CN108698849B - Production of graphene-based composite nanostructures by growing zinc oxide nanorods or nanorods on suspended non-loaded graphene nanoplates - Google Patents
Production of graphene-based composite nanostructures by growing zinc oxide nanorods or nanorods on suspended non-loaded graphene nanoplates Download PDFInfo
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Abstract
An innovative method enables control of the morphology of ZnO nanostructures and the coating density of graphene platelets to produce graphene nanoplatelets modified with zinc oxide nanorods or nanorods (possibly doped with a metal) with enhanced electrical, electronic and mechanical properties. The process is carried out in aqueous or hydroalcoholic suspension and results in the production of nanomaterials in which: it can be used as a filler in a polymer matrix to obtain nanocomposites with specific electrical, electromagnetic and electromechanical properties. The appropriate definition of the process conditions and, where appropriate, the deposition of a seed layer on the GNP surface and the use of a growth technique with continuous mixing of the suspension enables the morphology of the nanostructures to be controlled and makes it possible to obtain a high and uniform coating density of the GNP surface.
Description
The present invention relates to the field of nanotechnology, and more precisely to an innovative process for the production of graphene nanoplatelets decorated with nanorods or nanorods of zinc oxide (possibly doped with a metal) having improved electrical, electronic and mechanical properties. Graphene Nanoplatelets (GNPs) are uniformly coated with Nanorods (NR) or nanorods (MR) (possibly doped with a metal) of zinc oxide (ZnO) over their entire surface (on both sides of the sheet). The morphological properties of the ZnO nanostructures and the coating density of the GNP surface can be controlled during the growth process.
The process is carried out in aqueous or hydroalcoholic suspension and results in the production of nanomaterials in which: the nanomaterials can be used as fillers in polymer matrices to obtain nanocomposites with specific electrical, electromagnetic and electromechanical properties.
The process used in the present invention is simple, economically advantageous, scalable for large scale production, does not require the use of catalysts, and the final product is free of impurities.
Technical Field
The present invention was developed within the framework of research aimed at providing novel nanostructured graphene-based materials with controlled electrical, electromagnetic and electromechanical properties.
GNPs modified with ZnO nano/micro rods have significant applications in a variety of fields, whether as mechanical reinforcement in composites or where it is possible to exploit their piezoelectric or electroactive properties, for the production of composites with desirable electrical and/or electromagnetic properties, such as radar absorbing materials, and catalytic or energy harvesting applications.
Disclosure of Invention
According to the present invention, ZnO-GNP hybrid nano/micro structures are produced in the presence of a seed layer that facilitates nucleation of ZnO structures and results in uniform and high density coating of GNPs. The deposition of the seed layer is performed while maintaining suspension of GNPs under agitation to control the density and uniformity of the coating by various techniques as described below.
The main innovative feature of the present invention is the simplicity and cheapness of the proposed method, which enables the production of ZnO modified GNPs with controlled morphological characteristics by appropriately defining the operating conditions during the steps of depositing said seed layer and growing the ZnO micro/nanostructures.
Several studies exist in the literature that show that it is feasible to grow ZnO nanorods on GNPs from aqueous solutions without previously depositing a seed layer on the GNPs. However, it can be seen from these studies that there is no satisfactory control of the quality and morphology of the ZnO micro/nanostructures produced in this way, and that the coating density of the GNP surface is found to be poor, with limited uniformity of the micro/nanostructure distribution thereon.
In other studies, it was shown how the presence of a seed layer makes it possible to obtain high coating densities of thin sheets of GO (graphene oxide) or rGO (reduced graphene oxide) or supported graphene.
According to the literature, the hydrothermal growth of ZnO nanostructures is usually carried out under static conditions.
In contrast, according to the present invention, for the growth of ZnO micro/nanorods (possibly doped with metals) with the desired morphology, three different growth techniques (i.e. static hydrothermal-HT-growth, dynamic HT-growth and growth by probe ultrasonic PS) are proposed in order to be able to control the morphological characteristics (i.e. diameter and length) of the produced structures.
The production techniques developed according to the present invention are economically advantageous and suitable for large-scale production.
Background
Composite materials based on graphene and zinc oxide (ZnO) nanostructures are the subject of much research due to their potential application in the production of new multifunctional materials with improved electrical and mechanical properties and new devices for the electronic and optical fields [1, 2 ]. It has been shown in the literature that inorganic materials such as zinc oxide have significantly improved electronic properties when combined with graphene [3 ]. ZnO nanostructures typically behave as n-type semiconductors and therefore have the ability to be electron doped on graphene. Thus, modification of graphene by ZnO nanostructures enables the production of novel graphene nanomaterials with additional features such as higher electrical conductivity, improved energy absorption capacity associated with electromagnetic fields when used as fillers in polymer matrices, higher electron emission and detection capabilities [4, 5, 6] and better electrochemical properties [7, 8 ]. In previous studies [9], composites consisting of Graphene Nanoplatelets (GNPs) and ZnO nanowires have been produced by using suspension mixing and vacuum filtration. The porous composite materials thus produced have shown beneficial electrical properties. In particular, it has been emphasized that there is an optimal weight concentration of ZnO nanowires with respect to GNPs, which corresponds to the greatest improvement in the electrical conductivity of the composite, confirming the hypothesis that ZnO nanostructures can induce electron doping effects on graphene.
