CN105642910A - Au nanoparticle composite nanosheets and preparation method thereof - Google Patents
Au nanoparticle composite nanosheets and preparation method thereof Download PDFInfo
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- CN105642910A CN105642910A CN201610052266.XA CN201610052266A CN105642910A CN 105642910 A CN105642910 A CN 105642910A CN 201610052266 A CN201610052266 A CN 201610052266A CN 105642910 A CN105642910 A CN 105642910A
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0551—Flake form nanoparticles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides Au-ZnSe-Amine composite nanosheets, which comprise ZnSe-Amine inorganic-organic hybrid nanosheets and Au nanoparticles combined at edges of the sheet layers thereof. The present invention also provides Au-ZnSe composite nanosheets, comprising ZnSe nanosheets and Au nanoparticles combined at edges of the sheet layers thereof. The Au-ZnSe-Amine composite nanosheets provided by the present invention are obtained by realizing selective edge growth of the Au nanoparticles on the ZnSe-Amine inorganic-organic hybrid nanosheets in accordance with the principles of layered orientation and defect preferred growth of organic-inorganic hybrid materials.
Description
Technical field
The present invention relates to nano material synthesis technical field, be specifically related to a kind of Au nano-particles reinforcement nanometer sheet and preparation method thereof.
Background technology
Au is a kind of precious metal material, and chemical property is highly stable, and Au nano-particle has followed this character of its body phase material, therefore has relatively stable, but has very abundant chemical physical property. the surface plasma body resonant vibration wavelength of gold nano grain can change with length-width ratio, from visible (550nm) to near-infrared (1550nm) continuously adjustabe, high surface field intensity enhancing effect (high to 10e7 times), great optical absorption and scattering section, and from 50% to 100% continuously adjustable photo-thermal conversion efficiency. optics due to these uniquenesses, photoelectricity, photo-thermal, photochemistry, and molecule biological property, Au nano-particle is just receiving strong concern in material supply section educational circles, and cause numerous material scholar, biochemist, physician, physicist, it is carried out extensive research by the researchers such as microelectronic engineering teacher, in life sciences, catalytic field, sensor aspect, optical element, thin-film solar cells, nano step standard, false proof, have a wide range of applications in the fields such as optical information storage and nano optoelectronics, particularly in biomarker, sensor builds, optical probe, electrochemical probe, tissue repair, DNA, the specific aspects such as glucose sensor.
Se is extraordinary mould material in nano material synthesis technical field. As " materials chemistry impurity " (JournalofMaterialsChemistry, 2006,16 volumes, 3893-3897 page) summarizes the selenides nano material synthetic technology being template with Se simple substance nanometer material. The organic-inorganic hybrid material of selenides has been similarly subjected to the great attention of scientist, such as Germany " advanced material " (AdvancedMaterials, 2005,17 volumes, 2,799 2802 pages) report in ternary mixed solvent (hydrazine hydrate: diethylenetriamine: water=5:14:16) and dissolve ZnSO4��7H2O and Na2SeO3, transfer in autoclave, synthesize [ZnSe] (DETA) by reacting 12h at 180 DEG C of temperature of hydro-thermal method0.5Two-dimensional nano band. [ZnSe] (DETA) that this method obtains0.5Nano belt pattern is homogeneous, and inside has many layer structures, has good ultraviolet-visible absorption and fluorescence property. For another example the report of " Germany applied chemistry " (AngewandteChemieInternationalEdition, 2012,51 volumes, 3211-3215 page) has modified synthetic method, ZnSO4��7H2O changes Zn (OAC) into2��2H2O, and strengthen throwing amount, hydro-thermal reaction 12h at 150 DEG C of temperature, synthesize ZnSe (DETA)0.5Nanometer sheet, the nanometer sheet obtained is wider longer than original nano belt, and length has micron order, width to have hundreds of nanometers, and has higher yield.Thus, selenides nano material has a wide range of applications in the field such as quasiconductor, catalysis.
In the art, the synthesis of a lot of selenides composite nano materials is all with selenides for template, it is re-introduced into metal ion, domestic and international periodical is of common occurrence about the report of " noble metal-quasiconductor " composite nano materials, in ZnS substrate, such as grow Au cluster (Nanotechnology,, 26 volumes, 325702 (9pp.) page in 2015), in ZnS-CdS hetero-junctions nanometer rods selective growth Au nano-particle etc.
