CN1759965A - Method for synthesizing Nano balls of cuprous oxide, and application of Nano balls of cuprous oxide - Google Patents
Method for synthesizing Nano balls of cuprous oxide, and application of Nano balls of cuprous oxide Download PDFInfo
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- CN1759965A CN1759965A CN 200510086782 CN200510086782A CN1759965A CN 1759965 A CN1759965 A CN 1759965A CN 200510086782 CN200510086782 CN 200510086782 CN 200510086782 A CN200510086782 A CN 200510086782A CN 1759965 A CN1759965 A CN 1759965A
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Abstract
A process for synthesizing the cuprous oxide nanoballs includes such steps as dissolving the Cu salt in water-soluble organic solvent, sequentially adding non-ionic surfactant and strong reducer, and reflux at 70-90 deg.C in an open system to obtain quasi-single-dispersed cuprous oxide nanoballs. Said cuprous oxide can be self-assembled on silicon chip or electrically conductive glass to form 2D or 3D structure for meeting the requirement of solar cell or microelectronic device.
Description
The technical field is as follows:
the invention relates to the technical field of methods for controlling the appearance of P-type semiconductor oxide and forming a composite core-shell structure with other N-type semiconductors in the appearance control synthesis of inorganic functional materials.
Background art:
cuprous oxide and copper oxide are good P-type semiconductors, and can be applied to the fields of solar energy conversion, microelectronics, magnetic storage, catalysis, gas sensitivity and the like. After reaching the nanometer level, the nanometer-level composite material has great potential application in solar cells, microelectronic devices, gas catalysis, gas sensors and the like due to the large specific surface area and excellent surface physical and chemical properties.
So far, the research reports at home and abroad mainly focus on controlling the nanometer morphology. The shapes of the cuprous oxide nanowires, nanowhiskers, nano cubes and the like have been reported or patented. For example, micron single crystal cubic blocks are synthesized by the national Qianyitai group. Copper oxide microspheres and cuprous oxide hollow spheres have been reported by Zeng et al abroad. Although cuprous oxide microspheres have been reported abroad, the reaction temperature is high, the reaction time is long, and the large-scale production is not facilitated. The low-temperature synthesis of monodisperse (uniform in size and shape) cuprous oxide nanospheres has not been reported at home and abroad.
The invention content is as follows:
the invention aims to provide a method for quickly synthesizing quasi-monodisperse cuprous oxide nanospheres at low temperature, which can synthesize a large amount of quasi-monodisperse cuprous oxide nanospheres at low temperature by using a simple reflux device and cheap and easily-obtained raw materials. Due to the uniform size and shape, the obtained cuprous oxide can form a two-dimensional or three-dimensional self-assembly mode on a silicon wafer or conductive glass so as to meet the stricter requirements on the aspects of solar cells ormicroelectronic devices. The cuprous oxide nanospheres obtained by the method are used as raw materials, and the quasi-monodisperse copper oxide or copper nanospheres are obtained by a gas phase reduction or oxidation method. The obtained cuprous oxide or cupric oxide is combined with other N-type semiconductors to form various P-N core-shell semiconductor composite structures so as to meet the requirements of gas sensors, microelectronic devices and the like. The main chemical reaction involved is as follows:
the invention is characterized in that: it comprises the following steps in sequence:
1) dissolving copper salt in an organic solvent which can be mutually dissolved with water to prepare a copper ion solution with the concentration of 0.025-0.2 mol/l;
2) adding a nonionic surfactant into the copper ion solution, stirring and dissolving, wherein the concentration of the nonionic surfactant is 0.005-0.05 mol/l;
3) adding a strong reducing agent into the solution prepared in the step 2), wherein the concentration of the strong reducing agent is 0.025-0.2 mol/l;
4) and (3) keeping the temperature of the solution prepared in the step (3) at 70-90 ℃, and refluxing in an open system to obtain the quasi-monodisperse cuprous oxide nanospheres.
The water-miscible organic solvent is N, N dimethylformamide, ethylene glycol or ethanol. The copper salt is copper acetate, copper sulfate, copper nitrate or copper chloride. The nonionic surfactant is polyvinylpyrrolidone or polyethylene glycol. The strong reducing agent is sodium borohydride or potassium borohydride.
