CN115028187A - Chemical preparation method of copper oxide nanoparticles - Google Patents
Chemical preparation method of copper oxide nanoparticles Download PDFInfo
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- CN115028187A CN115028187A CN202210921281.9A CN202210921281A CN115028187A CN 115028187 A CN115028187 A CN 115028187A CN 202210921281 A CN202210921281 A CN 202210921281A CN 115028187 A CN115028187 A CN 115028187A
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- sodium oleate
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- 239000005751 Copper oxide Substances 0.000 title claims abstract description 72
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 72
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 13
- 238000005285 chemical preparation method Methods 0.000 title claims abstract description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000005303 weighing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 25
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 abstract description 19
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 20
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- HAFAJCGPTCWGHB-UHFFFAOYSA-J [OH-].[OH-].[OH-].[OH-].[Cu+4] Chemical compound [OH-].[OH-].[OH-].[OH-].[Cu+4] HAFAJCGPTCWGHB-UHFFFAOYSA-J 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a chemical preparation method of copper oxide nano particles, which comprises the steps of weighing copper acetate powder, measuring deionized water, and carrying out ultrasonic treatment until copper acetate is completely dissolved to prepare a copper acetate aqueous solution; weighing sodium oleate, measuring an alcohol solvent, mixing the alcohol solvent and the sodium oleate, stirring and heating to completely dissolve the sodium oleate to obtain a sodium oleate-alcohol solution; adding a copper acetate aqueous solution into the sodium oleate-alcohol solution to obtain a nano copper oxide reaction system, and finally obtaining the nano copper oxide under the conditions of 80-120 ℃ and magnetic stirring. The method can solve the problems of large particle size, difficult control, complex operation and the like in the preparation of the nano copper oxide by the conventional method.
Description
Technical Field
The invention belongs to the synthesis technology of a solution chemical method, relates to a chemical preparation method of copper oxide nanoparticles, and belongs to the technical field of material preparation.
Background
The nano material has many characteristics which are not possessed by large-scale particles, and when the size of the material is small to a certain degree, the performance of the material can be greatly changed. The nano material has attracted much attention due to the surface effect, small size effect, quantum size effect, macroscopic quantum tunneling effect, coulomb blockade effect and the like.
The nano copper oxide has extremely wide application in the fields of ceramics, antibiosis, catalysis and the like, and can be used as a negative electrode material of a lithium battery, a rocket-propelled burning rate catalyst and the like; the nano copper oxide has small particles and has better performance than large-size copper oxide powder.
When the diameter of the nano copper oxide particle is not more than 10nm, the function can be exerted more greatly, and the current methods for producing the nano copper oxide have various problems, but the current preparation method generally has the following problems: the reaction is difficult to control, the preparation process is complex, the preparation cost is high, the particle size of the prepared product is large, and the like, so that the nano copper oxide particles with smaller sizes cannot be stably and efficiently produced. The method requires continuous exploration and improvement on the existing method, and finds the most suitable preparation method for stably and efficiently producing the nano copper oxide.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a chemical preparation method of copper oxide nanoparticles, which aims to solve the problems of difficult control of reaction, complex preparation process, high preparation cost, larger particle size of prepared products and the like in the existing preparation method.
The technical scheme is as follows:
a chemical preparation method of copper oxide nano particles comprises the following steps:
weighing copper acetate powder and measuring deionized water, wherein the mass ratio of the deionized water to the copper acetate is 20-80: 1, performing ultrasonic treatment until copper acetate is completely dissolved to prepare a copper acetate aqueous solution;
weighing sodium oleate, measuring an alcohol solvent, mixing the alcohol solvent and the sodium oleate, stirring and heating to 80-120 ℃ to completely dissolve the sodium oleate to obtain a sodium oleate-alcohol solution;
and (3) adding a copper acetate aqueous solution into the sodium oleate-alcohol solution to obtain a nano copper oxide reaction system, wherein the volume ratio of the copper acetate aqueous solution added into the reaction system to the sodium oleate-alcohol solution is 1: 11.5-49, reacting for 30min at 80-120 ℃ under the condition of magnetic stirring to finally obtain the nano copper oxide.