The present invention is therefore within the framework of this research and proposes an innovative technique for the production of graphene modified with nano/micro structures (nanorods or nanorods with controlled morphological properties, where appropriate) of ZnO or ZnO doped with metals. The graphene nanoplatelets according to the present invention constitute a growth matrix of ZnO nano/micro structure, thus being able to maximize the effect of the interaction between the nano-structured ZnO and graphene. Growth of ZnO nanostructures occurs in aqueous solutions, in which graphene nanoplatelets are dispersed in a suspension. Suitable definition of the process conditions, in particular the use of deposition and growth techniques of the seed layer on the GNP surface, including continuous mixing of the suspension, enables control of the morphology of the nanostructures and the high and uniform coating density of the GNP surface to be obtained.
Various studies in the scientific and patent literature have been directed to the production of hybrid composites typically composed of Graphene Oxide (GO) and ZnO nano/micro structures [10, 12 ]. However, most of these studies use graphene oxide as the starting material [7, 10], which is not known to be a good electrical conductor. Therefore, in these studies, treatment steps dedicated to the reduction of the obtained GO-ZnO hybrid material are always involved, especially in such applications: the purpose of this (as mentioned above) is to take advantage of the effect of the electrical/electronic property enhancement of the final material resulting from the interaction effect between the ZnO nanostructures and graphene, for example in capacitors, photodetectors and sensors.
Specifically, Junwei Ding et al [10] have grown mixed zinc oxide structures composed of nanoparticles and micro-spindles by hydrothermal synthesis on reduced graphene oxide in aqueous solution and without the use of a seed layer. GO was obtained by a modified Hummer process, followed by reduction of GO by glucose and ammonia. However, ZnO micron spindles exhibit rGO flake coating densities lower than those obtainable according to this patent.
In another study, Chien-Te Hsieh et al [11] reported the growth of ZnO nanocrystals by microwave heating. GO obtained by the modified Hummer method was coated with the ZnO nanocrystals produced under high shear stress mixing. In this case also no seed layer is used.
Whereas few studies using non-graphene oxide as a growth matrix for ZnO nanostructures started anyway with GO and performed the step of reducing GO to rGO before nanostructure growth, which generally involved the use of toxic and hazardous reagents.
In any case, the quality of the grown nanostructures was poor in the above studies. Typical morphologies of note are nanoparticle or nanorod morphologies with very low aspect ratios, with rather inhomogeneous properties, and rather low coating densities of graphene surfaces. Furthermore, there is no possibility of growing ZnO nanostructures doped with metals.
Other studies have shown the growth of ZnO nanostructures on supported graphene sheets grown by Chemical Vapor Deposition (CVD) techniques [11] or obtained by mechanical exfoliation of graphite [12 ]. Ren-JelChung et al [11] synthesized ZnO nanorods on supported graphene using hydrothermal techniques, the graphene being grown by CVD and using a 100nm seed layer obtained by evaporation activated by electron beam. In addition to the high cost, the methods used are not easily scalable. Yong-Jin Kim et al [12] reported the growth of ZnO nanorods on multilayer graphene obtained by mechanical exfoliation without the use of a seed layer. The grown structures have a diameter of 230 to 800 nm. The methods used are laborious, expensive and not easily scalable.
It should be noted, however, that none of the above techniques is suitable for large-scale production of ZnO-modified unsupported graphene sheets for the production of new materials and multifunctional devices.
The patent literature, which will be briefly analyzed in the following, also does not provide innovative procedures enabling, for example, the realization of high-density growth of ZnO nano/micro structures on unsupported GNPs, which will be uniform over the entire surface of the GNPs and will be economically viable and suitable for large-scale production.
Patent KR20140037518(a) "ZnO nanostructures comprising graphene" relates to the deposition of a ZnO nanostructure layer on a graphene sheet grown by CVD and supported by a matrix, for application in devices for optical detection. This patent KR20140037518 relates to the use of a support for growing graphene, has a high cost, is not easily scalable, and enables the growth of ZnO nanostructures on only one face of the graphene plane.
Patent CN102157315(a) "emission cathode based on graphene/zinc oxide nanowire composite and its preparation" relates to the production of electron field emission cathodes for FEDs (field emission displays) consisting of a conductive electrode coated with graphene and covered with a ZnO nanowire array. Conductive electrodes (typically composed of glass coated with a metal layer by PVD) are coated with graphene layers from a previously sonicated aqueous suspension using various techniques such as spraying or electrophoresis. The ZnO nanowires may then be grown by hydrothermal techniques or CVD or PVD, preferably CVD. As in the former case, patent CN102157315 also relates to the use of growth substrates and to the use of expensive devices. Furthermore, the nanostructures are grown on only one side of the graphene plane.