Thus, how to utilize substrate material compound Au nano-particle, obtain more diversified nano composite material, it has also become forward position scholar is in one of direction carrying out breakthrough exploration of nanometer synthesis technical field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is in that to provide a kind of Au nano-particles reinforcement nanometer sheet and preparation method thereof, particularly a kind of Au-ZnSe-Amine composite nano plate and preparation method thereof and Au-ZnSe composite nano plate and preparation method thereof, Au nano-particles reinforcement nanometer sheet provided by the invention and preparation method, can controllably optionally at the marginal growth Au nano-particle of substrate lamella, the composite nano plate obtained has good photoelectric characteristic, has a good application prospect in opto-electronic conversion.
The invention provides a kind of Au-ZnSe-Amine composite nano plate, including ZnSe-Amine inorganic-organic hybridization nanometer sheet and the Au nano-particle being compounded in its lamella edge.
Preferably, described ZnSe-Amine inorganic-organic hybridization nanometer sheet is [ZnSe] (DETA)0.5Nanometer sheet.
The invention provides a kind of Au-ZnSe composite nano plate, including ZnSe nanometer sheet and the Au nano-particle being compounded in its lamella edge.
Preferably, in described composite nano plate, the mol ratio of Au and Se is 1:(2��4).
The preparation method that the invention provides a kind of Au-ZnSe-Amine composite nano plate, comprises the following steps:
A), after gold chloride, ZnSe-Amine inorganic-organic hybridization nanometer sheet and water being carried out hybrid reaction, Au-ZnSe-Amine composite nano plate is obtained.
Preferably, described ZnSe-Amine nanometer sheet is (2��4) with the mol ratio of gold chloride: 1.
Preferably, described step A) particularly as follows:
A1), after ZnSe-Amine inorganic-organic hybridization nanometer sheet and water being mixed, dispersion liquid is obtained;
A2), after the dispersion liquid aqueous solution addition above-mentioned steps of described gold chloride obtained reacting, Au-ZnSe-Amine composite nano plate is obtained.
Preferably, the concentration of the aqueous solution of described gold chloride is less than or equal to 2mg/mL;
Described being incorporated as is slowly added to, described in the speed that is slowly added to for less than or equal to 2mL/min.
The preparation method that the invention provides a kind of Au-ZnSe composite nano plate, comprises the following steps:
Under protective atmosphere; by the Au-ZnSe-Amine composite nano plate described in any one in technique scheme or Au-ZnSe-Amine composite nano plate prepared by any one in technique scheme; after carrying out high-temperature process, obtain Au-ZnSe composite nano plate.
Preferably, the temperature of described high-temperature process is 250��350 DEG C; The time of described high-temperature process is 1��4 hour.
The invention provides a kind of Au-ZnSe-Amine composite nano plate, including ZnSe-Amine inorganic-organic hybridization nanometer sheet and the Au nano-particle being compounded in its lamella edge. Present invention also offers a kind of Au-ZnSe composite nano plate, including ZnSe nanometer sheet and the Au nano-particle being compounded in its lamella edge.Compared with prior art, the present invention utilizes organic-inorganic hybrid material stratiform orientation and defect preferred growth principle, on ZnSe-Amine inorganic-organic hybridization composite nano plate, it is achieved that selectivity marginal growth Au nano-particle, obtain Au-ZnSe-Amine composite nano plate. This composite nano plate is under the high temperature conditions, it is possible to obtain on edge the selective growth Au-ZnSe inorganic composite nano sheet of Au nano-particle further. Test result indicate that, Au nano-particles reinforcement nanometer sheet provided by the invention and preparation method, can controllably optionally at the marginal growth Au nano-particle of substrate lamella, the composite nano plate obtained has good photoelectric characteristic, shows good application prospect in opto-electronic conversion.