Preferably, in the step (2), the molar ratio of the sodium oleate to the nano copper oxide in the reaction system is 1: 2.
preferably, the alcohol solution in step (2) is ethanol, n-butanol or hexanol, respectively.
Preferably, the mass ratio of the deionized water to the copper acetate in the step (1) is 20: 1.
preferably, the volume ratio of the copper acetate aqueous solution to the sodium oleate-alcohol solution in the step (3) is 1: 49.
has the beneficial effects that:
the invention adopts a solution chemistry method, adopts ethanol, n-butanol and n-hexanol as alcohol solvents, and prepares the nano-copper oxide by changing the concentration of copper acetate aqueous solution, the addition amount of deionized water, the reaction temperature and other conditions. The method has the advantages of simple preparation process, few experimental steps, low cost, mild reaction conditions, easy control and the like. The prepared nano copper oxide has small grain diameter and good dispersibility, and the nano copper oxide with ultra-small size can be prepared by adjusting some reaction conditions.
Drawings
FIG. 1 is an XRD pattern of nano-copper oxide generated by using ethanol as an alcohol solvent and adding different amounts of copper acetate aqueous solution in example 1 of the present invention;
FIG. 2 is a TEM spectrum of nano-copper oxide generated by using ethanol as an alcohol solvent and adding different amounts of copper acetate aqueous solutions in example 1 of the present invention;
FIG. 3 is an XRD (X-ray diffraction) spectrum of nano-copper oxide generated by using n-butanol as an alcohol solvent and setting different reaction temperatures in embodiment 2 of the invention;
FIG. 4 is a TEM spectrum of nano-copper oxide generated by using n-butanol as an alcohol solvent and setting different reaction temperatures in example 2 of the present invention;
FIG. 5 is an XRD spectrum of nano-copper oxide generated by using n-hexanol as an alcohol solvent and setting different reaction temperatures in embodiment 3 of the present invention;
FIG. 6 is a TEM spectrum of nano-copper oxide generated by using n-hexanol as an alcohol solvent and setting different reaction temperatures in example 3 of the present invention;
FIG. 7 is a UV spectrum of an aqueous solution of copper acetate, as used in an example of the present invention.
FIG. 8 is a UV spectrum of nano-copper oxide formed based on the addition of 4ml of aqueous copper acetate solution without the addition of sodium oleate in example 1 of the present invention.
FIG. 9 is the ultraviolet spectrum of the nano-copper oxide produced by adding sodium oleate into the copper acetate solution of 4ml in example 1.
Detailed Description
The invention provides a chemical preparation method of copper oxide nanoparticles, which is a preparation method for controlling the particle size of nano copper oxide by changing the conditions of the addition amount of a copper acetate aqueous solution, the reaction temperature and the like by using copper acetate (also called copper acetate) as a copper source, sodium oleate as a surfactant, ethanol, n-butanol or n-hexanol as an alcohol solvent and adding a small amount of deionized water. The experimental method is simple, the experimental conditions are mild, the operation is easy, and the particle size of the prepared nano copper oxide is small.
Example 1
A preparation method of nano copper oxide comprises the following steps:
(1) respectively weighing (0.1g), (0.5 g), (0.25 g), (0.167 g), (0.125 g) copper acetate, adding the copper acetate into a corresponding 10ml volumetric flask filled with 10ml deionized water (wherein, in the experiment, (no deionized water is added), correspondingly, part of alcohol solvent in the step (2) is taken, and the copper acetate is dissolved in part of alcohol solvent), and preparing the copper acetate with the concentration of (0) (0.1g) and (2.5 multiplied by 10) respectively - 1 mol·L -1 ③1.25×10 -1 mol·L -1 ④8.35×10 -2 mol·L -1 ⑤6.25×10 -2 mol·L -1 And (4) carrying out ultrasonic treatment until copper acetate is completely dissolved to prepare a copper acetate aqueous solution with the required concentration.
