 DEG C using the recycling bath for being connected to hot cryostat.It is ultrasonically treated the glue for generating GNP
Liquid suspension, lateral dimension are 1 μm to 5 μm, and thickness is 1nm to 20nm.Then solvent is removed by centrifugation.
Embodiment 2- deposited seed layers on GNP by magnetic agitation
By the way that with the speed magnetic agitation 20 to 60 minutes of 400-600rpm, by zinc acetate dihydrate, (concentration exists
Between 0.001M and 0.010M) it is dissolved in the solution prepared in isopropanol for deposition.It, will be previous before deposited seed layer
The GNP obtained in step is rinsed with isopropanol, and solvent is removed by centrifugation.Then by be vigorously stirred in centrifuge tube by
GNP disperses in the solution to form seed layer.Then suspension is transferred in glass beaker and with 250rpm magnetic agitations 30
Minute is to obtain uniform coating of the seed layer to GNP.Then suspension is further centrifuged to (3095g, 30 minutes) to remove kind
Sublayer growth solution.Then the sediment of acquisition is heat-treated 10 minutes extremely in Muffle furnace at a temperature of 200 DEG C to 400 DEG C
The 60 minutes time, to obtain the GNP for being coated with the ZnO nano particle for being constituted seed layer.
Fig. 1 shows SEM images of the GNP with the seed layer obtained by magnetic agitation under different amplification.
Nano particle has the size usually between 10nm and 30nm.
Embodiment 3- deposited seed layers on GNP by probe sonication
The solution for deposited seed layer is obtained as described in example 2 above.The suspension of GNP is prepared as described in example 2 above
Liquid.Then suspension is transferred in glass beaker and is ultrasonically treated by ultrasonic probe 5 minutes to 30 minutes time, will visit
Head oscillation amplitude is fixed between the 20% of maximum value and 80%.Then suspension is further centrifuged (3095g, 30 minutes) with
Remove seed layer growth solution.Then the sediment of acquisition is heat-treated 10 in Muffle furnace at a temperature of 200 DEG C to 400 DEG C
The time of minute to 60 minutes, to obtain the GNP for being coated with the ZnO nano particle for being constituted seed layer.
Fig. 2 shows the GNP coated with the seed layer obtained by probe sonication under a scanning electron microscope
The image of acquisition.Compared with Example 2, it can be noted that the size for providing the nano particle of seed layer is usually less than 10 to 20nm
And it is evenly coated with the surface of GNP.Compared with the magnetic agitation the case where, the coating on the surfaces GNP is close in the case of supersound process
Spend higher.
Embodiment 4- is grown by the seed layer generated by mechanical agitation on GNP using hydro-thermal method in a static condition
ZnO nanorod
As described in example 2 above, it is micro- that ZnO is grown on the GNP for being pre-coated with the seed layer generated by mechanical agitation
Rice/nanometer rods.Aqueous growth solution is prepared as the step i) in the stage 3 of page 15 is described.Then pass through magnetic agitation at room temperature
Mechanical mixture acquired solution, to obtain without turbidity solution.Before growth, it is rinsed again coated with seed layer with distilled water
GNP, and water is removed by centrifugation.Then equably divided by being vigorously stirred the GNP that will be recycled from sediment in centrifuge tube
It is dispersed in growth solution.Then suspension is transferred in glass beaker to and is put into 70 DEG C to 150 DEG C of the baking oven suitably preheated
In 1 hour to 10 hours time (hydrothermal technique under static conditions).Once growth step is completed, suspension is centrifuged
(3095g, 30 minutes) is used in combination distilled water to wash twice to remove growth solution.By the sediment of acquisition in an oven at 70 DEG C
To dry 10 minutes to 60 minutes at a temperature of 180 DEG C time.Final product is by the GNP structures coated with ZnO nano/micron bar
At.From SEM micrograph shown in Fig. 3 it is noted that they with about 40nm to 150nm diameter and 500nm to 2 μm
Length in range.
Embodiment 5- is grown by the seed layer generated by mechanical agitation on GNP using hydro-thermal method in a dynamic condition
ZnO nanorod
As described in example 2 above, ZnO is grown on the GNP for being pre-coated with the seed layer generated by mechanical agitation to receive
Rice stick.As the step i) in the stage 3 of page 15 preparations grow aqueous solution.Then use mechanical agitator machinery mixed at room temperature
Acquired solution is closed, to obtain without turbidity solution.Before growth, the GNP coated with seed layer is rinsed with distilled water again, and is led to
It crosses and is centrifuged off water.Then it is evenly dispersed in growth by being vigorously stirred the GNP that will be recycled from sediment in centrifuge tube
In solution.Then suspension is transferred in glass beaker, is placed on the hot plate being heated between 40 DEG C and 100 DEG C, and lead to
Cross magnetic stirring apparatus continuously mixing 1 hour to 10 hours.During the reaction, solution keeps constant temperature.Once growth step is completed,
By suspension centrifugation (3095g, 30 minutes) to remove growth solution and be washed twice with distilled water.The sediment of acquisition is being dried
In case at a temperature of 70 DEG C to 180 DEG C dry 10 minutes to 60 minutes time.Final product is by coated with ZnO nanorod
GNP is constituted.From SEM micrograph shown in Fig. 4 it is noted that their diameter is between about 20nm and 30nm, and
Length is between about 400nm and 600nm.