Accompanying drawing explanation
Fig. 1 is the reaction process schematic diagram of the preparation method of Au-ZnSe-Amine composite nano plate provided by the invention;
Fig. 2 is the ZnSe (DETA) of the embodiment of the present invention 1 preparation0.5The TEM photo of inorganic-organic hybridization nanometer sheet;
Fig. 3 is transmission electron microscope (TEM) photo of the Au-ZnSe-Amine composite nano plate of the embodiment of the present invention 2 preparation;
Fig. 4 is transmission electron microscope (TEM) photo of the Au-ZnSe-Amine composite nano plate of the embodiment of the present invention 2 preparation;
Fig. 5 is high resolution transmission electron microscopy (HRTEM) photo and the growth mechanism analysis schematic diagram of the Au-ZnSe-Amine composite nano plate of the embodiment of the present invention 2 preparation;
Fig. 6 is the ZnSe (DETA) of the embodiment of the present invention 1 preparation0.5With X-ray diffraction (XRD) the relative analysis collection of illustrative plates of the Au-ZnSe-Amine of embodiment 2 preparation, the form in the lower right corner is the EDS element ratio analytical data of Au, Zn, Se in Au-ZnSe-Amine composite nano plate;
Fig. 7 is transmission electron microscope (TEM) photo of the Au-ZnSe inorganic composite nano sheet of the embodiment of the present invention 3 preparation;
Fig. 8 is the XRD figure spectrum of the Au-ZnSe inorganic composite nano sheet of the embodiment of the present invention 3 preparation;
Fig. 9 is near-infrared (IR) absorption spectrum of the Au-ZnSe inorganic composite nano sheet of the embodiment of the present invention 3 preparation;
Figure 10 is ultraviolet-visible absorption spectroscopy and the photoelectric current test curve of Au-ZnSe inorganic composite nano sheet prepared by the present invention.
Detailed description of the invention
In order to further appreciate that the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but it is to be understood that these describe simply as to further illustrate the features and advantages of the present invention rather than the restriction to patent requirements of the present invention.
The all raw materials of the present invention, be not particularly limited its source, that commercially buy or prepare according to conventional method well known to those skilled in the art.
The all raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analytical pure.
The invention provides a kind of Au-ZnSe-Amine composite nano plate, including ZnSe-Amine inorganic-organic hybridization nanometer sheet and the Au nano-particle being compounded in its lamella edge.
Described ZnSe-Amine inorganic-organic hybridization nanometer sheet is not particularly limited by the present invention, and with ZnSe-Amine inorganic-organic hybridization nanometer sheet well known to those skilled in the art, the present invention is preferably [ZnSe] (DETA)0.5Nanometer sheet; The present invention is to described [ZnSe] (DETA)0.5The source of nanometer sheet is not particularly limited, those skilled in the art can according to know method preparation or commercially, the present invention is preferably with reference to reporting document (AdvancedMaterials, 2005,17 volumes, 2,799 2802 pages) and (AngewandteChemieInternationalEdition, 2012,51 volumes, 3211-3215 page) in method, Hydrothermal Synthesis ZnSe (DETA)0.5Inorganic-organic hybridization nanometer sheet.The present invention is to described [ZnSe] (DETA)0.5The specific nature of nanometer sheet is not particularly limited, and those skilled in the art can carry out selecting and adjusting according to said method, and the present invention is preferably described [ZnSe] (DETA)0.5Nano belt pattern is homogeneous, and inside has many layer structures, has good ultraviolet-visible absorption and fluorescence property.
Described compound is not particularly limited by the present invention, with the concept of compound well known to those skilled in the art, it is possible to be covering, half mulching, stacking or growth in one or more, the present invention be preferably growth. The lamella edge of described hybridized nanometer sheet is not particularly limited by the present invention, and with the concept at the edge of the single lamella of nanometer sheet well known to those skilled in the art, the present invention refers to the edge of single nanoscale twins surrounding. The particle diameter of described Au nano-particle is not particularly limited by the present invention, and those skilled in the art can require to be adjusted according to practical situation, technological parameter or properties of product, and the present invention is preferably 1��5nm, more preferably 2��4nm, it is most preferred that be 2.5��3.5nm. The present invention is in described Au-ZnSe-Amine composite nano plate, the mol ratio of Au and Se is not particularly limited, those skilled in the art can require to be adjusted according to actual growing state, technological parameter or properties of product, in composite nano plate of the present invention, the mol ratio of Au and Se is preferably 1:(2��4), it is more preferably 1:(2.25��3.75), it is more preferably 1:(2.5��3.5), it is most preferred that for 1:(2.75��3.25).
Present invention also offers a kind of Au-ZnSe composite nano plate, including ZnSe nanometer sheet and the Au nano-particle being compounded in its lamella edge.
Described ZnSe nanometer sheet is not particularly limited by the present invention, with ZnSe nanometer sheet well known to those skilled in the art; The source of described ZnSe nanometer sheet is not particularly limited by the present invention, and those skilled in the art can prepare according to the method known or commercially, the present invention is preferably obtained after high-temperature process by ZnSe-Amine inorganic-organic hybridization nanometer sheet.