Patent US20130099196a1 "semiconductor-graphene hybrid formed using solution growth" relates to the production of a composite material consisting of graphene and ZnO nano-nanorods to obtain a UV detector by aqueous solution growth of ZnO (without using a seed layer) on graphene grown by CVD and supported on a PMMA layer. An innovative aspect of this patent is that there is no seed layer present and growth can be carried out under the following conditions: the graphene matrix was placed face down on the free surface of the reaction beaker or face up on the bottom of the beaker and in this case supported by a Si or glass substrate.
However, this us patent is unable to grow ZnO micro/nanostructures on both sides of graphene sheets and involves the use of a substrate and expensive equipment.
Patent CN103734188(a) "preparation method and application of zinc oxide-graphene oxide composite nanomaterial" relates to the production of graphene oxide-zinc oxide composite material starting from a suspension of GO in alcohol and its use as an antibacterial agent, in particular as a preservative for biomedical instruments and devices. This patent relates to the production of composites of GO and ZnO nanoparticles, the production of which requires first obtaining GO, applying a modified form of the well-known Hummer process, and therefore using hazardous reagents.
Patent CN104007236(a) "preparation method and application of graphene/zinc oxide nanocomposite material" relates to the production of hybrid nanocomposite material based on graphene/ZnO obtained in aqueous suspension using ultrasound. This patent relates to the ultrasonic dissolution of zinc nitrate in aqueous solution, followed by the addition of GO and in situ reduction by ultrasound again using hydrazine. Patent CN104007236 also relates to the use of aggressive reagents both for the production step of GO and for its subsequent reduction. Furthermore, the various production steps involve a large number of flows, which makes their implementation long and technically demanding.
Patent CN103435033(a) "simple method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave" relates to the production of hybrid graphene-ZnO nanorod composite material from the starting of ultrasonic treatment of finely ground metallic Zn powder in the presence of expanded graphite suspended in an aqueous ethanol solution.
And (3) obtaining the production of the hybrid graphene-ZnO nanorod composite material through a long ultrasonic process lasting for 6-10 hours.
Patent CN102580716(a) "method for the synthesis of zinc oxide/graphene composites by solvothermal process" reports a production method of hybrid composite materials consisting of ZnO modified GO with photocatalytic properties. The process comprises solvothermal synthesis (with simultaneous partial reduction of GO) at a temperature lower than 200 ℃, carried out on a mixture of GO and zinc acetylacetonate in a suitable solvent, typically ethylene glycol or ethanol. This patent CN102580716 relates to the use of strong acids and oxidizing agents for the production of GO by a modified form of the known Hummer process.
Patent CN101857222(a) "preparation method of large-area continuous graphene/zinc oxide composite structure" relates to the preparation of composite material formed by G/GO and ZnO nanostructures starting from aqueous suspension of graphene or GO or suspension in organic solvent. After suspension of G/GO in a solvent by sonication, ZnO nanostructures (containing various geometries, including nanodots and nanowires/nanorods) were produced by hydrothermal growth starting from different reagents (zinc nitrate and HMTA or zinc acetate) depending on the structure to be obtained. Then reduction with hydrazine is carried out. This patent also relates to the use of aggressive reagents both for the GO production step and for its subsequent reduction. The different production steps also involve a large number of processes, which makes their implementation tedious and problematic.
Patent CN10342614(a) "preparation method of graphene-ZnO nanoparticle composite material" relates to the preparation of GO-ZnO nanoparticle composite material starting from simple Zn salts (nitrate, acetate, sulfate, chloride, etc.). The product (particle size 10nm) was obtained by simple mixing of the salts in aqueous GO solution and subsequent heat treatment between 150 ℃ and 1000 ℃. Patent CN103482614 uses GO as a precursor for the preparation of GO-ZnO nanoparticle composites. Furthermore, the methods employed include the use of high temperatures and long reaction times, even up to 10 hours.
Thus, there is clearly felt the need for a method for growing nano/micro structures of ZnO (possibly doped with metals) on unsupported GNPs dispersed in an aqueous suspension, which will coat (on both sides of the flakes) the entire surface of the GNPs and will enable mass production, wherein the morphological properties of the ZnO nanostructures and the coating density of the GNP surface can be controlled throughout the growth process.
Disclosure of Invention
Experiments carried out by the applicant have revealed the possibility of growing micro/nanostructures (possibly doped with metals) of ZnO on both sides of unsupported GNPs and in aqueous suspension, with a uniform and high density coating, without resorting to any reduction step involving the use of hazardous reagents. Furthermore, the correlation existing between the process conditions for growth and morphology, density and homogeneity of ZNO nanorods and nanorods grown on unsupported GNPs is also emphasized.
