CN112499662A - Copper oxide nano material and preparation method thereof - Google Patents
Copper oxide nano material and preparation method thereof Download PDFInfo
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- CN112499662A CN112499662A CN202011267086.6A CN202011267086A CN112499662A CN 112499662 A CN112499662 A CN 112499662A CN 202011267086 A CN202011267086 A CN 202011267086A CN 112499662 A CN112499662 A CN 112499662A
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 68
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 68
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 238000003756 stirring Methods 0.000 claims abstract description 101
- 239000000243 solution Substances 0.000 claims abstract description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 66
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 50
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 44
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 230000010355 oscillation Effects 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000005507 spraying Methods 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000779 smoke Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000010517 secondary reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention relates to the technical field of nano materials, in particular to a copper oxide nano material which is prepared from the following raw materials in parts by weight: 10-40 parts of copper powder, 50-80 parts of absolute ethyl alcohol, 20-50 parts of nitric acid, 15-30 parts of caustic soda solution and 15-30 parts of ammonium nitrate solution. A preparation method of a copper oxide nano material comprises the following steps: s1, preparing a copper reaction solution: adding nitric acid into an acid-resistant reactor with stirring, slowly adding copper powder under stirring for reaction, heating the solution after the reaction is finished, driving out nitrogen oxide gas, and filtering liquid impurities after the reaction to prepare copper reaction liquid; s2, high-pressure spraying: and (4) feeding the copper reaction solution and the caustic soda solution in the step (S1) into an ultrasonic stirring device through a mixed solution high-pressure spraying device. According to the invention, the ultrasonic stirring device is used for stirring and ultrasonic oscillation in the process of preparing the copper oxide, so that the prepared copper oxide has uniform particle size distribution, good crystal form, smaller particles and an average size of 10 nm.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a copper oxide nano material and a preparation method thereof.
Background
The copper oxide nano material is a p-type semiconductor oxide with a narrow band gap, is used as an important multifunctional inorganic material, and is applied to the fields of magnetic materials, light absorption, sensors, superconducting materials, catalysts, thermistors, magnetic storage, lithium ion batteries, biological medicines and the like.
Chinese patent No. 201610027887.2 relates to a method for growing copper oxide (CuO) flower-like nano material on ceramic tube. The method adopts copper acetate as a copper source, takes a ceramic tube as a carrier, and directly carries out hydrothermal reaction to grow the copper oxide flower-shaped nano-structure material on the ceramic tube under the alkaline condition. The invention prepares the copper oxide flower-shaped nano-structure material: the single-layer nano slice is composed of single-layer nano slices composed of nano particles with the particle size of 50-80, wherein the particles are mutually adhered, obvious pores are formed among the particles, and the slice with a network structure is formed, has high purity, is single-phase, is neat in flower-shaped structure and has the diameter of 6-11 microns. The invention does not adopt a surfactant, has simple production process and strong controllability; the structure of the material has wide application prospect in the fields of magnetic materials, light absorption, sensors, superconducting materials, catalysts, thermistors, magnetic storage, lithium ion batteries and biomedicine.
Although the 201610027887.2 patent mentioned above can produce the copper oxide nano material, the production process is simple, which results in uneven particle size distribution, poor crystal form, large particles, no gas protection during the production process, low purity of the copper oxide material, more impurities, and limited area of the ceramic tube, which results in low production rate of the copper oxide, so it is necessary to design a copper oxide nano material and a method for producing the same to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a copper oxide nano material and a preparation method thereof, and aims to solve the problems of uneven particle size distribution, poor crystal form, larger particles, low purity and low preparation rate in the background technology.
The technical scheme of the invention is as follows: the copper oxide nano material comprises the following raw materials in parts by weight: 10-40 parts of copper powder, 50-80 parts of absolute ethyl alcohol, 20-50 parts of nitric acid, 15-30 parts of caustic soda solution and 15-30 parts of ammonium nitrate solution.
