CN111517358B - Synthetic method and application of flower-shaped copper oxide nanospheres - Google Patents
Synthetic method and application of flower-shaped copper oxide nanospheres Download PDFInfo
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 60
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 60
- 239000002077 nanosphere Substances 0.000 title claims abstract description 42
- 238000010189 synthetic method Methods 0.000 title claims description 5
- 239000000243 solution Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000001308 synthesis method Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 239000002086 nanomaterial Substances 0.000 abstract description 15
- 238000001556 precipitation Methods 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- -1 ammonium cations Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J35/39—
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- B01J35/51—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention relates to a synthesis method of flower-shaped copper oxide nanospheres, which comprises the following steps: dissolving (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate in water to form a solution A; adding an ammonia water solution and a copper salt solution into the solution A under magnetic stirring to obtain a solution B; keeping the solution B at 120-125 ℃ for condensation reflux reaction to obtain brown solid C; carrying out ultrasonic reaction on the solid C to obtain a black solid D; centrifugally separating the black solid D, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain flower-shaped copper oxide nanospheres; and provides the application of the flower-like copper oxide nanospheres prepared by the synthesis method in degrading rhodamine B. The synthesis method of the flower-shaped copper oxide nanospheres provided by the technical scheme can effectively solve the problems that the copper oxide nanomaterial synthesized by the existing precipitation method is poor in appearance and size uniformity and small in specific surface area, and meanwhile, the flower-shaped copper oxide nanospheres can effectively carry out photocatalytic degradation on dye wastewater.
Description
Technical Field
The invention relates to the technical field of photocatalytic nano materials, in particular to a synthetic method and application of flower-shaped copper oxide nanospheres.
Background
The nano material is a material having a particle size of 1nm to 100nm, and has been found to exhibit excellent properties since the 20 th century, and has been favored by researchers because it exhibits many characteristics in optical, mechanical, electromagnetic, and biological aspects as compared to conventional materials.
Copper oxide is a p-type semiconductor oxide and has a narrow band gap, and a nano copper oxide material belongs to a typical metal oxide semiconductor nano material and has good application in gas sensors, lithium battery electrode materials, solar cells, catalytic reactions, biological pharmacy, environmental treatment and other aspects. In recent years, researchers actively explore and synthesize copper oxide nano materials with different morphologies, and at present, materials such as copper oxide nanowires, nanosheets, hollow microspheres and the like are successfully prepared by different synthesis methods. Among them, the flower-like copper oxide has a relatively high specific surface area, multiple active sites, low bulk density, etc., and thus has a wide application in environmental catalysis, and thus, the synthesis of the flower-like copper oxide is receiving much attention. However, the copper oxide nano material synthesized by the existing precipitation method is poor in shape and size uniformity under the protection of no inducer, so that the specific surface area of the copper oxide nano material is reduced, and the application is limited.
Disclosure of Invention
The invention aims to provide a synthesis method of flower-shaped copper oxide nanospheres, which can effectively solve the problems of poor uniformity of morphology and size and small specific surface area of a copper oxide nanomaterial synthesized by the existing precipitation method.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthetic method of flower-shaped copper oxide nanospheres is characterized by comprising the following steps:
(a) dissolving (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate in water to form a solution A;
(b) adding an ammonia water solution and a copper salt solution into the solution A under magnetic stirring, and stirring to obtain a blue solution B;
(c) keeping the solution B at 120-125 ℃ for condensation reflux reaction for 2-4 hours until the solution B is changed from blue to light yellow to obtain brown precipitate C;
(d) carrying out ultrasonic reaction on the precipitate C to obtain a black solid D;
(e) and (3) centrifugally separating the black solid D, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the flower-shaped copper oxide nanospheres.
Wherein the mass ratio of the (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate to the water in the step (a) is 0.37: 10.
Wherein the feeding mass ratio of the concentrated ammonia water in the ammonia water solution in the step (b) to the water is 0.35: 10.
Wherein, the copper salt in the step (b) is copper nitrate, copper chloride or copper acetate; and the mass ratio of copper salt to water in the copper salt solution is 0.60: 10.
Wherein the ultrasonic reaction in the step (d) is carried out for 5-7 hours at 45-50 ℃.
Wherein, the centrifugal separation rotating speed in the step (e) is 6000 r/min, and the time is 4-6 min.
Wherein the temperature of vacuum drying in the step (e) is 60-65 ℃, and the time is 9-11 h.
The flower-like copper oxide nanospheres prepared by the synthesis method are applied to degrading rhodamine B.