The method for further preparing the copper oxide nanospheres by using the cuprous oxide nanospheres prepared by the method is characterized in that the cuprous oxide nanospheres are subjected to heat treatment for more than 1 hour at the temperature of 300-600 ℃ under the air atmosphere to obtain the quasi-monodisperse copper oxide nanospheres.
The method for further preparing the copper nanospheres by using the cuprous oxide nanospheres prepared by the method is characterized in that the cuprous oxide nanospheres react for 1-2 hours at the temperature of 200-400 ℃ in a reducing atmosphere to obtain the quasi-monodisperse copper nanospheres.
The method for further preparing the metal oxide core-shell nano-sphere structure by utilizing the cuprous oxide nano-spheres prepared by the method is characterized in that,
1) soaking the cuprous oxide nanospheres in an aqueous solution or an organic solution of corresponding salt of N-type semiconductor metal oxide, adjusting the pH value to 7-9, stirring simultaneously, and then performing centrifugal treatment, wherein the concentration of the salt is 0.01-2 mmol/l;
2) and (3) in an air atmosphere or an inert gas atmosphere, performing high-temperature treatment at 300-600 ℃ on the product obtained through the centrifugal treatment to obtain a core-shell nano-sphere structure of cuprous oxide and N-type semiconductor metal oxide or a core-shell nano-sphere structure of cupric oxide and N-type semiconductor metal oxide.
The corresponding salt of the cuprous oxide N-type semiconductor metal oxide is a tin salt, a titanium salt, a zinc salt, or an indium salt.
The test proves that: the invention can synthesize a large amount of quasi-monodisperse cuprous oxide nanospheres, can further prepare the cuprous oxide nanospheres and the copper nanospheres by using the product cuprous oxide nanospheres as a raw material, can be combined with other N-type semiconductors to form various P-N core-shell semiconductor composite structures, and has wide application prospect in a plurality of fields such as solar cells, catalysts, gas sensors and the like.
Description of the drawings:
FIG. 1 cuprous oxide X-ray powder diffraction;
FIG. 2 cuprous oxide TEM and electron diffraction detection;
FIG. 3 is SEM electron microscope detection of cuprous oxide;
FIG. 4 is SEM electron microscope detection of regular two-dimensional and three-dimensional close packing of cuprous oxide;
FIG. 5 copper oxide X-ray diffraction analysis;
FIG. 6 detection of copper oxide by SEM electron microscope;
FIG. 7 copper X-ray diffraction analysis;
FIG. 8 copper SEM electron microscopy inspection;
FIG. 9 SEM electron microscopy analysis of copper oxide/tin oxide core-shell structures;
FIG. 10 EDS spectroscopy elemental analysis of copper oxide/tin oxide core-shell structures.
The specific implementation mode is as follows:
the following are examples of experiments and results of the preparation of the cuprous oxide nanospheres, the copper nanospheres, and the formation of the core-shell structure of the cuprous oxide nanospheres and other semiconductor materials by the method of the present invention.