An innovative approach suitable for large-scale production has therefore been developed, in which ZnO-GNP hybrid nano/micro structures are produced in the presence of a seed layer that facilitates nucleation of the ZnO structures and results in a uniform and high density coating of GNPs on both sides. Furthermore, the deposition of the seed layer is performed by keeping the GNPs in suspension under agitation using various techniques as described in detail below to control the density and uniformity of the coating of graphene flakes, thereby enabling control of the final properties of the material. Another innovative feature of the present invention relates to the possibility of doping ZnO micro/nanostructures grown on GNPs with metals. This feature is not described in the literature. The developed method comprises the following steps:
step 1: producing an aqueous suspension of Graphene Nanoplatelets (GNPs);
step 2: depositing a seed layer on unsupported GNPs in an aqueous suspension;
step 3: ZnO nanorods/nanorods were grown on unsupported GNPs in aqueous suspension.
The innovative aspect characterizing the present invention relates to steps 2 and 3 of the growth process of ZnO nano/micro structures, as described below.
In step 2, during the initial deposition of a Seed Layer (SL) on GNPs in suspension, the uniformity and size of the nanoparticles that make up the SL are controlled by:
sonication using a mixing technique (magnetic or mechanical type) or a probe; and
temperature of the subsequent heating step in an oven.
In step 3, three different growth techniques (static HT growth, dynamic HT growth and growth by PS) are proposed for the growth of micro/nanorods (possibly doped with metals) of ZnO with the desired morphology, in order to be able to control the morphological characteristics (i.e. diameter and length) of the resulting structure. In particular, the following techniques are proposed:
i) hydrothermal growth under static conditions for growing ZnO microrods (typically characterized by rod diameters in the range of 100nm to 300nm and lengths up to 1-2 μm);
ii) hydrothermal growth under dynamic conditions (i.e. continuously stirring the suspension) to obtain ZnO nanorods with high aspect ratio (typically characterized by a rod diameter of about 20-40nm and a length of up to 500-800 nm);
iii) growth by probe sonication for the production of ZnO nanorods with reduced aspect ratio (typically characterized by a diameter of 20-40nm and a length typically no greater than 300 nm).
Other characteristics and advantages of the invention will appear clearly from the detailed description which follows, which illustrates three steps of the production process in succession.
Step 1-production of aqueous suspensions of GNP
GNPs are produced according to prior art [13, 14, 15] starting from intercalated graphite compounds using thermochemical exfoliation techniques. However, the seed layer and the deposition method of ZnO nano/micro structures act in a similar way on graphene obtained by epitaxial growth, chemical vapour deposition, mechanical exfoliation and reduced graphene oxide (rGO). The advantage of using GNPs as starting graphene materials is the better electrical conductivity of GNPs compared to rGO [14], and in the production process of GNPs, which is economically advantageous, suitable for large-scale production, and does not use toxic substances.
Step 2-deposition of seed layer on unsupported GNP in aqueous solution
A seed layer for growing ZnO nano/micro rods was deposited on GNP in an aqueous suspension consisting of a mixture of water and isopropanol in which an appropriate amount of zinc acetate dihydrate (Zn (CH) with a concentration in the range of 1mM to 10mM) was dissolved3COO)22H2O)[16]。
The deposition process of the seed layer includes the sub-steps described below.
i) An aqueous solution of zinc acetate dihydrate (1mM to 10mM) was mixed with isopropanol by magnetic stirring at 400-.
ii) the GNPs obtained in step 1 (or graphene nanoplatelets of the type commercially available or GO or rGO) are rinsed with isopropanol and the solvent is removed by centrifugation. GNPs were then dispersed in an aqueous solution containing zinc acetate dihydrate by vigorous stirring in a centrifuge tube. The suspension was then transferred to a glass beaker and subjected to one of two different treatments as described below:
a) mechanically stirring at a speed of 100rpm to 500rpm or stirring with a magnetic bar for a time of 10 minutes to 60 minutes;
b) the probe is subjected to ultrasonic treatment for a time of 5 minutes to 30 minutes, and the oscillation amplitude of the probe is fixed between 20% and 80%;
iii) further centrifuging the suspension thus obtained to remove the growth solution of the seed layer;
iv) heat-treating the obtained precipitate in an oven at a temperature of 200 to 400 ℃ for a time of 10 to 60 minutes to obtain GNPs coated with nanoparticles constituting the seed layer, the size and coating density (on the GNPs) of which can be controlled by selecting mechanical/magnetic stirring techniques or ultrasonic treatment techniques and fixing the process temperature and time appropriately.