The specific nature of described ZnSe nanometer sheet is not particularly limited by the present invention, and those skilled in the art can carry out selecting and adjusting, and the preferred described ZnSe nanometer sheet pattern of the present invention is homogeneous, has good ultraviolet-visible absorption performance.
Described compound is not particularly limited by the present invention, with the concept of compound well known to those skilled in the art, it is possible to be covering, half mulching, stacking or growth in one or more, the present invention be preferably growth. The lamella edge of described ZnSe nanometer sheet is not particularly limited by the present invention, and with the concept at nanometer sheet lamella edge well known to those skilled in the art, the present invention refers to the edge of nanometer sheet surrounding. The particle diameter of described Au nano-particle is not particularly limited by the present invention, those skilled in the art can require to be adjusted according to practical situation, technological parameter or properties of product, and the present invention is preferably 10��30nm, more preferably 12��28nm, it is more preferably 15��25nm, it is most preferred that be 18��22nm. The present invention is in described Au-ZnSe composite nano plate, the mol ratio of Au and Se is not particularly limited, those skilled in the art can require to be adjusted according to actual growing state, technological parameter or properties of product, in composite nano plate of the present invention, the mol ratio of Au and Se is preferably 1:(2��4), it is more preferably 1:(2.25��3.75), it is more preferably 1:(2.5��3.5), it is most preferred that for 1:(2.75��3.25).
The preparation method that present invention also offers a kind of Au-ZnSe-Amine composite nano plate, comprises the following steps:
A), after gold chloride, ZnSe-Amine inorganic-organic hybridization nanometer sheet and water being carried out hybrid reaction, Au-ZnSe-Amine composite nano plate is obtained.
The optimum principles such as the character of raw material, structure and ratio described in preparation method of the present invention or concrete preferred version are all consistent with the optimum principle of aforementioned Au-ZnSe-Amine composite nano plate and concrete preferred version, and this is no longer going to repeat them.
The mol ratio of ZnSe-Amine nanometer sheet of the present invention and gold chloride is preferably (2��4): 1, it is more preferably (2.25��3.75): 1, it is more preferably (2.5��3.5): 1, it is most preferred that for (2.75��3.25): 1.
The present invention improves the performance of Au-ZnSe-Amine composite nano plate, described step A) preferably specifically carry out according to following steps:
A1), after ZnSe-Amine inorganic-organic hybridization nanometer sheet and water being mixed, dispersion liquid is obtained
A2), after the dispersion liquid aqueous solution addition above-mentioned steps of described gold chloride obtained reacting, Au-ZnSe-Amine composite nano plate is obtained.
The present invention obtains dispersion liquid after first ZnSe-Amine inorganic-organic hybridization nanometer sheet and water being mixed. The source of ZnSe-Amine inorganic-organic hybridization nanometer sheet of the present invention is consistent with the source of aforementioned ZnSe-Amine inorganic-organic hybridization nanometer sheet and optimum principle with optimum principle, and this is no longer going to repeat them. Described mixing is not particularly limited by the present invention, and with hybrid mode well known to those skilled in the art, the present invention is preferably stirring, more preferably magnetic agitation. The mixing speed of described stirring mixing is not particularly limited by the present invention, can better be dispersed in aqueous phase solvent for preferred version with ZnSe-Amine inorganic-organic hybridization nanometer sheet. The ratio of described ZnSe-Amine inorganic-organic hybridization nanometer sheet and water is not particularly limited by the present invention, those skilled in the art can require to be adjusted according to practical situation, technological parameter or properties of product, can be dispersed for preferred version with ZnSe-Amine inorganic-organic hybridization nanometer sheet.
The present invention obtains after dispersion liquid through above-mentioned steps, then after the aqueous solution of described gold chloride being added and reacting in the dispersion liquid that above-mentioned steps obtains, obtains Au-ZnSe-Amine composite nano plate.