A preparation method of a copper oxide nano material comprises the following steps:
s1, preparing a copper reaction solution: adding nitric acid into an acid-resistant reactor with stirring, slowly adding copper powder under stirring for reaction, heating the solution after the reaction is finished, driving out nitrogen oxide gas, and filtering liquid impurities after the reaction to prepare copper reaction liquid;
s2, high-pressure spraying: conveying the copper reaction solution and the caustic soda solution in the step S1 into a reactor provided with an ultrasonic stirring device through a mixed solution high-pressure spraying device for stirring reaction;
s3, ultrasonic oscillation: introducing the ammonium nitrate solution into an ultrasonic stirring device in S2 for reaction, and oscillating by using ultrasonic waves;
s4, adjusting pH: adding nitric acid into a reactor of the ultrasonic stirring device in the S3, stirring while adding, and stopping adding the nitric acid until the pH value is 4.2-4.3;
s5, stirring: continuously stirring the ultrasonic stirring device in the step S4 for 40-60 minutes until the pH value is 4.3-4.5, and stopping the reaction to obtain a synthetic liquid;
s6, washing: standing the synthetic solution in the S5, removing supernatant, and washing the precipitate with water;
s7, drying: separating the washed precipitate from water in S6, and drying the precipitate using a dryer;
s8, heating and pressurizing: dissolving the precipitate obtained in S7 in absolute ethyl alcohol, putting the absolute ethyl alcohol into a reaction kettle, and carrying out heating and pressurizing reaction;
and S9, cooling, maintaining the pressure of the reaction kettle in the S8 for a period of time, introducing nitrogen, cooling to room temperature, separating black powder, and cleaning with clear water to obtain the nano copper oxide.
Further, in S1, the reaction time was 8 hours, and the reaction was continued until no yellow smoke was generated.
Further, in the S1, the mass concentration of the nitric acid is 30-32%, and the heating temperature is 60-70 ℃.
Further, in the S2, the mass concentration of the caustic soda solution is 23-27%, and the temperature is 25-30 ℃.
Further, in the S3, the mass concentration of the ammonium nitrate solution is 1.0-1.4%, and the temperature is 25-30 ℃.
Further, in the step S2, the rotation speed of a stirring shaft of the ultrasonic stirring device is 200r/min, and the temperature is 25-30 ℃.
Further, in the step S3, the oscillation time of the ultrasonic stirring device is 80-100min, and the temperature is 25-30 ℃.
Further, in the step S4, the pH value in the ultrasonic stirring device is 6.2-6.3 when nitric acid is added.
Further, the pressure maintaining time in the S9 is 0.5-1h, and the cleaning times are 2-3 times.
The invention provides a copper oxide nano material and a preparation method thereof through improvement, and compared with the prior art, the copper oxide nano material has the following improvement and advantages:
(1) according to the invention, the ultrasonic stirring device is used for stirring and ultrasonic oscillation in the process of preparing the copper oxide, so that the prepared copper oxide has uniform particle size distribution, good crystal form, smaller particles and an average size of 10 nm.
(2) The invention utilizes nitrogen to be introduced into the reaction kettle, so that the copper oxide with higher temperature is not easy to have secondary reaction with other substances in the air, and the prepared nano-scale copper oxide material has higher purity and no other impurities.
(3) The invention utilizes the high-pressure spraying device to spray the copper reaction solution and the caustic soda solution, so that the copper reaction solution and the caustic soda solution react more thoroughly, and the effect of high preparation rate of the copper oxide nano material is further realized.
Drawings
The invention is further explained below with reference to the figures and examples:
FIG. 1 is an overall flow diagram of the present invention;
FIG. 2 is a flow chart of ultrasonic oscillation according to the present invention;
FIG. 3 is a flow diagram of the agitation of the present invention;
FIG. 4 is a drying flowchart of the present invention;
fig. 5 is an air drying flow chart of the present invention.
Detailed Description
The present invention will be described in detail with reference to fig. 1 to 5, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example one
The copper oxide nano material comprises the following raw materials in parts by weight: 40 parts of copper powder, 70 parts of absolute ethyl alcohol, 40 parts of nitric acid, 25 parts of caustic soda solution and 25 parts of ammonium nitrate solution.