Step 3-growing ZnO nanorods/nanorods on unsupported GNP in aqueous suspension
The growth of ZnO nanorods on unsupported GNPs dispersed in aqueous suspensions is carried out using hydrothermal methods [17] at low temperature under static or dynamic conditions, or using probe sonication techniques [18], following the following sub-steps.
i) An aqueous solution for growing ZnO nano/micro rods was prepared by dissolving equimolar amounts of zinc nitrate hexahydrate and Hexamethylenetetramine (HMTA) in double Distilled (DI) water at a concentration ranging from 2mM to 0.5M. To produce metal-doped ZnO nano/micro rods, metal nitrate hexahydrate or anhydrous metal nitrate was further added to the growth solution. The resulting solution was then magnetically stirred at room temperature at a speed in the range of 300rpm to 700rpm for a period of 20 minutes to 60 minutes, thereby obtaining a turbidity-free solution.
ii) by DIH2O rinse the GNPs coated with seed layer again and remove water by centrifugation.
iii) the GNPs recovered from the precipitate were then dispersed uniformly in the aqueous growth solution by vigorous stirring in a centrifuge tube.
iv) subsequent growth of ZnO nano/micro rods by one of the techniques described below:
a. hydrothermal growth under static conditions: the suspension of GNPs in the aqueous growth solution (which has been transferred to a glass beaker) is placed in an oven preheated at a temperature of 70-150 ℃ for 1 to 10 hours.
b. Hydrothermal growth under dynamic conditions: the suspension of GNPs in aqueous growth solution (which has been transferred into a glass beaker) is placed on a hot plate heated at 40 ℃ to 120 ℃ and mixed by a mechanical (or magnetic) stirrer for 1 to 10 hours. During the reaction, the temperature of the solution was kept constant between 30 ℃ and 80 ℃.
c. Ultrasonic treatment of the probe: the suspension of GNPs in aqueous growth solution (which has been transferred into a glass beaker) is subjected to probe sonication for a period of 5 to 60 minutes, fixing the oscillation amplitude of the probe between 20% and 100% (of its maximum).
v) once the growth step is complete, the suspension is centrifuged to remove the growth solution and washed twice with double distilled water.
vi) drying the resulting precipitate in an oven at a temperature of 70 ℃ to 180 ℃ for 10 to 30 minutes. The final product consists of GNPs coated with ZnO nano/micro rods.
Drawings
Further characteristics of the invention are illustrated by the examples provided below, which illustrate, purely by way of illustration and not by way of limitation, the various steps of the method with reference to the accompanying drawings, in which:
fig. 1a and 1b show SEM images of seed layer coated GNPs obtained by magnetic stirring at two different magnifications;
fig. 2a and 2b show SEM images of seed layer coated GNPs obtained by probe sonication at two different magnifications;
fig. 3a and 3b show SEM images of ZnO micro/nanorod coated GNPs obtained by creating a seed layer by mechanical stirring and then hydrothermally growing under static conditions at two different magnifications;
fig. 4a and 4b show SEM images at two different magnifications of ZnO nanorod coated GNPs obtained by creating a seed layer by mechanical stirring and then hydrothermally growing under dynamic conditions;
fig. 5a and 5b show SEM images of ZnO nanorod coated GNPs obtained by creating a seed layer by probe sonication followed by hydrothermal growth under dynamic conditions at two different magnifications;
fig. 6a and 6b show SEM images at two different magnifications of ZnO nanorod coated GNPs obtained by creating a seed layer by probe sonication and then growing at room temperature by probe sonication; and is
Fig. 7a and 7b show SEM images of ZnO nanorods doped with magnesium at two different magnifications.
Detailed Description
Examples
Example 1 preparation of GNP
GNPs were produced according to a method similar to that reported in [13-15], using Graphite Intercalation Compounds (GICs) as precursors. Briefly, the GIC was thermally expanded in a muffle furnace at 1150 ℃ for 5 seconds. Then 20mg of expanded graphite was immersed in ethanol (instead of acetone or acetone-DMF mixture or acetone-NMP mixture described in [13-15 ]) and exfoliated in the liquid phase by ultrasonic treatment with a probe for a total time of 15 to 30 minutes in a pulsed state, the oscillation amplitude of the probe was fixed at 70% and the temperature of the suspension was controlled at 15 ℃ by using a recirculating bath connected to a thermal cryostat. Sonication produces colloidal suspensions of GNPs with transverse dimensions of 1 to 5 μm and thicknesses of 1 to 20 nm. The solvent was then removed by centrifugation.
Example 2 deposition of seed layer on GNP by magnetic stirring
The solution for deposition was prepared by dissolving zinc acetate dihydrate (concentration between 0.001M and 0.010M) in isopropanol by magnetic stirring at 400-600rpm for 20 to 60 minutes. Before depositing the seed layer, GNPs obtained in the previous step were rinsed with isopropanol and the solvent was removed by centrifugation. GNPs were then dispersed in the solution by vigorous stirring in a centrifuge tube to form a seed layer. The suspension was then transferred into a glass beaker and magnetically stirred at 250rpm for 30 minutes to obtain a uniform coating of the GNPs by the seed layer. The suspension was then further centrifuged (3095g, 30 min) to remove the seed layer growth solution. The obtained precipitate is then heat-treated in a muffle furnace at a temperature of 200 ℃ to 400 ℃ for a time of 10 minutes to 60 minutes to obtain GNPs coated with ZnO nanoparticles constituting the seed layer.