The concentration of the aqueous solution of described gold chloride is not particularly limited by the present invention, those skilled in the art can require to be adjusted according to practical situation, technological parameter or properties of product, the present invention is preferably less than equal to 2mg/mL, it is more preferably less than equal to 1.8mg/mL, it is most preferred that for less than or equal to 1.5mg/mL. The mode of described addition is not particularly limited by the present invention, concentration with the chlorauric acid solution for this type of reaction well known to those skilled in the art, those skilled in the art can require to be adjusted according to practical situation, technological parameter or properties of product, the present invention is preferably and is slowly added to, it is more preferably dropping, more preferably utilize syringe pump to drip; The speed being slowly added to of the present invention is preferably less than equal to 2mL/min, more preferably less than or equal to 1.8mg/mL, it is most preferred that for less than or equal to 1.5mg/mL.
The present invention, after above-mentioned steps, obtains Au-ZnSe-Amine composite nano plate. The invention first in aqueous phase solvent, utilize the stratiform orientation selectivity growth noble metal of organic-inorganic hybrid material, and utilize defect preferred growth principle, on ZnSe-Amine inorganic-organic hybridization composite nano plate, achieve selective at lamella marginal growth Au nano-particle, obtain Au-ZnSe-Amine composite nano plate.And the present invention can also pass through adjustment ratio and condition, it is achieved controllability grows, thus adjusting the performance of follow-up opto-electronic conversion aspect.
Reaction process schematic diagram referring to the preparation method that Fig. 1, Fig. 1 are Au-ZnSe-Amine composite nano plate provided by the invention.
The preparation method that the invention provides a kind of Au-ZnSe composite nano plate, comprises the following steps:
Under protective atmosphere; by the Au-ZnSe-Amine composite nano plate described in any one in technique scheme or Au-ZnSe-Amine composite nano plate prepared by any one in technique scheme; after carrying out high-temperature process, obtain Au-ZnSe composite nano plate.
The optimum principles such as the character of raw material, structure and ratio described in preparation method of the present invention or concrete preferred version are all consistent with the optimum principle of aforementioned Au-ZnSe composite nano plate and concrete preferred version, and this is no longer going to repeat them.
The Au-ZnSe-Amine composite nano plate that the present invention will obtain through above-mentioned steps, after carrying out high-temperature process, obtains Au-ZnSe composite nano plate. The condition of described high-temperature process is not particularly limited by the present invention, the condition of organic element is removed with inorganic-organic hybridization nanometer sheet well known to those skilled in the art, the temperature of high-temperature process of the present invention is preferably 250��350 DEG C, it is more preferably 260��340 DEG C, it is more preferably 270��330 DEG C, more preferably 290��310 DEG C; The time of described high-temperature process is preferably 1��4 hour, more preferably 1.5��3.5 hours, more preferably 2��3 hours, it is most preferred that be 2.2��2.8 hours. Described protective atmosphere is not particularly limited by the present invention, and with protective atmosphere well known to those skilled in the art, the present invention is preferably nitrogen or noble gas, more preferably nitrogen. The equipment of described high-temperature process is not particularly limited by the present invention, and with the equipment of high-temperature process well known to those skilled in the art, the present invention is preferably tube furnace.
The present invention eliminates the Amine of Au-ZnSe-Amine composite nano plate by high-temperature process, obtains Au-ZnSe inorganic composite nano sheet.
The present invention utilizes organic-inorganic hybrid material stratiform orientation and defect preferred growth principle, on ZnSe-Amine inorganic-organic hybridization composite nano plate, achieve selectivity marginal growth Au nano-particle, obtain Au-ZnSe-Amine composite nano plate, then proceed by high-temperature process, obtain on nanometer sheet edge the selective growth Au-ZnSe inorganic composite nano sheet of Au nano-particle further. Test result indicate that, Au nano-particles reinforcement nanometer sheet provided by the invention and preparation method, can controllably optionally at the marginal growth Au nano-particle of substrate lamella, the composite nano plate obtained has good photoelectric characteristic, shows good application prospect in opto-electronic conversion.
In order to be further appreciated by the present invention; below in conjunction with embodiment, a kind of Au-ZnSe-Amine composite nano plate provided by the invention and preparation method thereof and Au-ZnSe composite nano plate and preparation method thereof being illustrated, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Preparation ZnSe-Amine nanometer sheet substrate:
With reference to reported document (AdvancedMaterials, 2005,17 volumes, 2,799 2802 pages; AngewandteChemieInternationalEdition, 2012,51 volumes, 3,211 3215 pages) Hydrothermal Synthesis ZnSe (DETA)0.5Inorganic-organic hybridization nanometer sheet.Concrete grammar is as follows:
In the beaker of 100ml, add 5ml hydrazine hydrate, 14ml diethylenetriamine and 16ml water, continuous magnetic agitation 10min mix homogeneously, add Zn (OAC)2��2H2O (3mmol) and Na2SeO3(3mmol), it is stirred for 10min and forms homogeneous solution, transfer in 50ml autoclave, heat the 12h time at 140 DEG C of temperature. After natural cooling, centrifuging and taking precipitate. Be respectively adopted JEOLJEM-2011 transmission electron microscope (TEM), gained solid product sample is characterized by PW1710X-x ray diffractometer x (XRD).