According to the synthesis method of the flower-shaped copper oxide nanosphere, a cold-hot reflux method is adopted, copper ammine complex ions are formed in a solution, and (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate forms (Z) -2-methoxyimino-2- (furan-2-yl) acetic acid anions and ammonium cations in a solution phase, the (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate anions and the ammonium cations interact with the copper ammine complex ions under the electrostatic action to form a micelle aggregate with a certain structure, and in the reaction process, along with the volatilization of ammonia gas, under the induction of redundant (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate, deamination is gradually carried out to generate black copper oxide solids; in the reaction process, the (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate can play a good role in protection, so that the obtained nanosphere structure has uniform appearance and size, and the problems that the copper oxide nanomaterial prepared by the existing precipitation method is poor in appearance and size uniformity, small in specific surface area and limited in application are solved. In addition, the copper oxide nano material is prepared by adopting a common condensation reflux method in a water system at normal temperature and normal pressure, the requirement on reaction equipment is low, and the cost is low; meanwhile, (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate is used as a protective agent, so that the synthesis of the nano material with uniform appearance and size can be controlled, and the organic dye can be treated under ultraviolet light.
Finally, compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a method for preparing flower-shaped copper oxide nanospheres, reagents required by experiments can be purchased in the market, and the cost is low; and a condensation reflux method at normal temperature and normal pressure is adopted, the production process is simple and easy to implement, and large-scale production is easy to realize.
(2) The invention relates to a method for preparing a flower-shaped copper oxide nanosphere material, which adopts (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate as a protective agent, realizes the synthesis of copper oxide nanospheres with uniform appearance by using a one-step synthesis method, has larger specific surface area compared with the traditional synthesized copper oxide, and is more favorable for photocatalytic degradation of dye wastewater.
Drawings
FIG. 1 is an SEM image of flower-like copper oxide nanospheres obtained in the example of the present invention;
FIG. 2 is an XRD diagram of flower-like copper oxide nanospheres obtained in the example of the present invention;
FIG. 3 is an XPS graph of flower-like copper oxide nanospheres obtained in the example of the present invention;
FIG. 4 is an XPS copper element 2p narrow spectrum of flower-like copper oxide nanospheres obtained in the example of the present invention;
FIG. 5 is an XPS carbon element 1s narrow spectrum of flower-like copper oxide nanospheres obtained in the example of the present invention;
FIG. 6 is an XPS oxygen element 1s narrow spectrum of flower-like copper oxide nanospheres obtained in the example of the present invention;
FIG. 7 is an ultraviolet-visible spectrum of rhodamine B photocatalytic degradation of the flower-like copper oxide nanospheres obtained in the example;
FIG. 8 is a graph of the degradation rate of rhodamine B over time in a photocatalytic experiment;
FIG. 9 is an SEM image of copper oxide nano-materials in comparative examples of the present invention.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the following description is given in conjunction with the accompanying examples. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
Examples
(a) Weighing 0.37g of (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate solid, and adding 10g of water to prepare a clear and transparent solution A;
(b) weighing 0.60g of copper salt, and adding 10g of water to prepare a clear and transparent solution E;
(c) measuring 0.35mL of strong ammonia water, and adding 10g of water to prepare a clear and transparent solution F;
(d) respectively transferring 0.1mL of solution A, 0.2mL of solution E, 2.0mL of solution F and 7.7mL of water under magnetic stirring to form a transparent solution B, and placing the transparent solution B in a round-bottom flask;
(e) heating and refluxing the mixed solution B under the stirring state, and reacting at 120 ℃ for about 3 hours until the solution B is changed from blue to light yellow to obtain a brown precipitate C;
(f) after the reaction, when the temperature of the system is reduced to 45 ℃, transferring the round-bottom flask to an ultrasonic machine for continuous reaction for 6 hours to obtain a black solid D;
(g) cooling the black solid to room temperature, centrifuging at 6000 rpm for 5min, removing supernatant, and washing precipitate with deionized water and anhydrous ethanol;
(h) and (3) drying the precipitate in a vacuum drying oven at the temperature of 60-65 ℃ for 10h to obtain the flower-shaped copper oxide nanospheres.
(i) Photocatalytic experiments: adopting GHX2 photochemical reaction instrument (Yangzhou university city science and technology Co., Ltd.) to carry out photocatalytic reaction, placing the prepared flower-shaped copper oxide nanospheres and rhodamine B solution in a quartz reactor, connecting with circulating water for cooling, stirring for 1.5h in the dark to reach adsorption balance, opening ultraviolet light, absorbing the moderating solution at regular intervals, measuring the absorbance of supernatant liquid of the moderating solution by using an ultraviolet visible spectrophotometer after centrifugal precipitation, and further calculating the degradation rate of the moderating solution, wherein the specific experimental results are shown in figures 7 and 8.
Comparative example
(a) Weighing 0.60g of copper salt, and adding 10g of water to prepare a clear and transparent solution E;
(b) measuring 0.35mL of strong ammonia water, and adding 10g of water to prepare a clear and transparent solution F;
(c) respectively transferring 0.2mL of solution E, 2.0mL of solution F and 7.8mL of water under magnetic stirring to form transparent solutions;
(d) heating and refluxing the mixed solution under the stirring state, and reacting for 3 hours at the temperature of 120 ℃;
(e) after the reaction, when the temperature of the system is reduced to 45 ℃, moving the reactor to an ultrasonic machine for continuous reaction for 6 hours;
(f) cooling to room temperature after the reaction is finished, centrifuging for 5min at the rotating speed of 6000 r/min, removing supernatant, and washing precipitated substances by using deionized water and absolute ethyl alcohol;
(g) drying for 10h at the temperature of 60-65 ℃ in a vacuum drying oven to obtain the copper oxide material, wherein the SEM photograph is shown in figure 9.
