CN115028187B - Chemical preparation method of copper oxide nano particles - Google Patents
Chemical preparation method of copper oxide nano particles Download PDFInfo
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- CN115028187B CN115028187B CN202210921281.9A CN202210921281A CN115028187B CN 115028187 B CN115028187 B CN 115028187B CN 202210921281 A CN202210921281 A CN 202210921281A CN 115028187 B CN115028187 B CN 115028187B
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 70
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 70
- 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 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 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 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 23
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 abstract description 21
- 238000002474 experimental method Methods 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000002211 ultraviolet spectrum Methods 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HAFAJCGPTCWGHB-UHFFFAOYSA-J [OH-].[OH-].[OH-].[OH-].[Cu+4] Chemical compound [OH-].[OH-].[OH-].[OH-].[Cu+4] HAFAJCGPTCWGHB-UHFFFAOYSA-J 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 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 Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- 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 copper acetate aqueous solution; weighing sodium oleate, measuring an alcohol solvent, mixing the alcohol solvent with the sodium oleate, stirring and heating to completely dissolve the sodium oleate, and obtaining a sodium oleate-alcohol solution; adding a copper acetate aqueous solution into a 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 existing method for preparing the nano copper oxide.
Description
Technical Field
The invention belongs to a solution chemical method synthesis technology, relates to a chemical preparation method of copper oxide nano particles, and belongs to the technical field of material preparation.
Background
Nanomaterials have many characteristics not possessed by large-scale particles, and when the size of the material is small to some extent, the properties of the material change significantly. The nano material has the advantages of surface effect, small-size effect, quantum size effect, macroscopic quantum tunneling effect, coulomb blockade effect and the like.
The nano copper oxide has very 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 combustion speed catalyst and the like; the nano copper oxide particles are small and have better performance than large-size copper oxide powder.
The function of the nano copper oxide can be exerted more when the diameter of the nano copper oxide particles is not more than 10nm, and various methods for producing the nano copper oxide exist at present, but the common problems of the existing preparation method are as follows: 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 nano copper oxide particles with smaller sizes cannot be stably and efficiently produced. This requires us to constantly explore and improve on the existing methods, and find the most suitable preparation method to stably and efficiently produce nano copper oxide.
Disclosure of Invention
The invention aims to: the invention provides a chemical preparation method of copper oxide nano particles, which aims to solve the problems of difficult control of reaction, complex preparation process, high preparation cost, larger particle size of the prepared product 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, completely dissolving copper acetate by ultrasonic treatment to prepare 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, and obtaining a sodium oleate-alcohol solution;
Step (3) adding a copper acetate aqueous solution into a sodium oleate-alcohol solution to obtain a nano copper oxide reaction system, wherein the volume ratio of the copper acetate aqueous solution to the sodium oleate-alcohol solution added into the reaction system is 1: 11.5-49, and reacting for 30min at 80-120 ℃ under the magnetic stirring condition to finally obtain the nano copper oxide.
Preferably, in the step (2), the molar ratio of sodium oleate to copper acetate in the nano copper oxide reflecting system is 1:2.
Preferably, the alcohol solution in the step (2) is ethanol, n-butanol or hexanol, respectively.
Preferably, in the step (1), the mass ratio of deionized water to copper acetate is 20:1.
Preferably, in the step (3), the volume ratio of the aqueous solution of copper acetate to the sodium oleate-alcohol solution is 1:49.
The beneficial effects are that:
The invention adopts a solution chemical method, adopts ethanol, n-butanol and n-hexanol as alcohol solvents, and prepares 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 particle size and good dispersibility, and can be prepared into ultra-small-size nano copper oxide by adjusting some reaction conditions.
Drawings
FIG. 1 shows XRD patterns of nano copper oxide prepared by adding different amounts of aqueous solution of copper acetate with ethanol as alcohol solvent in example 1 of the present invention;
FIG. 2 is a TEM spectrum of the nano copper oxide obtained by adding different amounts of aqueous solution of copper acetate with ethanol as alcohol solvent in the embodiment 1 of the present invention;
FIG. 3 shows XRD patterns of nano copper oxide generated by setting different reaction temperatures by using n-butanol as an alcohol solvent in the embodiment 2 of the invention;
FIG. 4 is a TEM spectrum of the nano copper oxide obtained by using n-butanol as an alcohol solvent and setting different reaction temperatures in the embodiment 2 of the present invention;
FIG. 5 shows XRD patterns of nano copper oxide prepared by using n-hexanol as alcohol solvent and setting different reaction temperatures in example 3;
FIG. 6 is a TEM spectrum of nano copper oxide obtained by using n-hexanol as 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 used in the examples of the present invention.