Embodiment 6- uses hydro-thermal method raw on GNP by the seed layer generated by probe sonication in a dynamic condition
Long ZnO nanorod
As described in example 3 above, it is grown on the GNP for being pre-coated with the seed layer generated by probe sonication
ZnO nanorod.Aqueous growth solution is prepared as described in the step i in the stage 3 of page 15.Then acquired solution is passed through at room temperature
Magnetic agitation is stirred, and obtains no turbidity solution.Before growth, the GNP coated with seed layer is rinsed again with distilled water,
And water is removed by centrifugation.Then it is evenly dispersed in by being vigorously stirred the GNP that will be recycled from sediment in centrifuge tube
In growth solution.Then suspension is transferred in glass beaker, is placed on the hot plate being heated between 40 DEG C and 100 DEG C,
And it is continuously mixed by magnetic stirring apparatus 1 hour to 10 hours.During the reaction, solution keeps constant temperature.Once growth step
It completes, by suspension centrifugation (3095g, 30 minutes) to remove growth solution, distilled water is used in combination to wash twice.By the precipitation of acquisition
Object dries 10 minutes to 60 minutes time at a temperature of 70 DEG C to 180 DEG C in an oven.Final product is received by being coated with ZnO
The GNP of rice stick is constituted.It is long from microphoto shown in Fig. 5 it is noted that their diameter is between about 40nm and 70nm
Degree is between about 300nm and 400nm.The coating density on the surfaces GNP is very high, and nanostructure distributes very evenly.
Embodiment 7- grows ZnO nano by the seed layer generated by probe sonication using probe sonication on GNP
Stick
As described in example 3 above, it is grown on the GNP for being pre-coated with the seed layer generated by probe sonication
ZnO nanorod.As the step i) in the stage 3 of page 15 preparations grow aqueous solution.Then it by acquired solution magnetic agitation, obtains
Without turbidity solution.Before growth, it rinses the GNP coated with seed layer again with distilled water, and water is removed by centrifugation.Then
It will be evenly dispersed in growth solution from the GNP recycled in sediment by being vigorously stirred in centrifuge tube.Then it will suspend
Liquid is transferred in glass beaker and carries out 5 minutes to the 60 minutes time of probe sonication at room temperature, by the oscillation of probe
Amplitude is fixed on (its maximum value) between 20% and 100%.Once growth step complete, by suspension centrifugation (3095g, 30
Minute) to remove growth solution and be washed twice with distilled water.The sediment of acquisition is dry in 70 DEG C to 180 DEG C of baking oven
10 minutes to 60 minutes time.Final product is made of the GNP coated with ZnO nanorod.The microphoto shown in Fig. 6
It is noted that the state of flower-shaped aggregation shape is presented in they.The diameter of nanostructure is between about 20nm and 40nm, and length
Degree is between about 150nm and 300nm.Due to the probe sonication during the growth step of nanostructure, coating density is low
The case where being reported in embodiment 6.
Embodiment 8- grows the ZnO nanorod doped with magnesium on GNP
Step according to page 15 (stage 3) grows the micron bar of the ZnO doped with magnesium, in micrometer/nanometer structure
Magnesium nitrate hexahydrate is added in the preparation process of growth solution.
As shown in Figure 7, perfect hexagonal cross-section is presented in thus obtained structure, and diameter is up to 500nm, length
Up to 2 to 3 μm.
Conclusion
Description and embodiment provided above from front clearly show the novel aspects and advantage of the present invention.
The growth of ZnO nano-structure is happened on graphene nanometer sheet (GNP), and not only as reported in the literature
It is happened in graphene oxide (rGO) nanometer sheet of reduction.This represent sizable advantages, because the production of GNP does not relate to
And toxic and dangerous reagent is used, and this is necessary to production rGO.
The modification of GNP ZnO nanorods using hydrothermal technique rather than CVD technology as reported in the literature come into
Row.This so that this method is economically advantageous and is easy to amplification for large-scale production.