The first embodiment is as follows:
0.4g of analytically pure copper acetate (Cu (CH)3COO)2.H2O) was placed in a 100ml three-necked flask, anddissolving 30ml of N, N-dimethylformamide, adding 0.165g of PVP (molecular weight 30000), stirring for dissolving, adding 0.04g of sodium borohydride, heating to 80 ℃ by using an oil bath or a water bath for 2 minutes until the color becomes orange red, and centrifuging to obtain orange powder. The product was identified as cubic cuprous oxide by X-ray powder diffraction, as shown in figure 1; and (3) detecting the product appearance by using an SEM (scanning electron microscope) and a TEM (transmission electron microscope): nanospheres of size 200 nm, electron diffraction of a single sphere demonstrated that the product had a tendency to become single crystal, as shown in figures 2 and 3. The obtained cuprous oxide was dispersed in ethanol to form an orange sol, which was dropped on a silicon wafer or conductive glass to form a self-assembly form in a close-packed form, as shown in fig. 4. Putting the obtained cuprous oxide powder on a porcelain boat or dropping ethanol sol of the cuprous oxide on a Si sheet, then putting the cuprous oxide powder in a muffle furnace, and heating the cuprous oxide powder to 500 ℃ at a heating rate of 500 ℃/hour for 1 hour under an air atmosphere to obtain copper oxide nanospheres; identified as monoclinic phase copper oxide by X-ray powder diffraction, as shown in FIG. 5; scanning electron microscopy showed that the morphology and size of the nanospheres were essentially unchanged, as shown in figure 6. Putting the cuprous oxide into a quartz tube furnace, and introducing CO + N2(volume ratio 1: 9) gas, heating up to 400 ℃ at a heating rate of 600 ℃/hour, reacting for 1 hour to obtain nanospheres of purple metal copper, and identifying the nanospheres as cubic phase metal copperby X-ray powder diffraction, as shown in figure 7; the product morphology is still nano-spherical as detected by SEM electron microscopy, as shown in FIG. 8. 0.5mmol of sodium stannate (Na) was dissolved2SnO3.3H2O) in 40ml of distilled water, then 0.1g of the obtained cuprous oxide nanosphere powder was added, stirred for 1.5 hours, then centrifuged, and the obtained precipitate was placed in a porcelain boat, and then heat-treated at 500 ℃ for 2 hours in an air atmosphere to obtain CuO/SnO2The core-shell structure of nanospheres. The product is detected by SEM electron microscope, the appearance is still spherical, the surface becomes rough, as shown in FIG. 9; EDS energy spectrum analysis shows that SnO exists on the surface of the sphere2As shown in fig. 10.
Example two: 0.1g of analytically pure copper acetate (Cu (CH)3COO)2.H2O) was placed in a 100ml three-necked flask, and 20ml was addedDissolving N, N-dimethylformamide, adding0.055g PVP (molecular weight 1300000), stirring to dissolve, adding 0.14g potassium borohydride, heating to 90 deg.C with oil bath or water bath, 4 min later, the color becomes orange red, and centrifuging to obtain orange powder. The product is identified as cubic phase cuprous oxide by X-ray powder diffraction; and (3) detecting the product appearance by using an SEM (scanning electron microscope) and a TEM (transmission electron microscope): nanospheres of size 250 nm, electron diffraction of individual spheres was the same as in example one. Putting the obtained cuprous oxide powder in a porcelain boat, then putting the porcelain boat in a muffle furnace, and heating the porcelain boat to 300 ℃ at a heating rate of 500 ℃/hour for 2 hours in an air atmosphere to obtain copper oxide nanospheres; the monoclinic phase copper oxide is identified by X-ray powder diffraction; the scanning electron microscope detection shows that the shapesand the sizes of the nanospheres are basically unchanged. Putting the cuprous oxide into a quartz tube furnace, and introducing CO + N2Gas (volume ratio 1: 9), heating up to 300 ℃ at a heating rate of 600 ℃/hour, reacting for 1.5 hours to obtain nanospheres of purple metal copper, and identifying the nanospheres as cubic phase metal copper by X-ray powder diffraction; the appearance of the product is still nano-spherical and the size of the product is basically unchanged through SEM electron microscope detection. Dissolving 0.05mmol of zinc acetate in 40ml of distilled water, then adding 0.1g of the obtained cuprous oxide nanosphere powder, stirring for 2 hours, then carrying out centrifugal filtration, placing the obtained precipitate in a porcelain boat, and then carrying out heat treatment for 2 hours at 400 ℃ in an air atmosphere to obtain the CuO/ZnO nanosphere core-shell structure. The product is detected by an SEM electron microscope, and the shape is still spherical; EDS spectroscopy showed the presence of zinc oxide on the surface of the spheres.