Referring to the ZnSe (DETA) that Fig. 2, Fig. 2 are the embodiment of the present invention 1 preparation0.5The TEM photo of inorganic-organic hybridization nanometer sheet. Referring to the ZnSe (DETA) that Fig. 6, Fig. 6 are the embodiment of the present invention 1 preparation0.5X-ray diffraction (XRD) relative analysis collection of illustrative plates with the Au-ZnSe-Amine of embodiment 2 preparation. Such as XRD figure spectrum it can be seen that the ZnSe (DETA) for preparing of the present invention0.5Consistent with bibliographical information.
Embodiment 2 grows Au nano-particle in substrate:
In the tap web bottle of 50ml, add 30ml deionized water, add 0.075mmolZnSe (DETA)0.5Nanometer sheet, continuing magnetic force dispersed with stirring is uniform, drips chlorauric acid solution 10ml (solution concentration is 1mg/ml, and injection speed is 1ml/min) with syringe pump. It is observed that the color of solution is turned black by white. Natural sedimentation, discards the supernatant, and taking precipitate washes with water repeatedly. Be respectively adopted JEOLJEM-2011 transmission electron microscope (TEM), gained solid product sample is characterized by PW1710X-x ray diffractometer x (XRD).
Transmission electron microscope (TEM) photo referring to the Au-ZnSe-Amine composite nano plate that Fig. 3, Fig. 3 are the embodiment of the present invention 2 preparation. Transmission electron microscope (TEM) photo referring to the Au-ZnSe-Amine composite nano plate that Fig. 4, Fig. 4 are the embodiment of the present invention 2 preparation. Schematic diagram analyzed by high resolution transmission electron microscopy (HRTEM) photo and growth mechanism referring to the Au-ZnSe-Amine composite nano plate that Fig. 5, Fig. 5 are the embodiment of the present invention 2 preparation.
By Fig. 3 and Fig. 4 it can be seen that gold grain is grown in ZnSe (DETA) equably0.5The edge of nanometer sheet. Again as shown in Figure 5, the lattice fringe illustrating edge granule of HRTEM apparent is consistent with the lattice fringe spacing of Au, further confirms that the granule at edge is Au nano-particle.
Au nanoparticulate selective is grown in ZnSe (DETA)0.5The reason at nanometer sheet edge is attributed to two aspects:
1��ZnSe(DETA)0.5The lattice fringe spacing that the nanometer sheet surface parallel with stratiform direction is mated with Au, so Au nano-particle is not easy in its superficial growth; 2, the ultra-thin inorganic sheet of the Amine that the preferential flank of hydrion inside chlorauric acid solution comes out, side place ZnSe is unstable, and lattice rearranges, and forms defect, and Au nano-particle preferred growth is in defect.
Referring back to the ZnSe (DETA) that Fig. 6, Fig. 6 are the embodiment of the present invention 1 preparation0.5X-ray diffraction (XRD) relative analysis collection of illustrative plates with the Au-ZnSe-Amine of embodiment 2 preparation. The form in the lower right corner is the EDS element ratio analytical data of Au, Zn, Se in Au-ZnSe-Amine composite nano plate. It will be appreciated from fig. 6 that XRD figure spectrum clearly show that lattice diffractive features peak and the ZnSe (DETA) of Au0.5The primitive character peak of nanometer sheet substrate, EDS power spectrum elementary analysis result draws Au:Se:Zn �� 0.5:1:1.
Embodiment 3 high-temperature process removes Amine:
Case study on implementation 2 products therefrom is placed in tube furnace, in a nitrogen atmosphere, calcines 2 hours for 300 degrees Celsius, recovery sample of annealing.It is respectively adopted JEOLJEM-2011 transmission electron microscope (TEM), PW1710X-x ray diffractometer x (XRD) and near-infrared (IR) absorption apparatus gained solid product sample is characterized.