A preparation method of a copper oxide nano material comprises the following steps:
s1, preparing a copper reaction solution: adding nitric acid into an acid-resistant reactor with stirring to prevent the nitric acid from reacting with a container, slowly adding copper powder under stirring to react, heating the solution after the reaction is finished, driving out nitrogen oxide gas, collecting the nitrogen oxide gas for harmless treatment, filtering liquid impurities after the reaction, and filtering to ensure that the prepared nano copper oxide is purer to prepare a copper reaction solution, wherein the main component of the copper reaction solution is copper nitrate;
s2, high-pressure spraying: conveying the copper reaction liquid and the caustic soda solution in the step S1 into a reactor provided with an ultrasonic stirring device through a liquid mixing high-pressure spraying device for stirring reaction, wherein the high-pressure spraying device is used for enabling the reaction of the copper reaction liquid and the caustic soda solution to be more uniform and thorough, the ultrasonic stirring device is S312-90 in model, and the ultrasonic stirring device is used for facilitating stirring and ultrasonic oscillation of the reaction;
s3, ultrasonic oscillation: introducing the ammonium nitrate solution into an ultrasonic stirring device in S2 for reaction, and oscillating by using ultrasonic waves to ensure that the ammonium nitrate solution reacts more thoroughly;
s4, adjusting pH: adding nitric acid into a reactor of an ultrasonic stirring device in S3, stirring while adding, fully mixing the nitric acid by using the ultrasonic stirring device, and stopping adding the nitric acid until the pH value is 4.2;
s5, stirring: continuing to stir the ultrasonic stirring device in the step S4 for 50 minutes until the pH value is 4.4, stopping the reaction to obtain a synthetic liquid, and stirring for 50 minutes to stabilize the pH value of the synthetic liquid;
s6, washing: standing the synthetic solution in the S5, removing supernatant, and washing the precipitate with water;
s7, drying: separating the washed precipitate from water in S6, and drying the precipitate using a dryer;
s8, heating and pressurizing: dissolving the precipitate obtained in the step S7 in absolute ethyl alcohol, putting the absolute ethyl alcohol into a reaction kettle, and carrying out heating and pressurizing reaction to ensure that the precipitate and the absolute ethyl alcohol are fully reacted;
and S9, cooling, namely maintaining the pressure of the reaction kettle in the S8 for a period of time, introducing nitrogen, cooling to room temperature, separating black powder, and cleaning with clear water to obtain the nano copper oxide, wherein the nitrogen is used for preventing the generated copper oxide nano material from carrying out secondary reaction with air, so that the purity of the nano copper oxide material is improved.
Further, in S1, the reaction time was 8 hours, and the reaction was continued until no yellow smoke was generated, so that the added copper powder could be sufficiently reacted, and the remaining unreacted copper powder was prevented, and further mixed with the produced copper oxide nanomaterial, affecting the purity of the copper oxide nanomaterial.
Further, in S1, the nitric acid was 30% by mass, and the copper powder was reacted with the nitric acid at 30% by mass, thereby preventing the reaction from being too severe, and the heating temperature was 60 ℃.
Further, in S2, the caustic soda solution has a mass concentration of 25% and a temperature of 30 ℃, and the reaction is favorably carried out using a moderate temperature of 30 ℃.
Further, in S3, the mass concentration of the ammonium nitrate solution is 1.0%, the participation of the ammonium nitrate solution with the mass concentration of 1.0% is utilized to prevent the reaction from being too violent, and the reaction temperature is 30 ℃, so that the reaction process is mild.
Further, in S2, the rotation speed of the stirring shaft of the ultrasonic stirring device is 200r/min, and the stirring and ultrasonic oscillation of the reaction by the ultrasonic stirring device are facilitated, so that the reaction is further completely performed, the occurrence of impurities is prevented, the particles of the generated copper oxide nano material are small and uniformly distributed, and the reaction temperature is 30 ℃.
Further, in S3, the time of oscillation of the ultrasonic stirring device was 80min, and the temperature was 30 ℃, so that the substances inside the reactor were sufficiently reacted with each other.
Further, in S4, the pH value in the ultrasonic stirring apparatus was 6.2 when nitric acid was added, and the pH value in the ultrasonic stirring apparatus was adjusted by adding nitric acid and other acid ions, and the reaction temperature was 30 ℃.
Further, the pressure maintaining time in S9 is 1h, so that the precipitate and absolute ethanol completely react, and the number of times of cleaning is 3, so that the obtained nano copper oxide material is relatively pure.
Example two
The copper oxide nano material comprises the following raw materials in parts by weight: 30 parts of copper powder, 70 parts of absolute ethyl alcohol, 40 parts of nitric acid, 25 parts of caustic soda solution and 25 parts of ammonium nitrate solution.