Example three: 0.24g of analytically pure copper nitrate (Cu (NO) was taken3)2.3H2O) was placed in a 100ml three-necked flask, dissolved with 20ml of absolute ethanol, added with 0.111g of PVP (molecular weight 30000), stirred to dissolve, and then added with 0.01g of potassium borohydride, heated to 70 ℃ with an oil bath or water bath for 5 minutes, and then the color changed to orange-red, and centrifuged to obtain orange powder. The product is identified as cubic phase cuprous oxide by X-ray powder diffraction; and (3) detecting the product appearance by using an SEM (scanning electron microscope) and a TEM (transmission electron microscope): hollow nanospheres of size-250 nm. Putting the obtained cuprous oxide powder in a porcelain boat, then putting the porcelain boat in a muffle furnace, and heating the porcelain boat to 400 ℃ at a heating rate of 500 ℃/hour for 2 hours in an air atmosphere to obtain copper oxide nanospheres; by X-rayPowder diffraction was identified as monoclinic phase copper oxide; scanning electron microscope examination shows that the size of the nanosphere is not substantially changed. Putting the cuprous oxide into a quartz tube furnace, and introducing CO + N2Gas (volume ratio 1: 9), heating up to 400 ℃ at a heating rate of 600 ℃/hour, reacting for 1 hour to obtain nanospheres of purple metal copper, and identifying the nanospheres as cubic phase metal copper by X-ray powder diffraction; the appearance of the product is still nano-spherical and the size of the product is basically unchanged through SEM electron microscope detection. Dissolving 0.5ml of tetrabutyl titanate in 20ml of absolute ethyl alcohol; adding 0.2g of cuprous oxide nanosphere into 15ml of ethanol, stirring to form sol, adjusting the pH value of the cuprous oxide sol to be about 8-9 by using dilute ammonia water (10 percent, volume content), slowly dropwise adding an ethanol solution of tetrabutyl titanate into the cuprous oxide ethanol sol, stirring for 1 hour, and then carrying out centrifugal filtration to obtain Cu2O/TiO2The core-shell structure of (1) is spherical and uniform in morphology detected by a TEM (transmission electron microscope), and the XRD and EDS (electron-diffraction spectroscopy) energy spectrum analysis shows that TiO (titanium dioxide) is contained2Is present. Placing the obtained precipitate in a porcelain boat, and then performing heat treatment at 600 ℃ for 1 hour in an air atmosphere to obtain CuO/TiO2The core-shell structure of (1). The product is detected by a TEM electron microscope, and the appearance is still spherical basically; XRD and EDS energy spectrum analysis shows that CuO and TiO exist2Is present.
Example four: 0.5g of analytically pure copper sulfate (CuSO) was taken4.5H2O) was placed in a 100ml three-necked flask, and 20ml of B was addedGlycol is stirred and dissolved, 0.011g PVP (molecular weight 30000) is added, stirring and dissolving are carried out, 0.015g sodium borohydride is added, then the mixture is heated to 90 ℃ by using an oil bath or a water bath, after 2 minutes, the color is changed into orange red, and the mixture is centrifuged to obtain orange powder. The product is identified as cubic phase cuprous oxide by X-ray powder diffraction; and (3) detecting the product appearance by using an SEM (scanning electron microscope) and a TEM (transmission electron microscope): nanospheres of size-200 nm. Putting the obtained cuprous oxide powder into a muffle furnace, heating to 600 ℃ at a heating rate of 500 ℃/h, and carrying out heat treatment for 1 h in an air atmosphere to obtain copper oxide nanospheres; the monoclinic phase copper oxide is identified by X-ray powder diffraction; scanning electron microscope examination shows that the size of the nanosphere is not substantially changed. Putting the cuprous oxide into a quartz tube furnace, and introducing CO + N2(volume ratio 1: 9) gas, temperature rise rate of 600 ℃/hourRaising the temperature to 350 ℃, reacting for 2 hours to obtain nanospheres of purple metal copper, and identifying the nanospheres as cubic phase metal copper by X-ray powder diffraction; the appearance of the product is still nano-spherical and the size of the product is basically unchanged through SEM electron microscope detection. 0.1mmol of sodium stannate (Na) was dissolved2SnO3.3H2O) in 30ml of distilled water, then 0.1g of the obtained cuprous oxide nanosphere powder is added, stirred for 1 hour, then centrifugally filtered, the obtained precipitate is placed in a porcelain boat, and then heat treated for 2 hours at 500 ℃ in an air atmosphere to obtain CuO/SnO2The core-shell structure of nanospheres. The product is detected by an SEM electron microscope, the appearance is still spherical and basically has no size change; EDS energy spectrum analysis shows that SnO exists on the surface of the sphere2Is present.