FIG. 8 is a UV spectrum of nano-copper oxide produced in example 1 of the present invention based on the addition of 4ml of aqueous copper acetate without sodium oleate.
FIG. 9 is a UV spectrum of nano-copper oxide produced by adding sodium oleate based on the addition of 4ml of aqueous solution of copper acetate in example 1 of the present invention.
Detailed Description
The invention provides a chemical preparation method of copper oxide nano particles, which is a preparation method for controlling the particle size of nano copper oxide by taking copper acetate (also called copper acetate) as a copper source, sodium oleate as a surfactant, ethanol, n-butyl alcohol or n-hexyl alcohol as an alcohol solvent, adding a small amount of deionized water and changing the conditions of the addition amount of a copper acetate aqueous solution, the reaction temperature and the like. The experimental method is simple, the experimental condition is mild, the operation is easy, and the particle size of the prepared nano copper oxide is small.
Example 1
The preparation method of the nano copper oxide comprises the following steps:
(1) ①0.1g②0.5g③0.25g④0.167g⑤ 0.125.125 g of copper acetate is weighed respectively, added into a corresponding 10ml volumetric flask filled with 10ml of deionized water (wherein deionized water is not added in experiment ①, and partial alcohol solvent in step (2) is taken correspondingly, and copper acetate is dissolved in partial alcohol solvent) to prepare copper acetate aqueous solution with required concentration by ultrasound until copper acetate is completely dissolved and the copper acetate concentration is ①0(0.1g)②2.5×10- 1mol·L-1③1.25×10-1mol·L-1④8.35×10-2mol·L-1⑤6.25×10-2mol·L-1, respectively.
(2) 5 Parts of 0.076g of sodium oleate are respectively weighed, ①100ml②98ml③96ml④94ml⑤ ml of ethanol is respectively measured by using a measuring cylinder, sodium oleate and corresponding ethanol are poured into a three-neck flask, stirred and heated to 80 ℃ in a magnetic heating stirrer until 5 parts of sodium oleate are completely dissolved, and sodium oleate-alcohol solution is obtained.
(3) And (3) respectively measuring ①0ml②2ml③4ml④6ml⑤ ml of copper acetate aqueous solution in the step (1), correspondingly adding the copper acetate aqueous solution into sodium oleate-alcohol solution of the three-neck flask with the corresponding serial number in the step (2) (specific operation data are shown in table 1), so that the total sum of each part is 100ml, the requirement that the actual addition amount of the copper acetate in each parallel experiment is unchanged, and the total amount of alcohol-water is unchanged is met. And (3) reacting for 30min under the conditions of constant temperature of 80 ℃ and magnetic stirring, and finally obtaining the nano copper oxide.
Table 1 experimental parameter table for changing water addition amount of ethanol system
From the experimental results, it was found that when no deionized water was added to the system in experiment ①, the solution was blue-green, and the copper oxide was black, so that the reaction did not occur in the reaction in which no water was added to the system. The reason is that the addition of deionized water can hydrolyze Cu 2+ and C 17H33COO- in the reaction system, and the reaction can be smoothly carried out. in fig. 1 a, b, c, d, in an ethanol system, ②2ml、③4ml、④6ml、⑤ ml of copper acetate aqueous solution is added to prepare an XRD pattern of a nano copper oxide product, and according to a comparison of copper oxide standard cards, a, b, c, d is formed by copper oxide, and in particular, in fig. 1 (in a similar processing manner in fig. 3 and fig. 5), for convenience of comparison of differences between performances of nano copper oxide obtained by parallel experiments in the same system, the XRD pattern of the same system is put in a graph, and is translated up and down for convenience of viewing. fig. 2 is a TEM photograph of an ethanol system changing an added aqueous solution of copper acetate (a, b, c, d corresponds to 2, 4,6, 8ml of aqueous solution of copper acetate, respectively), and it can be seen from the TEM photograph of fig. 2 that the size of nano copper oxide prepared under the ethanol system is about 5nm, and as the aqueous solution of copper acetate added into the ethanol system increases, the particle size of the generated nano copper oxide is increased and then decreased, and when the addition amount is 2ml, the size of the generated nano copper oxide is overall smaller and is approximately distributed about 2.5nm, so that in a parallel experiment of the ethanol system changing the aqueous solution of copper acetate, the addition of 2ml of aqueous solution of copper acetate is the optimal experiment. Subsequent experiments will be based on the conclusion of the experiment, namely: referring to ethanol system experiment ②, 2ml of copper acetate aqueous solution was added to the reaction system, and the influence of temperature on the experimental result was investigated by changing the alcohol solvent and the reaction temperature.