Fig. 1 shows SEM images of GNPs with seed layers obtained by magnetic stirring at different magnifications. The nanoparticles have a size typically between 10nm and 30 nm.
Example 3 deposition of seed layer on GNP by Probe sonication
A solution for depositing a seed layer was obtained as described in example 2. Suspensions of GNPs were prepared as described in example 2. The suspension was then transferred into a glass beaker and sonicated by an ultrasonic probe for a period of 5 to 30 minutes, fixing the probe oscillation amplitude between 20% and 80% of the maximum. The suspension was then further centrifuged (3095g, 30 min) to remove the seed layer growth solution. The obtained precipitate is then heat-treated in a muffle furnace at a temperature of 200 ℃ to 400 ℃ for a time of 10 minutes to 60 minutes to obtain GNPs coated with ZnO nanoparticles constituting the seed layer.
Fig. 2 shows an image obtained under a scanning electron microscope of GNPs coated with a seed layer obtained by probe sonication. Compared to example 2, it can be noted that the nanoparticles providing the seed layer are typically smaller in size than 10 to 20nm and uniformly coat the surface of the GNPs. The coating density of the GNP surface is higher in the case of ultrasonic treatment than in the case of magnetic stirring.
Example 4 growth of ZnO nanorods on GNP from seed layer produced by mechanical stirring under static conditions using hydrothermal method
ZnO micro/nanorods were grown on GNPs previously coated with a seed layer generated by mechanical stirring as described in example 2. The aqueous growth solution was prepared as described in step i) of page 15, stage 3. The resulting solution was then mechanically mixed by magnetic stirring at room temperature to obtain a turbidity-free solution. Prior to growth, GNPs coated with seed layer were rinsed again with double distilled water and water was removed by centrifugation. The GNPs recovered from the precipitate were then dispersed evenly in the growth solution by vigorous stirring in a centrifuge tube. The suspension was then transferred into a glass beaker and placed in a suitably preheated oven at 70 ℃ to 150 ℃ for a period of 1 hour to 10 hours (hydrothermal technique under static conditions). Once the growth step was complete, the suspension was centrifuged (3095g, 30 min) to remove the growth solution and washed twice with double distilled water. The obtained precipitate is dried in an oven at a temperature of 70 ℃ to 180 ℃ for a time of 10 minutes to 60 minutes. The final product consisted of GNPs coated with ZnO nano/micro rods. As can be noted from the SEM micrograph shown in fig. 3, they have a diameter of about 40nm to 150nm and a length in the range of 500nm to 2 μm.
Example 5 growth of ZnO nanorods on GNP from seed layer generated by mechanical stirring under dynamic conditions Using hydrothermal method
ZnO nanorods were grown on GNPs previously coated with a seed layer generated by mechanical stirring, as described in example 2. The aqueous growth solution was prepared as described in step i) of phase 3, page 15. The resulting solution was then mechanically mixed using a mechanical stirrer at room temperature to obtain a turbidity-free solution. Prior to growth, GNPs coated with seed layer were again rinsed with double distilled water and the water was removed by centrifugation. The GNPs recovered from the precipitate were then dispersed evenly in the growth solution by vigorous stirring in a centrifuge tube. The suspension was then transferred to a glass beaker, placed on a hot plate heated to between 40 ℃ and 100 ℃ and mixed continuously by a magnetic stirrer for 1 to 10 hours. During the reaction, the solution was kept at a constant temperature. Once the growth step was complete, the suspension was centrifuged (3095g, 30 min) to remove the growth solution and washed twice with double distilled water. The obtained precipitate is dried in an oven at a temperature of 70 ℃ to 180 ℃ for a time of 10 minutes to 60 minutes. The final product consists of GNPs coated with ZnO nanorods. As can be noted from the SEM micrograph shown in fig. 4, they are between about 20nm and 30nm in diameter and between about 400nm and 600nm in length.
Example 6 growth of ZnO nanorods on GNP from seed layer produced by Probe sonication under dynamic conditions Using hydrothermal method
ZnO nanorods were grown on GNPs previously coated with a seed layer produced by probe sonication as described in example 3. An aqueous growth solution was prepared as described in page 15, stage 3, step i. The resulting solution was then stirred at room temperature by magnetic stirring to give a turbidity-free solution. Prior to growth, GNPs coated with seed layer were rinsed again with double distilled water and water was removed by centrifugation. The GNPs recovered from the precipitate were then dispersed evenly in the growth solution by vigorous stirring in a centrifuge tube. The suspension was then transferred to a glass beaker, placed on a hot plate heated to between 40 ℃ and 100 ℃ and mixed continuously by a magnetic stirrer for 1 to 10 hours. During the reaction, the solution was kept at a constant temperature. Once the growth step was complete, the suspension was centrifuged (3095g, 30 min) to remove the growth solution and washed twice with double distilled water. The obtained precipitate is dried in an oven at a temperature of 70 ℃ to 180 ℃ for a time of 10 minutes to 60 minutes. The final product consists of GNPs coated with ZnO nanorods. It can be noted from the micrograph shown in fig. 5 that they have a diameter of between about 40nm and 70nm and a length of between about 300nm and 400 nm. The coating density of the GNP surface is very high and the distribution of the nanostructures is very uniform.