Product identification
FIG. 1 is an SEM image of flower-like copper oxide nanospheres prepared in this example; SEM shows that the synthesized flower-shaped copper oxide nanospheres are uniform in shape and size, the diameter of the flower is about 1 mu m, and the flower is composed of nano petals with the thickness of 50-80 nm.
FIG. 2 is an XRD diagram of flower-like copper oxide nanospheres obtained according to the invention; the figure is obtained on an X' Pert3Powder type polycrystalline Powder diffractometer of the Panalytical company in the Netherlands, an XRD spectrogram shows that the most intense peak 2 theta is positioned at 38.6598 degrees and corresponds to a (111) crystal face, the second intense peak 2 theta is positioned at 35.4805 degrees and corresponds to a (002) crystal face, the other peaks 2 theta are respectively positioned at 32.4044 degrees, 48.8256 degrees, 58.0826 degrees, 61.5329 degrees and the like and respectively correspond to (-110), (-202), (202) and (-113) crystal faces and the like, the result is consistent with the standard card 045-0937 of copper oxide, and the crystal structure is a monoclinic crystal form.
FIGS. 3 to 6 are XPS diagrams of flower-like copper oxide nanospheres obtained by the present invention, which are obtained on an ESCALB 250XiX ray photoelectron spectrometer of the United states of America and thermal power company, and show that the full spectrum of the XPS diagrams shows that the synthesized black solid surface is composed of three elements of carbon, copper and oxygen, and the high resolution spectrum of copper shows that the binding energy of the copper element in the XPS diagram corresponds to the 2p orbital of + 2-valent copper; the high resolution spectrum of oxygen shows that the binding energy of the oxygen element in the substance corresponds to the 1s orbital of-2-valent oxygen, further indicating that the synthesized black solid is a copper oxide nano material.
Fig. 7 and 8 are experimental diagrams of degrading rhodamine B solution under ultraviolet irradiation of the flower-like copper oxide nanospheres obtained by the present invention, and the results show that the rhodamine B solution can be completely degraded after 50min under ultraviolet irradiation, wherein the degradation rate reaches 99.98%, and further show that the flower-like copper oxide nanospheres synthesized by the present invention are good photocatalysts and have good applications in the field of photocatalysis.
Fig. 9 is an SEM image of the copper oxide nanomaterial obtained by the comparative example of the present invention, which shows that the synthesized copper oxide nanomaterial is not already a flower-like structure, and it is illustrated that flower-like copper oxide nanospheres with uniform morphology and size can be obtained only by strictly following the conditions in the present invention.
The present invention is not limited to the above embodiments, and those skilled in the art can make various equivalent changes and substitutions without departing from the principle of the present invention after learning the content of the present invention, and these equivalent changes and substitutions should be considered as belonging to the protection scope of the present invention.
Claims (8)
1. A synthetic method of flower-shaped copper oxide nanospheres is characterized by comprising the following steps:
(a) dissolving (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate in water to form a solution A;
(b) adding an ammonia water solution and a copper salt solution into the solution A under magnetic stirring, and stirring to obtain a blue solution B;
(c) keeping the solution B at 120-125 ℃ for condensation reflux reaction until the solution B is changed from blue to light yellow to obtain brown precipitate C;
(d) carrying out ultrasonic reaction on the precipitate C to obtain a black solid D;
(e) and (3) centrifugally separating the black solid D, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the flower-shaped copper oxide nanospheres.
2. The method for synthesizing flower-shaped copper oxide nanospheres according to claim 1, wherein: the mass ratio of (Z) -2-methoxyimino-2- (furan-2-yl) ammonium acetate to water in the step (a) is 0.37: 10.
3. The method for synthesizing flower-shaped copper oxide nanospheres according to claim 1, wherein: the feeding mass ratio of the concentrated ammonia water in the ammonia water solution in the step (b) to the water is 0.35: 10.
4. The method for synthesizing flower-shaped copper oxide nanospheres according to claim 1, wherein: the copper salt in the step (b) is copper nitrate or copper chloride or copper acetate; and the mass ratio of copper salt to water in the copper salt solution is 0.60: 10.
5. The method for synthesizing flower-shaped copper oxide nanospheres according to claim 1, wherein: the ultrasonic reaction in the step (d) is carried out for 5-7 hours at the temperature of 45-50 ℃.
6. The method for synthesizing flower-shaped copper oxide nanospheres according to claim 1, wherein: and (e) performing centrifugal separation at 6000 rpm for 4-6 min.
7. The method for synthesizing flower-shaped copper oxide nanospheres according to claim 1, wherein: in the step (e), the temperature of vacuum drying is 60-65 ℃, and the time is 9-11 h.
8. Application of flower-like copper oxide nanospheres prepared by the synthesis method of any one of claims 1-7 in degradation of rhodamine B.
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