Transmission electron microscope (TEM) photo referring to the Au-ZnSe inorganic composite nano sheet that Fig. 7, Fig. 7 are the embodiment of the present invention 3 preparation. As seen from Figure 7, Au nano-particle is still at the edge of nanometer sheet substrate, but the size of Au nano-particle becomes greatly relative to embodiment 2. XRD figure spectrum referring to the Au-ZnSe inorganic composite nano sheet that Fig. 8, Fig. 8 are the embodiment of the present invention 3 preparation. Being composed by the XRD figure of Fig. 8, products therefrom is Au and ZnSe complex, containing a small amount of AuSe impurity. Near-infrared (IR) absorption spectrum referring back to the Au-ZnSe inorganic composite nano sheet that Fig. 9, Fig. 9 are the embodiment of the present invention 3 preparation. Being shown by the IR absorption spectroanalysis of Fig. 9, Organic substance removes, and products therefrom is Au-ZnSe inorganic composite nano sheet.
Embodiment 4 performance test:
The ultraviolet-visible absorption spectroscopy scope of Au-ZnSe inorganic composite nano sheet prepared by above-described embodiment and photo-current intensity carry out test and characterize.
Ultraviolet-visible absorption spectroscopy test condition: using ShimadzuUV-240 ultra-violet absorption spectrum instrument, scanning optical spectrum ranges for 200-900nm, medium sweep.
Photo-current intensity test condition:
(1) sampling. Disperse 1mg solid sample with 1ml ethanol, drop in ITO mono-, the 500rpm spin coating 30s (the effective spin coating area of ITO is 1*1cm, blocks diffusion path with adhesive tape, and the sample lens paper diffused out is wiped) of 1*5cm.
(2) test condition. Light source is the xenon lamp of 300W, and intensity of illumination is 50mW.cm-2; The ITO of sample preparation makes working electrode, and Ag/AgCl makes reference electrode, and Pt sheet makes auxiliary electrode, uses 0.5MNa2SO4Make electrolyte. Testing on CHI760D electrochemical workstation, bias voltage ranges is from-0.4 to 0.8V.
Referring to the ultraviolet-visible absorption spectroscopy that Figure 10, Figure 10 are Au-ZnSe inorganic composite nano sheet prepared by the present invention and photoelectric current test curve. As shown in Figure 10, the light of 200��900nm wave-length coverage is had certain Absorption by this material, and its absworption peak is near 300nm. Under given test condition, the photo-current intensity of this material shows as tens and arrives hundreds of microampere; Prolongation over time, shows faint decay. Above-mentioned test result shows, this material has good application prospect in opto-electronic conversion.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention. It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention. The multiple amendment of these embodiments be will be apparent from for those skilled in the art, and generic principles defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments. Therefore, the present invention is not intended to be limited to the embodiments shown herein, and is to fit to the widest scope consistent with principles disclosed herein and features of novelty.
Claims (10)
1. an Au-ZnSe-Amine composite nano plate, it is characterised in that include ZnSe-Amine inorganic-organic hybridization nanometer sheet and be compounded in the Au nano-particle at its lamella edge.
2. composite nano plate according to claim 1, it is characterised in that described ZnSe-Amine inorganic-organic hybridization nanometer sheet is [ZnSe] (DETA)0.5Nanometer sheet.
3. an Au-ZnSe composite nano plate, it is characterised in that include ZnSe nanometer sheet and be compounded in the Au nano-particle at its lamella edge.
4. the composite nano plate according to claims 1 to 3 any one, it is characterised in that in described composite nano plate, the mol ratio of Au and Se is 1:(2��4).
5. the preparation method of an Au-ZnSe-Amine composite nano plate, it is characterised in that comprise the following steps:
A), after gold chloride, ZnSe-Amine inorganic-organic hybridization nanometer sheet and water being carried out hybrid reaction, Au-ZnSe-Amine composite nano plate is obtained.
6. preparation method according to claim 5, it is characterised in that the mol ratio of described ZnSe-Amine nanometer sheet and gold chloride is (2��4): 1.
7. preparation method according to claim 5, it is characterised in that described step A) particularly as follows:
A1), after ZnSe-Amine inorganic-organic hybridization nanometer sheet and water being mixed, dispersion liquid is obtained;
A2), after the dispersion liquid aqueous solution addition above-mentioned steps of described gold chloride obtained reacting, Au-ZnSe-Amine composite nano plate is obtained.