Example 7-use of Probe sonication to grow ZnO nanorods on GNP from seed layers generated by Probe sonication
ZnO nanorods were grown on GNPs previously coated with a seed layer produced by probe sonication as described in example 3. The aqueous growth solution was prepared as described in step i) of phase 3, page 15. The resulting solution was then magnetically stirred to give a turbidity-free solution. Prior to growth, GNPs coated with seed layer were rinsed again with double distilled water and water was removed by centrifugation. The GNPs recovered from the precipitate were then dispersed evenly in the growth solution by vigorous stirring in a centrifuge tube. The suspension was then transferred into a glass beaker and sonicated at room temperature for a period of 5 to 60 minutes, fixing the oscillation amplitude of the probe between 20% and 100% (of its maximum). Once the growth step was complete, the suspension was centrifuged (3095g, 30 min) to remove the growth solution and washed twice with double distilled water. The precipitate obtained is dried in an oven at 70 ℃ to 180 ℃ for a time ranging from 10 minutes to 60 minutes. The final product consists of GNPs coated with ZnO nanorods. As can be noted from the photomicrograph shown in fig. 6, they assume a state of flower-like aggregate shape. The nanostructures are between about 20nm and 40nm in diameter and between about 150nm and 300nm in length. Due to the probe sonication during the growth step of the nanostructures, the coating density was lower than in the case reported in example 6.
Example 8 growth of ZnO nanorods doped with magnesium on GNP
The magnesium doped ZnO nanorods were grown according to the procedure described on page 15 (stage 3), magnesium nitrate hexahydrate was added in the preparation step of the micro/nanostructure growth solution.
The structure thus obtained exhibits a perfect hexagonal cross-section, as shown in fig. 7, with a diameter of up to 500nm and a length of up to 2 to 3 μm.
Conclusion
The innovative aspects and advantages of the present invention are apparent from the foregoing description and the embodiments provided above.
Growth of ZnO nanostructures occurs on Graphene Nanoplatelets (GNPs), not just on reduced graphene oxide (rGO) nanoplatelets as reported in the literature. This represents a considerable advantage, since the production of GNPs does not involve the use of toxic and hazardous reagents, which are necessary for the production of rGO.
Modification of GNPs with ZnO nanorods was performed using hydrothermal techniques instead of CVD techniques as reported in the literature. This makes the process economically advantageous and easy to scale up for large scale production.
Growth of ZnO nanostructures occurs on both sides of GNPs, for which reason they are suspended in aqueous solution. In contrast, in the studies given in the literature, the modification of graphene with ZnO nanostructures usually takes place on nanosheets or graphene sheets placed on a substrate and is therefore only carried out on the free surface of the graphene. Furthermore, growth in aqueous suspension allows GNP powders modified with ZnO nanorods to be obtained by a simple drying process. These powders can then be used as fillers in matrices of different nature to obtain multifunctional materials.
Control of the size of the ZnO nanostructures and their coating density on GNPs is obtained by appropriate definition of the deposition process of the seed layer and formation of a system for hydrothermal growth under dynamic conditions. The mixing of the growth suspension enables the morphology of the structure to be controlled. This aspect is not found in the prior art documents, including patent documents, and constitutes a substantial improvement introduced by the present invention over the prior art.
Main field of application
The field to which the invention relates is in the field of nanostructures and nanocomposites with enhanced electrical, electronic, electromagnetic, mechanical and catalytic properties. Possible subjects involved in the present invention are companies operating in the field of advanced materials and composites and piezoresistive and piezoelectric materials, in the field of sensors and in the production of water-based paints for providing radar-absorbing thin coatings or coatings with sensing properties.
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Claims (12)
1. A process for the production of graphene nanoplatelets modified with zinc oxide nanorods or nanorods, said graphene nanoplatelets having improved electrical, electronic and mechanical properties, characterized in that it comprises the following three steps:
step 1: producing an aqueous suspension of graphene nanoplatelets in a water and alcohol mixture; wherein the graphene nanoplatelets are rinsed with isopropanol and dispersed in an aqueous solution containing zinc acetate dihydrate by vigorous stirring in a centrifuge tube after the solvent is removed by centrifugation;
step 2: depositing a seed layer on unsupported graphene nanoplatelets suspended in an aqueous solution consisting of a mixture of water and alcohol; and
and step 3: growing ZnO nanorods/nanorods on the non-supported graphene nanosheets deposited with the seed layers in the aqueous suspension;
wherein the content of the first and second substances,
i) magnetically stirring at 400-;
ii) transferring the suspension of graphene nanoplatelets dispersed in the aqueous solution containing zinc acetate dihydrate by vigorous stirring into a glass beaker and performing one of the following two treatments:
a) mechanically stirring at a speed of 100rpm to 500rpm or stirring with a magnetic bar for a time of 10 minutes to 60 minutes; or
b) The probe is subjected to ultrasonic treatment for a time of 5 minutes to 30 minutes, and the oscillation amplitude of the probe is fixed between 20% and 80%; the suspension thus obtained was further centrifuged to remove the growth solution of the seed layer; and is
iii) heat-treating the obtained precipitate in an oven at a temperature of 200 to 400 ℃ for a time of 10 to 60 minutes, and in step 3, for the growth of ZnO nanorods/nanorods with the desired morphology, by means of a growth technique selected from three different growth techniques, namely static hydrothermal growth, dynamic hydrothermal growth and growth by sonication.