The growth of ZnO nano-structure is happened on two faces of GNP, and for this reason, they are suspended in aqueous solution
In.On the contrary, in the research provided in the literature, the modification of graphene ZnO nano-structure, which is usually happened at, to be placed on substrate
Nanometer sheet or graphene film on, and therefore only carried out on the Free Surface of graphene.In addition, the growth in aqueous suspension
Allow to the GNP powder modified by simple drying means acquisition ZnO nanorod.Then these powder may be used as not
Filler in connatural matrix, to obtain multifunctional material.
By suitably limiting the deposition process of seed layer and forming the system for hydrothermal growth in a dynamic condition,
Obtain the control of the coating density to the size of ZnO nano-structure and its on GNP.The hybrid mode of growth suspension makes it possible to
The form of enough control structures.This respect is not found in the existing literature including patent document, and constitute with it is existing
Technology compares the substantial improvements introduced through the invention.
Main application fields
Field according to the present invention is electrical property, Electronic Performance, electromagnetic performance, mechanical performance and catalysis with enhancing
The nanostructure and field of nanocomposite materials of performance.Involved possible theme is in advanced material and compound in the present invention
In material and pressure drag and piezoelectric material field, in sensor field and for providing radar absorption shallow layer or with sense
Survey the company operated in the production of the water based paint of the coating of performance.
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Claims (12)
1. the graphene nanometer sheet that one kind is modified for production zinc oxide nano rod or micron bar (may be doped with metal)
There is improved electrical property, Electronic Performance and mechanical performance, the method to be characterized in that it for method, the graphene nanometer sheet
Including following three steps:
Step 1:Produce the aqueous suspension of graphene nanometer sheet (GNP);
Step 2:Deposited seed layer on non-loading type GNP in aqueous suspension;With
Step 3:Growing ZnO nanorod/micron bar on non-loading type GNP in aqueous suspension,
Wherein, in step 2, during the embryo deposit on the GNP in seed layer (SL) in suspension, seed layer (SL) is constituted
Nano particle uniformity and size control in the following manner:
(magnetic force or machinery) stirring technique or Probe Ultrasonic Searching is used to handle;With
The temperature for the step of then heating in an oven, and
In step 3, for the growth of ZnO micron bars/nanometer rods (may be doped with metal) with required form, by choosing
From the growing technology of three kinds of different growing technologies, i.e. static hydrothermal growth, Dynamic Hydrothermal grows and is grown by being ultrasonically treated, with
Just the morphological feature of structure, i.e. diameter and length caused by capable of controlling.
2. according to the method described in claim 1, it is characterized in that, the hydrothermal growth under selection static conditions is for growing ZnO
Micron bar, the ZnO micron bars are usually characterized by the stick diameter of 100-300nm and up to 1-2 μm of length.
3. according to the method described in claim 1, it is characterized in that, selecting the hydrothermal growth under dynamic condition, i.e., by continuous
Stirred suspension has Gao Zong by acquisition usually characterized by the length of the stick diameter of 20-40nm and up to 500-800nm
The ZnO nanorod of horizontal ratio.
4. according to the method described in claim 1, it is characterized in that, selection grown by probe sonication, for
The ZnO nano with the aspect ratio that reduces of the production usually characterized by the diameter of 20-40nm and no more than the length of 300nm
Stick.
5. according to the method described in claim 1, it is characterized in that, in step 2, the deposition process of seed layer includes following retouches
The sub-step stated:
I) with the speed magnetic agitation of 400-600rpm 20-60 minutes, isopropanol is added to the solution of zinc acetate dihydrate
(1mM to 10mM);
Ii) GNP obtained in step 1 is rinsed with isopropanol, and after solvent is removed by centrifugation, by acute in centrifuge tube
GNP is scattered in the aqueous solution containing zinc acetate dihydrate by strong stirring;Then suspension is transferred in glass beaker simultaneously
Carry out one of following two processing:
A) 10 minutes to 60 minutes time is stirred with the stirring of the speed mechanical of 100rpm to 500rpm or with magnetic bar;Or
The oscillation amplitude of probe is fixed between 20% and 80% by b) 5 minutes to the 30 minutes time of probe sonication;
Iii) thus obtained suspension is further centrifuged to remove the growth solution of seed layer;And
Iv) sediment of acquisition is heat-treated at a temperature of 200 DEG C to 400 DEG C in an oven 10 minutes to 60 minutes when
Between, to obtain the GNP for being coated with the nano particle for being constituted seed layer,
The coating density and size of GNP passes through in sub-step ii) machinery/magnetic agitation technology is selected in the process or is ultrasonically treated skill
Art and suitably technique for fixing temperature and time is controlled.