A preparation method of a copper oxide nano material comprises the following steps:
s1, preparing a copper reaction solution: adding nitric acid into an acid-resistant reactor with stirring to prevent the nitric acid from reacting with a container, slowly adding copper powder under stirring to react, heating the solution after the reaction is finished, driving out nitrogen oxide gas, collecting the nitrogen oxide gas for harmless treatment, filtering liquid impurities after the reaction, and filtering to ensure that the prepared nano copper oxide is purer to prepare a copper reaction solution, wherein the main component of the copper reaction solution is copper nitrate;
s2, high-pressure spraying: conveying the copper reaction liquid and the caustic soda solution in the step S1 into a reactor provided with an ultrasonic stirring device through a liquid mixing high-pressure spraying device for stirring reaction, wherein the high-pressure spraying device is used for enabling the reaction of the copper reaction liquid and the caustic soda solution to be more uniform and thorough, the ultrasonic stirring device is S312-90 in model, and the ultrasonic stirring device is used for facilitating stirring and ultrasonic oscillation of the reaction;
s3, ultrasonic oscillation: introducing the ammonium nitrate solution into an ultrasonic stirring device in S2 for reaction, and oscillating by using ultrasonic waves to ensure that the ammonium nitrate solution reacts more thoroughly;
s4, adjusting pH: adding nitric acid into a reactor of an ultrasonic stirring device in S3, stirring while adding, fully mixing the nitric acid by using the ultrasonic stirring device, and stopping adding the nitric acid until the pH value is 4.2;
s5, stirring: continuing to stir the ultrasonic stirring device in the step S4 for 50 minutes until the pH value is 4.4, stopping the reaction to obtain a synthetic liquid, and stirring for 50 minutes to stabilize the pH value of the synthetic liquid;
s6, washing: standing the synthetic solution in the S5, removing supernatant, and washing the precipitate with water;
s7, drying: separating the washed precipitate from water in S6, and drying the precipitate using a dryer;
s8, heating and pressurizing: dissolving the precipitate obtained in the step S7 in absolute ethyl alcohol, putting the absolute ethyl alcohol into a reaction kettle, and carrying out heating and pressurizing reaction to ensure that the precipitate and the absolute ethyl alcohol are fully reacted;
and S9, cooling, namely maintaining the pressure of the reaction kettle in the S8 for a period of time, introducing nitrogen, cooling to room temperature, separating black powder, and cleaning with clear water to obtain the nano copper oxide, wherein the nitrogen is used for preventing the generated copper oxide nano material from carrying out secondary reaction with air, so that the purity of the nano copper oxide material is improved.
Further, in S1, the reaction time was 8 hours, and the reaction was continued until no yellow smoke was generated, so that the added copper powder could be sufficiently reacted, and the remaining unreacted copper powder was prevented, and further mixed with the produced copper oxide nanomaterial, affecting the purity of the copper oxide nanomaterial.
Further, in S1, the nitric acid was 30% by mass, and the copper powder was reacted with the nitric acid at 30% by mass, thereby preventing the reaction from being too severe, and the heating temperature was 60 ℃.
Further, in S2, the caustic soda solution has a mass concentration of 25% and a temperature of 30 ℃, and the reaction is favorably carried out using a moderate temperature of 30 ℃.
Further, in S3, the mass concentration of the ammonium nitrate solution is 1.0%, the participation of the ammonium nitrate solution with the mass concentration of 1.0% is utilized to prevent the reaction from being too violent, and the reaction temperature is 30 ℃, so that the reaction process is mild.
Further, in S2, the rotation speed of the stirring shaft of the ultrasonic stirring device is 200r/min, and the stirring and ultrasonic oscillation of the reaction by the ultrasonic stirring device are facilitated, so that the reaction is further completely performed, the occurrence of impurities is prevented, the particles of the generated copper oxide nano material are small and uniformly distributed, and the reaction temperature is 30 ℃.
Further, in S3, the time of oscillation of the ultrasonic stirring device was 80min, and the temperature was 30 ℃, so that the substances inside the reactor were sufficiently reacted with each other.
Further, in S4, the pH value in the ultrasonic stirring apparatus was 6.2 when nitric acid was added, and the pH value in the ultrasonic stirring apparatus was adjusted by adding nitric acid and other acid ions, and the reaction temperature was 30 ℃.
Further, the pressure maintaining time in S9 is 1h, so that the precipitate and absolute ethanol completely react, and the number of times of cleaning is 3, so that the obtained nano copper oxide material is relatively pure.
EXAMPLE III
The copper oxide nano material comprises the following raw materials in parts by weight: 20 parts of copper powder, 70 parts of absolute ethyl alcohol, 40 parts of nitric acid, 25 parts of caustic soda solution and 25 parts of ammonium nitrate solution.