(2) Respectively weighing 5 parts of 0.076g of sodium oleate, respectively weighing (100 ml), (98 ml), (96 ml), (94 ml), (92 ml) of ethanol by using a measuring cylinder, pouring the sodium oleate and the corresponding ethanol into a three-neck flask, stirring and heating in a magnetic heating stirrer to 80 ℃ until 5 parts of the sodium oleate are completely dissolved to obtain the sodium oleate-alcohol solution.
(3) Respectively measuring 0ml, 2ml, 4ml, 6ml, 8ml of copper acetate aqueous solution in the step (1) and correspondingly adding the copper acetate aqueous solution into the sodium oleate-alcohol solution of the three-neck flask with the corresponding number in the step (2) (the specific operation data is shown in table 1), so that the total volume of each part is 100ml, and the requirements that the actual adding amount of the components of the copper acetate in each parallel experiment is not changed and the total amount of the alcohol-water is not changed are met. Reacting for 30min at the constant temperature of 80 ℃ under the condition of magnetic stirring to finally obtain the nano copper oxide.
TABLE 1 Experimental parameters table for changing water addition amount in ethanol system
It can be seen from the experimental phenomenon that in the first experiment, when no deionized water is added into the system, the solution is blue-green, and since the copper oxide is black, the reaction does not occur in the reaction in which no water is added into the system. The reason is that the addition of deionized water can lead Cu in the reaction system 2+ And C 17 H 33 COO - Hydrolysis occurs and the reaction can proceed smoothly. In the figure 1, a, b, c and d are respectively the XRD patterns of the nano copper oxide product prepared by adding 2ml, 4ml, 6ml and 8ml of copper acetate aqueous solution, and the comparison of the copper oxide standard card shows that a, b, c and d all have copper oxide, particularly, the figure 1 is taken as an example (similar processing mode is shown in figures 3 and 5), so that the differences of the nano copper oxide performance obtained by parallel experiments under the same system are conveniently compared, the XRD patterns of the same system are placed in one figure, and the up-and-down translation is carried out for convenient viewing. FIG. 2 is BThe alcohol system changes the TEM photograph of the added copper acetate aqueous solution (a, b, c, d correspond to 2, 4, 6, 8ml of copper acetate aqueous solution respectively), and as can be seen from the TEM photograph of fig. 2, the size of the nano copper oxide prepared in the alcohol system is smaller, and is all around 5nm, the particle size of the generated nano copper oxide is increased and then decreased with the increase of the copper acetate aqueous solution added in the system, when the adding amount is 2ml, the size of the generated nano copper oxide is smaller overall and is approximately distributed around 2.5nm, so in the parallel experiment of the alcohol system changing the copper acetate aqueous solution, 2ml of the copper acetate aqueous solution is added as the optimal experiment. Subsequent experiments will be based on the conclusion of the experiment, namely: referring to an ethanol system experiment, 2ml of copper acetate aqueous solution is added into the reaction system, and the influence of the temperature on the experiment result is researched by changing the alcohol solvent and the reaction temperature.
Example 2
A preparation method of nano copper oxide comprises the following steps:
(1) weighing 0.5g of copper acetate, weighing 10ml of deionized water, putting the two into a 10ml volumetric flask, performing ultrasonic treatment until the copper acetate is completely dissolved, and preparing the mixture into the solution with the concentration of 2.5 multiplied by 10 -1 mol·L -1 The aqueous copper acetate solution of (1).
(2) Weighing 0.076g of sodium oleate, weighing 98ml of n-butyl alcohol, pouring the two into a three-neck flask, stirring in a magnetic heating stirrer, and respectively heating to 80 ℃, 90 ℃, 100 ℃ and 110 ℃ to perform four groups of parallel tests.
(3) After the sodium oleate is completely dissolved, 2ml of copper acetate aqueous solution in the step (1) is weighed and added into the sodium oleate-alcohol solution in the three-neck flask in the step (2), and the mixture reacts for 30min at the temperature of 80 ℃, 90 ℃, 100 ℃ and 110 ℃ respectively under the condition of magnetic stirring, so that the nano copper oxide is finally obtained.