6. according to the method described in claim 1, it is characterized in that, in step 3, ZnO nanorod/micron bar is being scattered in water
The growth on non-loading type GNP in solution follows following sub-steps and carries out:
I) by by the zinc nitrate hexahydrate of equimolar amounts and hexa (HMTA) with the concentration within the scope of 2mM to 0.5M
It is dissolved in double steaming (DI) water, prepares the aqueous solution for growing ZnO nanorod/micron bar;
Ii) and then by acquired solution at room temperature with the speed magnetic agitation 20 minutes to 60 points within the scope of 300rpm to 700rpm
The time of clock, to obtain without turbidity solution;
Iii the GNP coated with seed layer) is rinsed with double (DI) water that steam, and water is removed by centrifugation;And
Iv it) and then by being vigorously stirred in centrifuge tube will be evenly dispersed in growth aqueous solution from the GNP of recycling precipitate.
7. according to the method described in claim 6, it is characterized in that, in order to produce metal-doped ZnO nanorod/micron bar,
Other six hydrated metals nitrate or anhydrous metal nitrate are added to the growth solution obtained according to sub-step i).
8. according to the method described in claim 6, it is characterized in that, sub-step iv) in be dispersed in growth aqueous suspension
The growth of ZnO nanorod/micron bar is carried out using the hydrothermal technique under static conditions:GNP is outstanding in aqueous growth solution
It is placed 1 hour to 10 hours in the baking oven that supernatant liquid (having been transferred in glass beaker) preheats at a temperature of 70 DEG C -150 DEG C.
9. according to the method described in claim 6, it is characterized in that, sub-step iv) in be dispersed in growth aqueous suspension
The growth of ZnO nanorod/micron bar is carried out using hydrothermal technique in a dynamic condition:By GNP in aqueous growth solution
Suspension (having been transferred in glass beaker) is placed on the hot plate heated at a temperature of 40 DEG C to 120 DEG C and with machinery (or magnetic
Power) blender mix 1 hour to 10 hours, during the reaction the temperature of solution kept between 30 DEG C and 80 DEG C
It is constant.
10. according to the method described in claim 6, it is characterized in that, sub-step iv) in be dispersed in growth aqueous suspension
ZnO nanorod/micron bar grows through the progress of probe sonication technology:(by suspension of the GNP in growing aqueous solution
It is transferred in glass beaker) 5 minutes to the 60 minutes time of probe sonication is carried out, the oscillation amplitude of probe is fixed on
(its maximum value) is between 20% and 100%.
11. according to the method described in claim 1, it is characterized in that, once growth step is completed, by suspension centrifugation to remove
Growth solution simultaneously steams (DI) water washing twice with double;And
Obtained sediment is 10 to 30 minutes dry at a temperature of 70 DEG C to 180 DEG C in an oven, and final products are by coating
There is the GNP of ZnO nanorod/micron bar to constitute.
12. according to the method described in claim 1, it is characterized in that, since step 1, received using the graphene of commercially available type
Either graphene oxide (GO) or the graphene oxide (rGO) of reduction replace GNP to rice piece.
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| PCT/IB2016/057818 WO2017109693A1 (en) | 2015-12-21 | 2016-12-20 | Production of graphene based composite nanostructures obtained through the growth of zinc-oxide nanorods or microrods on unsupported graphene nanoplatelets in suspension |
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| CN112374528A (en) * | 2020-09-30 | 2021-02-19 | 中国科学院苏州纳米技术与纳米仿生研究所广东(佛山)研究院 | Graphene surface-loaded zinc oxide nanoparticle composite material and preparation method and application thereof |
| CN115504501A (en) * | 2021-06-22 | 2022-12-23 | 中国科学院理化技术研究所 | Microwave heating body zinc oxide and preparation method and application thereof |
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| CA3068161A1 (en) * | 2017-07-13 | 2019-01-17 | Carbon Upcycling Technologies Inc. | A mechanochemical process to produce exfoliated nanoparticles |
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| KR102035553B1 (en) * | 2018-02-12 | 2019-10-23 | 경희대학교 산학협력단 | Method for Patterned Metal Oxide Nanorods |
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| CN111437834B (en) * | 2020-05-19 | 2022-07-12 | 福州大学 | Method for constructing in-situ heterojunction based on sulfur indium zinc nanosheets and application |
| CN111874939A (en) * | 2020-08-14 | 2020-11-03 | 山东理工大学 | Rapid batch preparation method of nano metal oxide |
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| CN112885964B (en) * | 2021-01-28 | 2022-11-01 | 北京航空航天大学合肥创新研究院(北京航空航天大学合肥研究生院) | Multi-field regulation memristor and preparation method thereof |
| CN113055573A (en) * | 2021-03-26 | 2021-06-29 | 平安开诚智能安全装备有限责任公司 | Mining ann's type intelligent recognition appearance of making a video recording |
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