8. preparation method according to claim 7, it is characterised in that the concentration of the aqueous solution of described gold chloride is less than or equal to 2mg/mL;
Described being incorporated as is slowly added to, described in the speed that is slowly added to for less than or equal to 2mL/min.
9. the preparation method of an Au-ZnSe composite nano plate, it is characterised in that comprise the following steps:
Under protective atmosphere; by the Au-ZnSe-Amine composite nano plate described in any one in claim 1��2 or Au-ZnSe-Amine composite nano plate prepared by any one in claim 5��8; after carrying out high-temperature process, obtain Au-ZnSe composite nano plate.
10. preparation method according to claim 9, it is characterised in that the temperature of described high-temperature process is 250��350 DEG C; The time of described high-temperature process is 1��4 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321368A (en) * | 2017-08-17 | 2017-11-07 | 中国科学技术大学先进技术研究院 | A kind of CoSe of Au atoms modification2Nanobelt and its preparation method and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1857575A2 (en) * | 2006-05-16 | 2007-11-21 | Samsung Electronics Co., Ltd. | Semiconductor nanocrystal-metal complex and method of preparing the same |
| US20080102201A1 (en) * | 2006-10-30 | 2008-05-01 | Samsung Electronics Co., Ltd. | Method For Dispersing Nanoparticles and Methods for Producing Nanoparticle Thin Films By Using The Same |
| WO2009026141A1 (en) * | 2007-08-17 | 2009-02-26 | University Of Florida Research Foundation, Inc. | Supercrystalline colloidal particles and method of production |
| CN102211198A (en) * | 2011-05-25 | 2011-10-12 | 云南大学 | Method for synthesizing water-soluble Pt: ZnSe(S) alloyed nanometer crystal by using hydro-thermal method |
| CN103840052A (en) * | 2012-11-23 | 2014-06-04 | 乐金显示有限公司 | Quantum rod and method of fabricating same |
| CN104445102A (en) * | 2014-11-27 | 2015-03-25 | 中国科学技术大学 | Method for synthesizing ultrathin Se nanosheet through acidification, stripping and oxidization of precursors and application of ultrathin Se nanosheet |
| CN104646658A (en) * | 2013-11-16 | 2015-05-27 | 西安交大京盛科技发展有限公司 | Method for preparing hybridized nanocrystallines |
-
2016
- 2016-01-25 CN CN201610052266.XA patent/CN105642910B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1857575A2 (en) * | 2006-05-16 | 2007-11-21 | Samsung Electronics Co., Ltd. | Semiconductor nanocrystal-metal complex and method of preparing the same |
| US20080102201A1 (en) * | 2006-10-30 | 2008-05-01 | Samsung Electronics Co., Ltd. | Method For Dispersing Nanoparticles and Methods for Producing Nanoparticle Thin Films By Using The Same |
| WO2009026141A1 (en) * | 2007-08-17 | 2009-02-26 | University Of Florida Research Foundation, Inc. | Supercrystalline colloidal particles and method of production |
| CN102211198A (en) * | 2011-05-25 | 2011-10-12 | 云南大学 | Method for synthesizing water-soluble Pt: ZnSe(S) alloyed nanometer crystal by using hydro-thermal method |
| CN103840052A (en) * | 2012-11-23 | 2014-06-04 | 乐金显示有限公司 | Quantum rod and method of fabricating same |
| CN104646658A (en) * | 2013-11-16 | 2015-05-27 | 西安交大京盛科技发展有限公司 | Method for preparing hybridized nanocrystallines |
| CN104445102A (en) * | 2014-11-27 | 2015-03-25 | 中国科学技术大学 | Method for synthesizing ultrathin Se nanosheet through acidification, stripping and oxidization of precursors and application of ultrathin Se nanosheet |
Non-Patent Citations (1)
| Title |
|---|
| XUAN WU,ET AL: "Synthesis of Hollow CdxZn1-xSe Nanoframes through the Selective Cation Exchange of Inorganic–Organic Hybrid ZnSe–Amine Nanoflakes with Cadmium Ions", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321368A (en) * | 2017-08-17 | 2017-11-07 | 中国科学技术大学先进技术研究院 | A kind of CoSe of Au atoms modification2Nanobelt and its preparation method and application |
| CN107321368B (en) * | 2017-08-17 | 2020-05-08 | 中国科学技术大学先进技术研究院 | Au atom modified CoSe2Nanobelt and preparation method and application thereof |
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