As shown in FIG. 3, the XRD patterns of the n-butanol system with changed reaction temperature (a, b, c, d correspond to 80, 90, 100, 110 ℃ of the n-butanol system respectively) show that nano copper oxide can be generated by changing the temperature in the system, except that the generated nano copper oxide has sharper diffraction peak and better crystallinity along with the increase of the temperature. According to a TEM (transmission electron microscope) graph (a, b, c and d respectively correspond to 80, 90, 100 and 110 ℃ of the n-butyl alcohol system) of fig. 4, the size of the nano copper oxide prepared under the system is reduced firstly and then increased along with the rise of the temperature, but the size of the nano copper oxide is within 5nm and is distributed mostly around 2.5nm, wherein the grain diameter of the nano copper oxide generated under the condition of 100 ℃ is the minimum in the experiment, so that the optimal experiment is carried out when the temperature is 100 ℃ in a parallel experiment that the n-butyl alcohol system changes the reaction temperature. It can be seen that temperature is also a factor affecting the particle size of the nano-copper oxide.
Example 3
A preparation method of nano copper oxide comprises the following steps:
(1) weighing 0.5g of copper acetate, weighing 10ml of deionized water, putting the two into a 10ml volumetric flask, performing ultrasonic treatment until the copper acetate is completely dissolved, and preparing the mixture into the solution with the concentration of 2.5 multiplied by 10 -1 mol·L -1 The aqueous copper acetate solution of (1).
(2) Weighing 0.076g of sodium oleate, weighing 98ml of n-hexanol by using a measuring cylinder, pouring the two into a three-neck flask, stirring in a magnetic heating stirrer, and respectively heating to 80 ℃, 100 ℃ and 120 ℃ to perform three parallel experiments.
(3) After the sodium oleate is completely dissolved, 2ml of copper acetate aqueous solution is measured and added into a three-neck flask, and the mixture reacts for 30min under the conditions of 80 ℃, 100 ℃ and 120 ℃ and magnetic stirring, so that the nano copper oxide is finally obtained.
As can be seen from the XRD patterns (a, b and c respectively correspond to 80, 100 and 120 ℃ of the n-hexanol system) of FIG. 5, and the TEM patterns (a and b respectively correspond to 100 and 120 ℃ of the n-hexanol system) of FIG. 6, when the temperature is 80 ℃ in the system, no copper oxide is generated, when the temperature is raised to 100 ℃, the nano copper oxide can be successfully prepared, in the system, the XRD diffraction peak is relatively clear and sharp, and the size of the prepared nano copper oxide increases along with the temperature increase, so that when the solvent is n-hexanol, the relatively low temperature (which is 100 ℃ in this system) enables the produced nano-copper oxide to have a smaller particle size, which is mostly distributed around 2.5nm, and therefore, in parallel experiments with the n-hexanol system varying the reaction temperature, a temperature of 100 ℃ was the most preferred experiment.
The effect of sodium oleate in the system was next analyzed. Fig. 7 is a uv spectrum of an aqueous copper acetate solution, and fig. 8 and 9 are uv spectra of sodium oleate-free and sodium oleate-added when 4ml of an aqueous copper acetate solution was added to the ethanol system of example 1, respectively, wherein each experiment was performed for 30min, and samples were taken every 10min for uv testing. From the analyses of FIGS. 7, 8 and 9, it can be concluded that the reaction has not started yet, similarly to FIG. 7, in the case where sodium stearate is not added (corresponding to FIG. 8) the map of the time 10min before the addition of sodium stearate; when sodium oleate was added, the ultraviolet spectrum at 10min was significantly changed from that of fig. 7, and it can be seen that the addition of sodium oleate accelerates the reaction rate. If the sodium oleate is too little, the reaction rate can be greatly reduced although the particle size of the prepared nano copper oxide is smaller; if the sodium oleate is excessive, the reaction rate is accelerated, but the particle size of the generated nano copper oxide is increased, so that the particle size of the nano copper oxide and the reaction rate are balanced, and a relatively optimal proportion is adopted, namely the molar ratio of the sodium oleate to the copper acetate actually added for reaction is 1: 2.