A preparation method of a copper oxide nano material comprises the following steps:
s1, preparing a copper reaction solution: adding 30% nitric acid into an acid-resistant reactor with a stirrer to prevent the nitric acid from reacting with a container, wherein the reaction temperature is 60 ℃, copper powder is slowly added under stirring to react, the reaction time is 8 hours after the reaction is finished, the solution is heated until no yellow smoke is generated, nitrogen oxide gas is expelled, the nitrogen oxide gas is collected and subjected to harmless treatment, liquid impurities after the reaction are filtered, and the prepared nano copper oxide is purer through filtering to prepare a copper reaction liquid, wherein the main component of the copper reaction liquid is copper nitrate;
s2, high-pressure spraying: conveying the copper reaction liquid and the caustic soda solution with the mass concentration of 25% in the S1 into a reactor provided with an ultrasonic stirring device through a liquid mixing high-pressure spraying device for stirring reaction, wherein the high-pressure spraying device is used for enabling the copper reaction liquid and the caustic soda solution to react more uniformly and thoroughly, the ultrasonic stirring device is S312-90 in model, the ultrasonic stirring device is used for facilitating stirring and ultrasonic oscillation of the reaction, and the reaction temperature is 30 ℃;
s3, ultrasonic oscillation: introducing an ammonium nitrate solution with the mass concentration of 1.0% into an ultrasonic stirring device in S2 for reaction at the reaction temperature of 30 ℃, and oscillating by using ultrasonic waves for 80min, so that the ammonium nitrate solution is reacted more thoroughly;
s4, adjusting pH: adding nitric acid into a reactor of an ultrasonic stirring device in the S3, stirring while adding, wherein the rotating speed of the ultrasonic stirring device is 200r/min, fully mixing the nitric acid by using the ultrasonic stirring device, and stopping adding the nitric acid until the pH value is 4.2;
s5, stirring: continuing to stir the ultrasonic stirring device in the step S4 for 50 minutes until the pH value is 4.4, stopping the reaction to obtain a synthetic liquid, and stirring for 50 minutes to stabilize the pH value of the synthetic liquid;
s6, washing: standing the synthetic solution in the S5, removing supernatant, and washing the precipitate with water;
s7, drying: separating the washed precipitate from water in S6, and drying the precipitate using a dryer;
s8, heating and pressurizing: dissolving the precipitate obtained in the step S7 in absolute ethyl alcohol, putting the absolute ethyl alcohol into a reaction kettle, and carrying out heating and pressurizing reaction to ensure that the precipitate and the absolute ethyl alcohol are fully reacted;
and S9, cooling, namely maintaining the pressure of the reaction kettle in the S8 for a period of time, introducing nitrogen, cooling to room temperature, separating black powder, and cleaning with clear water to obtain the nano copper oxide, wherein the nitrogen is used for preventing the generated copper oxide nano material from carrying out secondary reaction with air, so that the purity of the nano copper oxide material is improved.
Further, in S1, the reaction time was 8 hours, and the reaction was continued until no yellow smoke was generated, so that the added copper powder could be sufficiently reacted, and the remaining unreacted copper powder was prevented, and further mixed with the produced copper oxide nanomaterial, affecting the purity of the copper oxide nanomaterial.
Further, in S1, the nitric acid was 30% by mass, and the copper powder was reacted with the nitric acid at 30% by mass, thereby preventing the reaction from being too severe, and the heating temperature was 60 ℃.
Further, in S2, the caustic soda solution has a mass concentration of 25% and a temperature of 30 ℃, and the reaction is favorably carried out using a moderate temperature of 30 ℃.
Further, in S3, the mass concentration of the ammonium nitrate solution is 1.0%, the participation of the ammonium nitrate solution with the mass concentration of 1.0% is utilized to prevent the reaction from being too violent, and the reaction temperature is 30 ℃, so that the reaction process is mild.
Further, in S2, the rotation speed of the stirring shaft of the ultrasonic stirring device is 200r/min, and the stirring and ultrasonic oscillation of the reaction by the ultrasonic stirring device are facilitated, so that the reaction is further completely performed, the occurrence of impurities is prevented, the particles of the generated copper oxide nano material are small and uniformly distributed, and the reaction temperature is 30 ℃.