Example five: 0.2g of analytically pure copper acetate (Cu (CH)3COO)2.H2O) was placed in a 100ml three-necked flask, dissolved with 20ml of absolute ethanol, added with 0.111g of PVP (molecular weight 1300000), stirred to dissolve, then added with 0.02g of sodium borohydride, heated to 70 ℃ with an oil bath or water bath for 6 minutes, changed in color to orange-red, and centrifuged to obtain an orange powder. The product is identified as cubic phase cuprous oxide by X-ray powder diffraction; and (3) detecting the product appearance by using an SEM (scanning electron microscope) and a TEM (transmission electron microscope): nanospheres of size-90 nm. Putting the obtained cuprous oxide powder in a porcelain boat, then putting the porcelain boat in a muffle furnace, and heating the porcelain boat to 300 ℃ at a heating rate of 500 ℃/hour for 3 hours in an air atmosphere to obtain copper oxide nanospheres; the monoclinic phase copper oxide is identified by X-ray powder diffraction; the scanning electron microscope detection shows that the shapes and the sizes of the nanospheres are basically unchanged. Putting the cuprous oxide into a quartz tube furnace, and introducing CO + N2Gas (volume ratio 1: 9), heating up to 300 ℃ at a heating rate of 600 ℃/hour, reacting for 1.5 hours to obtain nanospheres of purple metal copper, and identifying the nanospheres as cubic phase metal copper by X-ray powder diffraction; the appearance of the product is still nano-spherical and the size of the product is basically unchanged through SEM electron microscope detection. Dissolving 0.02mmol of manganese acetate in 40ml of distilled water, adding 0.2g of the obtained cuprous oxide nanosphere powder, stirring for 1 hour, centrifuging, filtering, placing the obtained precipitate in a porcelain boat, and performing heat treatment at 500 ℃ in air atmosphere for 1 hour to obtain CuO/MnO2Of (2) isA spherical core-shell structure. The product is detected by an SEM electron microscope, and the shape is still spherical; XRD and EDS energy spectrum analysis show that the nanosphere is CuO/MnO2。
Example six: 0.8g of analytically pure copper acetate (Cu (CH)3COO)2.H2O) was placed in a 100ml three-necked flask, and 20ml of N, N dimethylformamide was added to dissolve it, 0.02g of polyethylene glycol (molecular weight 5000) was added thereto, and stirred to dissolve it, and then 0.05g of sodium borohydride was added thereto, followed by heating to 90 ℃ with an oil bath or water bath for 2 minutes, whereupon the color changed to orange-red, and centrifugation was carried out to obtain an orange powder. The product is identified as cubic phase cuprous oxide by X-ray powder diffraction; and (3) detecting the product appearance by using an SEM (scanning electron microscope) and a TEM (transmission electron microscope): nanospheres of size-200 nm. Dropping the obtained ethanol sol of cuprous oxide onto Si sheet, placing in muffle furnace at 500 deg.CRaising the temperature to 500 ℃ at the hour heating speed, and carrying out heat treatment for 1 hour in the air atmosphere to obtain copper oxide nanospheres; the monoclinic phase copper oxide is identified by X-ray powder diffraction; the scanning electron microscope detection shows that the shapes and the sizes of the nanospheres are basically unchanged. Putting the cuprous oxide into a quartz tube furnace, and introducing CO + N2Gas (volume ratio 1: 9), heating up to 300 ℃ at a heating rate of 600 ℃/hour, reacting for 1 hour to obtain nanospheres of purple metal copper, and identifying the nanospheres as cubic phase metal copper by X-ray powder diffraction; the appearance of the product is still nano-spherical and the size of the product is basically unchanged through SEM electron microscope detection. Dissolving 0.2ml of tetrabutyl titanate in 20ml of absolute ethyl alcohol; adding 0.2g of cuprous oxide nanosphere into 15ml of ethanol, stirring to form sol, adjusting the pH value of the cuprous oxide sol to be about 8-9 by using dilute ammonia water (10 percent, volume content), slowly dropwise adding an ethanol solution of tetrabutyl titanate into the cuprous oxide ethanol sol, stirring for 1 hour, and then carrying out centrifugal filtration to obtain Cu2O/TiO2The core-shell structure of (1) is spherical and uniform in morphology detected by a TEM (transmission electron microscope), and the XRD and EDS (electron-diffraction spectroscopy) energy spectrum analysis shows that TiO (titanium dioxide) is contained2Is present. Placing the obtained precipitate in a porcelain boat, and then performing heat treatment at 600 ℃ for 1 hour in an air atmosphere to obtain CuO/TiO2The core-shell structure of (1). The product is detected by a TEM electron microscope, and the appearance is still spherical basically; XRD and EDS energy spectrum analysis show that TiO is contained2Is present.