the reaction principle is as follows: the main hydrolysis of copper acetate solution in sodium oleate-ethanol solution is Cu 2+ And CH 3 COO - 、C 17 H 33 COO - (ii) a Wherein, C 17 H 33 COO - Degree of hydrolysis of (2) to CH 3 COO - Larger, so hydrolysis of sodium oleate may be OH - Of major origin, Cu 2+ With OH - Formation of Cu (OH) 2 And further generating Cu (OH) under an alkaline environment 4 2- (tetrahydroxy copper ion). If the copper tetrahydroxy complex is in a sodium oleate-ethanol system under alkaline conditions, two out-of-plane points are likely to be combined with water molecules and can also be combined with oleic acid radicals, and the two points have a competitive relationship. When the proportion of oleate radicals in the reaction system is far greater than that of water, the oleate radicals partially replace the water and occupy more positions to form the modification of the nanoparticles. Cu (OH) 4 2- The process of the change of the glycidyl group into polymerized CuO is not infinite due to the modification of the oleic acid group. The oleate radical is combined on the surface of the nano particle in a mode that lone pair electrons enter into the empty orbit of copper,the more oleic acid groups are combined, the larger the steric hindrance on the surface of the CuO nanoparticles is, the further occurrence of the glycidyl polymerization reaction can be blocked, and the system is balanced. From the above analysis, sodium oleate has two roles in the system: firstly, providing an alkaline environment to accelerate the reaction rate; and secondly, modifying the nano particles, and blocking the polycondensation reaction to obtain the nano particles with uniform particle size.
The invention prepares the small-sized nano copper oxide by changing the reaction temperature, the actual addition amount of deionized water, the concentration of copper acetate and alcohol. The sodium oleate is added as the surfactant, so that the reaction rate and the growth of the size of the copper oxide can be controlled, and the particle size of the prepared nano copper oxide is smaller. In the experiment, the ethanol system changes the addition of the copper acetate aqueous solution, but the quality of the actual addition reaction of the copper acetate is ensured to be unchanged, which is equivalent to changing the addition of deionized water, and along with the increase of the water amount added into the reaction system, the particle size of the nano copper oxide is increased and then reduced, and in addition, the size of the nano copper oxide is influenced to a certain extent by the selection of the temperature. Therefore, the particle size of the nano copper oxide can be controlled by regulating and controlling the addition of deionized water, the concentration of copper acetate, the reaction temperature and the type of alcohol in the experiment.
Claims (5)
1. A chemical preparation method of copper oxide nanoparticles is characterized by comprising the following steps:
weighing copper acetate powder and measuring deionized water, wherein the mass ratio of the deionized water to the copper acetate is 20-80: 1, performing ultrasonic treatment until copper acetate is completely dissolved to prepare a copper acetate aqueous solution;
weighing sodium oleate, measuring an alcohol solvent, mixing the alcohol solvent and the sodium oleate, stirring and heating to 80-120 ℃ to completely dissolve the sodium oleate to obtain a sodium oleate-alcohol solution;
and (3) adding a copper acetate aqueous solution into the sodium oleate-alcohol solution to obtain a nano copper oxide reaction system, wherein the volume ratio of the copper acetate aqueous solution added into the reaction system to the sodium oleate-alcohol solution is 1: 11.5-49, reacting for 30min at 80-120 ℃ under the condition of magnetic stirring to finally obtain the nano copper oxide.
2. The method for preparing nano copper oxide according to claim 1, wherein the molar ratio of sodium oleate to copper acetate in the reaction system of nano copper oxide in the step (2) is 1: 2.
3. the method as claimed in claim 1, wherein the alcohol solution in step (2) is ethanol, n-butanol or hexanol.
4. The method for preparing nano copper oxide according to claim 1, wherein the mass ratio of the deionized water to the copper acetate in the step (1) is 20: 1.
5. the method for preparing nano copper oxide according to claim 1, wherein the volume ratio of the copper acetate aqueous solution to the sodium oleate-alcohol solution in the step (3) is 1: 49.
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