2. The method of claim 1,
in step 3, the growth of ZnO nanorods/nanorods on unsupported graphene nanoplatelets deposited with a seed layer dispersed in an aqueous solution comprises the following steps:
i) preparing an aqueous solution for growing ZnO nanorods/nanorods by dissolving equimolar amounts of zinc nitrate hexahydrate and Hexamethylenetetramine (HMTA) in deionized water at a concentration ranging from 2mM to 0.5M;
ii) the resulting solution is then magnetically stirred at room temperature at a speed in the range of 300rpm to 700rpm for a time of 20 minutes to 60 minutes, thereby obtaining a turbidity-free solution;
iii) rinsing the graphene nanoplatelets coated with the seed layer with deionized water;
iv) removing water by centrifugation; and is
v) then uniformly dispersing the graphene nanoplatelets recovered from the precipitate in the growing aqueous solution by vigorous stirring in a centrifuge tube.
3. The method of claim 1, wherein the graphene nanoplatelets modified with zinc oxide nanorods or nanorods are doped with a metal.
4. The method according to claim 3, characterized in that for the production of graphene nanoplatelets modified with metal-doped zinc oxide nanorods or nanorods, further metal nitrate hexahydrate or anhydrous metal nitrate is added to the growth solution obtained according to substep i).
5. The process according to claim 1, characterized in that the growth of ZnO nanorods/nanorods dispersed in a growing aqueous suspension is carried out using a hydrothermal technique under static conditions, wherein a suspension of graphene nanoplatelets deposited with a seed layer, which has been transferred into a glass beaker, in an aqueous growth solution is placed in an oven preheated at a temperature of 70-150 ℃ for 1 to 10 hours.
6. The process according to claim 1, characterized in that the growth of the ZnO nanorods/nanorods dispersed in the growing aqueous suspension is carried out using a hydrothermal technique under dynamic conditions, wherein the suspension of graphene nanoplatelets in the aqueous growing solution deposited with the seed layer, which has been transferred into a glass beaker, is placed on a hot plate heated at a temperature of 40 ℃ to 120 ℃ and mixed with a mechanical or magnetic stirrer for 1 hour to 10 hours, the temperature of the solution being kept constant in the range between 30 ℃ and 80 ℃ during the reaction.
7. The method according to claim 1, characterized in that the growth of ZnO nanorods/nanorods dispersed in the growing aqueous suspension is carried out by a probe sonication technique, wherein the suspension in the growing aqueous solution of graphene nanoplatelets coated with a seed layer from step 2, which has been transferred into a glass beaker, is sonicated by a probe processor for a time comprised between 5 minutes and 60 minutes, fixing the oscillation amplitude of the probe between 20% and 100% of its maximum value.
8. The method according to any one of the preceding claims, wherein once the growth step is completed, the suspension is centrifuged to remove the growth solution and washed twice with deionized water; and is
The resulting precipitate is dried in an oven at a temperature of 70 ℃ to 180 ℃ for 10 to 30 minutes.
9. The method according to claim 1, characterized in that, starting from step 1, Graphene Oxide (GO) or reduced graphene oxide (rGO) is used instead of graphene nanoplatelets.
10. Graphene nanoplatelets modified with zinc oxide nanorods or nanorods having a diameter of 100-300nm and a length of 1-2 μm obtained using the method according to any one of claims 1-4, 8-9 and using the hydrothermal technique under static conditions as described in claim 5.
11. Graphene nanoplatelets modified with zinc oxide nanorods obtained using the method according to any one of claims 1 to 4, 8 to 9 and using the hydrothermal technique under dynamic conditions as described in claim 6, wherein the zinc oxide nanorods have a diameter of 20 to 40nm and a length of 500-800 nm.
12. Graphene nanoplatelets modified with zinc oxide nanorods, obtained using the method according to any one of claims 1-4, 8-9 and using the probe described in claim 7, wherein the zinc oxide nanorods have a diameter of 20-40nm and a length of not more than 300nm, having a reduced aspect ratio compared to zinc oxide nanorods or nanorods grown on seed coated graphene nanoplatelets obtained according to claims 5 and 6.
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