Example 2
The preparation method of the nano copper oxide comprises the following steps:
(1) Weighing 0.5g of copper acetate, weighing 10ml of deionized water, placing the two into a10 ml volumetric flask, and performing ultrasonic treatment until the copper acetate is completely dissolved to prepare a copper acetate aqueous solution with the concentration of 2.5X10 -1mol·L-1.
(2) 0.076G of sodium oleate is weighed, 98ml of n-butanol is measured, the two are poured into a three-neck flask, stirred and heated to ①80、②90、③ ℃ and ④ ℃ respectively in a magnetic heating stirrer, and four groups of parallel tests are carried out.
(3) After the sodium oleate is completely dissolved, 2ml of copper acetate aqueous solution in the step (1) is measured and added into the sodium oleate-alcohol solution in the three-neck flask in the step (2), and the reaction is carried out for 30min under the conditions of ①80、②90、③ ℃ and ④ ℃ respectively and magnetic stirring, so that the nano copper oxide is finally obtained.
As can be seen from XRD patterns (a, b, c, d corresponds to 80, 90, 100 and 110 ℃ respectively) of the n-butanol system in FIG. 3, the nano copper oxide can be generated by changing the temperature in the system, and the difference is that the sharper the diffraction peak of the generated nano copper oxide is, the better the crystallinity is along with the increase of the temperature. As can be seen from the TEM spectrum (a, b, c, d corresponds to 80, 90, 100 and 110 ℃ of the n-butanol system respectively) of the n-butanol system changing reaction temperature in FIG. 4, the size of the nano copper oxide prepared under the system is firstly reduced and then increased along with the increase of the temperature, but the total size is within 5nm and is distributed at most about 2.5nm, wherein the particle size of the nano copper oxide generated under the condition of the experiment ③ at 100 ℃ is the smallest, so that in the parallel experiment of the n-butanol system changing the reaction temperature, the temperature is the optimal experiment at 100 ℃. It can be seen that temperature is also a factor affecting the particle size of the nano-copper oxide.
Example 3
The preparation method of the nano copper oxide comprises the following steps:
(1) Weighing 0.5g of copper acetate, weighing 10ml of deionized water, placing the two into a10 ml volumetric flask, and performing ultrasonic treatment until the copper acetate is completely dissolved to prepare a copper acetate aqueous solution with the concentration of 2.5X10 -1mol·L-1.
(2) 0.076G of sodium oleate is weighed, 98ml of n-hexanol is measured by using a cylinder, the two are poured into a three-neck flask, stirred and heated to ①80、② ℃ and ③ ℃ respectively in a magnetic heating stirrer, and three groups of parallel experiments are carried out.
(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 reaction is carried out for 30min under the conditions of ①80、② ℃ and ③ ℃ and magnetic stirring, so that the nano copper oxide is finally obtained.
As is clear from XRD patterns (a, b, c correspond to 80, 100, 120 ℃ C.) of the n-hexanol system in FIG. 5 and TEM patterns (a, b correspond to 100, 120 ℃ C.) of the n-hexanol system in FIG. 6, respectively, when the temperature is 80 ℃ C. In this system, no copper oxide is generated, and when the temperature is raised to 100 ℃ C., nano copper oxide can be successfully produced, and in this system, XRD diffraction peaks are clear as a whole and the diffraction peaks are sharp, and as the temperature is raised, the size of the produced nano copper oxide increases as the temperature is raised, so that when the solvent is n-hexanol, the relatively low temperature (100 ℃ C. In this system) can make the particle size of the produced nano copper oxide smaller and distributed in most cases of about 2.5nm, therefore, in parallel experiments in which the temperature is 100 ℃ C. In the n-hexanol system is the reaction temperature is changed, the experiment is the best experiment.
The effect of sodium oleate in the system was next analyzed. Fig. 7 is an ultraviolet spectrum of a copper acetate aqueous solution, and fig. 8 and 9 are ultraviolet spectra of an ethanol system in example 1 without adding sodium oleate and sodium oleate when adding 4ml of the copper acetate aqueous solution, respectively, wherein each experiment was performed for 30min, and samples were taken every 10min for ultraviolet test. From the analysis of FIGS. 7, 8 and 9, it can be inferred that the reaction has not been started, as shown in FIG. 7, the graph of the first 10min before the addition of sodium oleate (corresponding to FIG. 8) is similar to that of FIG. 7; when sodium oleate is added, the ultraviolet spectrum at 10min is obviously changed compared with that of FIG. 7, so that the reaction rate is accelerated by adding sodium oleate. If the sodium oleate is too little, the reaction rate is 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 weighed, and a relatively optimal proportion is taken, namely, the molar ratio of the sodium oleate to the copper acetate actually added into the reaction is 1:2.