Claims (9)
1. A method for synthesizing quasi-monodisperse cuprous oxide is characterized by comprising the following steps in sequence:
1) dissolving copper salt in an organic solvent which can be mutually dissolved with water to prepare a copper ion solution with the concentration of 0.025-0.2 mol/l;
2) adding a nonionic surfactant into the copper ion solution, stirring and dissolving, wherein the concentration of the nonionic surfactant is 0.005-0.05 mol/l;
3) adding a strong reducing agent into the solution prepared in the step 2), wherein the concentration of the strong reducing agent is 0.025-0.2 mol/l;
4) and (3) keeping the temperature of the solution prepared in the step (3) at 70-90 ℃, and refluxing in an open system to obtain the quasi-monodisperse cuprous oxide nanospheres.
2. A method of synthesizing quasi-monodisperse cuprous oxide as claimed in claim 1 wherein said water-miscible organic solvent is N, N dimethylformamide, ethylene glycol or ethanol.
3. A method of synthesizing quasi-monodisperse cuprous oxide as claimed in claim 1 wherein said copper salt is copper acetate, copper sulfate, copper nitrate or copper chloride.
4. A method of synthesizing quasi-monodisperse cuprous oxide as claimed in claim 1 wherein said non-ionic surfactant is polyvinylpyrrolidone or polyethylene glycol.
5. A method of synthesizing quasi-monodisperse cuprous oxide as claimed in claim 1 wherein said strong reducing agent is sodium borohydride or potassium borohydride.
6. The method for further preparing the copper oxide nanospheres by using the cuprous oxide nanospheres prepared by the method of claim 1, wherein the cuprous oxide nanospheres are subjected to heat treatment at 300-600 ℃ for more than 1 hour in an air atmosphere to obtain the quasi-monodisperse copper oxide nanospheres.
7. The method for further preparing the copper nanospheres by using the cuprous oxide nanospheres prepared by the method of claim 1, wherein the cuprous oxide nanospheres are reacted for 1-2 hours at the temperature of 200-400 ℃ in a reducing atmosphere to obtain the quasi-monodisperse copper nanospheres.
8. The method for further preparing the metal oxide core-shell nanosphere structure by using the cuprous oxide nanospheres prepared by the method of claim 1,
1) soaking the cuprous oxide nanospheres in an aqueous solution or an organic solution of corresponding salt of N-type semiconductor metal oxide, adjusting the pH value to 7-9, stirring simultaneously, and then performing centrifugal treatment, wherein the concentration of the salt is 0.01-2 mmol/l;
2) and (3) in an air atmosphere or an inert gas atmosphere, performing high-temperature treatment at 300-600 ℃ on the product obtained through the centrifugal treatment to obtain a core-shell nano-sphere structure of cuprous oxide and N-type semiconductor metal oxide or a core-shell nano-sphere structure of cupric oxide and N-type semiconductor metal oxide.
9. The method of preparing a metal oxide core shell nanosphere structure of claim 8 wherein said cuprous oxide N-type semiconductor metal oxide corresponding salt is a tin salt, titanium salt, zinc salt or indium salt.
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