Reaction principle: the main hydrolysis of the aqueous solution of copper acetate in the sodium oleate-ethanol solution is Cu 2+ and CH 3COO-、C17H33COO-; of these, C 17H33COO- hydrolyzes to a greater extent than CH 3COO-, so sodium oleate may be the major source of OH -, cu 2+ with OH - forming Cu (OH) 2, and further Cu (OH) 4 2- (tetrahydroxy copper ion) in alkaline environments. If the tetrahydroxy copper is in an alkaline sodium oleate-ethanol system, two out-of-plane points can be possibly combined with water molecules and also can be combined with oleate, and the two points have a competitive relationship. When the proportion of oleic acid radical in the reaction system is far greater than that of water, the oleic acid radical takes the place of water, and more oleic acid radical occupies the position, so that the modification of nano particles is formed. The shrinkage of Cu (OH) 4 2- to polymeric CuO is no longer infinite due to modification of the oleic acid groups. The oleic acid radical is combined to the surface of the nano particle in a mode that lone pair electrons enter an empty track of copper, the more the oleic acid radical is combined, the larger the steric hindrance on the surface of the CuO nano particle is, the further occurrence of the glycidyl polymerization reaction is blocked, and the system reaches balance. From the above analysis, sodium oleate has two roles in the system: 1. providing an alkaline environment, and accelerating the reaction rate; 2. modifying the nano particles, blocking polycondensation reaction, and obtaining 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. As sodium oleate is added as a surfactant, the reaction rate and the growth of the copper oxide size can be controlled, so that the particle size of the prepared nano copper oxide is smaller. In the experiment, the ethanol system changes the adding amount of the copper acetate aqueous solution, but ensures that the actual adding reaction quality of the copper acetate is unchanged, which is equivalent to changing the adding amount of deionized water, and the particle size of the nano copper oxide is firstly increased and then decreased along with the increase of the water amount added into the reaction system, and in addition, the size of the nano copper oxide is influenced by the selection of the temperature to a certain extent. Therefore, the experiment can control the particle size of the nano copper oxide by regulating and controlling the adding amount of deionized water, the concentration of copper acetate, the reaction temperature and the type of alcohol.
Claims (2)
1. The chemical preparation method of the copper oxide nano-particles 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 20:1, completely dissolving copper acetate by ultrasonic treatment to prepare 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, and obtaining a sodium oleate-alcohol solution; the molar ratio of sodium oleate to copper acetate in the nano copper oxide reaction system is 1:2;
step (3) adding a copper acetate aqueous solution into the sodium oleate-alcohol solution to obtain a nano copper oxide reaction system;
The volume ratio of the aqueous solution of copper acetate and the sodium oleate-alcohol solution added into the reaction system is 1:49, reacting for 30min at 100-120 ℃ under the magnetic stirring condition, and finally obtaining the nano copper oxide.
2. The method for preparing nano copper oxide according to claim 1, wherein the alcohol solvent in the step (2) is n-butanol or hexanol.
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| CN202210921281.9A CN115028187B (en) | 2022-08-02 | 2022-08-02 | Chemical preparation method of copper oxide nano particles |
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| JP2003183024A (en) * | 2001-12-18 | 2003-07-03 | Asahi Kasei Corp | Method for producing cupric oxide fine particle |
| CN101302032A (en) * | 2008-01-08 | 2008-11-12 | 上海谐尔纳米科技有限公司 | Preparation of cupric oxide nano-material |
| CN101805009A (en) * | 2010-03-18 | 2010-08-18 | 同济大学 | Simple and controllable method for preparing lobate micron/nano copper oxide two-dimensional assembly |
| CN104445358A (en) * | 2014-11-06 | 2015-03-25 | 国核电力规划设计研究院 | Cuprous oxide nano microspheres in double-layered structure and preparation method thereof |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-like nanometer copper |
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| JP2003183024A (en) * | 2001-12-18 | 2003-07-03 | Asahi Kasei Corp | Method for producing cupric oxide fine particle |
| CN101302032A (en) * | 2008-01-08 | 2008-11-12 | 上海谐尔纳米科技有限公司 | Preparation of cupric oxide nano-material |
| CN101805009A (en) * | 2010-03-18 | 2010-08-18 | 同济大学 | Simple and controllable method for preparing lobate micron/nano copper oxide two-dimensional assembly |
| CN104445358A (en) * | 2014-11-06 | 2015-03-25 | 国核电力规划设计研究院 | Cuprous oxide nano microspheres in double-layered structure and preparation method thereof |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-like nanometer copper |
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| 超顺磁单分散性Fe_3O_4磁纳米粒的制备及性能表征;江雯;温贤涛;王伟;吴尧;顾忠伟;;无机材料学报(04);全文 * |
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