Further, in S3, the time of oscillation of the ultrasonic stirring device was 80min, and the temperature was 30 ℃, so that the substances inside the reactor were sufficiently reacted with each other.
Further, in S4, the pH value in the ultrasonic stirring apparatus was 6.2 when nitric acid was added, and the pH value in the ultrasonic stirring apparatus was adjusted by adding nitric acid and other acid ions, and the reaction temperature was 30 ℃.
Further, the pressure maintaining time in S9 is 1h, so that the precipitate and absolute ethanol completely react, and the number of times of cleaning is 3, so that the obtained nano copper oxide material is relatively pure.
The conditions are the same except for the different parts of the added copper powder in the three examples, and the weight of the copper oxide nano material of the black powder obtained by comparing the three examples is as follows in sequence: in the first, second and third examples, the weight of the copper oxide nano material in the third example is the smallest, but the black powder in the first example has a small amount of yellow particles, and is judged to be unreacted copper powder according to experience.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A copper oxide nanomaterial, characterized in that: the feed is prepared from the following raw materials in parts by weight: 10-40 parts of copper powder, 50-80 parts of absolute ethyl alcohol, 20-50 parts of nitric acid, 15-30 parts of caustic soda solution and 15-30 parts of ammonium nitrate solution.
2. A preparation method of a copper oxide nano material is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a copper reaction solution: adding nitric acid into an acid-resistant reactor with stirring, slowly adding copper powder under stirring for reaction, heating the solution after the reaction is finished, driving out nitrogen oxide gas, and filtering liquid impurities after the reaction to prepare copper reaction liquid;
s2, high-pressure spraying: conveying the copper reaction solution and the caustic soda solution in the step S1 into a reactor provided with an ultrasonic stirring device through a mixed solution high-pressure spraying device for stirring reaction;
s3, ultrasonic oscillation: introducing the ammonium nitrate solution into an ultrasonic stirring device in S2 for reaction, and oscillating by using ultrasonic waves;
s4, adjusting pH: adding nitric acid into a reactor of the ultrasonic stirring device in the S3, stirring while adding, and stopping adding the nitric acid until the pH value is 4.2-4.3;
s5, stirring: continuously stirring the ultrasonic stirring device in the step S4 for 40-60 minutes until the pH value is 4.3-4.5, and stopping the reaction to obtain a synthetic liquid;
s6, washing: standing the synthetic solution in the S5, removing supernatant, and washing the precipitate with water;
s7, drying: separating the washed precipitate from water in S6, and drying the precipitate using a dryer;
s8, heating and pressurizing: dissolving the precipitate obtained in S7 in absolute ethyl alcohol, putting the absolute ethyl alcohol into a reaction kettle, and carrying out heating and pressurizing reaction;
and S9, cooling, maintaining the pressure of the reaction kettle in the S8 for a period of time, introducing nitrogen, cooling to room temperature, separating black powder, and cleaning with clear water to obtain the nano copper oxide.
3. The method for preparing a copper oxide nanomaterial according to claim 2, wherein the method comprises the following steps: in the S1, the reaction time was 8 hours, and the reaction was continued until no yellow smoke was generated.
4. The method for preparing a copper oxide nanomaterial according to claim 2, wherein the method comprises the following steps: in the S1, the mass concentration of nitric acid is 30-32%, and the heating temperature is 60-70 ℃.
5. The method for preparing a copper oxide nanomaterial according to claim 2, wherein the method comprises the following steps: in the S2, the mass concentration of the caustic soda solution is 23-27%, and the temperature is 25-30 ℃.
6. The method for preparing a copper oxide nanomaterial according to claim 2, wherein the method comprises the following steps: in the S3, the mass concentration of the ammonium nitrate solution is 1.0-1.4%, and the temperature is 25-30 ℃.
7. The method for preparing a copper oxide nanomaterial according to claim 2, wherein the method comprises the following steps: in the step S2, the rotating speed of a stirring shaft of the ultrasonic stirring device is 200r/min, and the temperature is 25-30 ℃.
8. The method for preparing a copper oxide nanomaterial according to claim 2, wherein the method comprises the following steps: in S3, the oscillation time of the ultrasonic stirring device is 80-100min, and the temperature is 25-30 ℃.
9. The method for preparing a copper oxide nanomaterial according to claim 2, wherein the method comprises the following steps: and in the step S4, the pH value in the ultrasonic stirring device is 6.2-6.3 when the nitric acid is added.
10. The method for preparing a copper oxide nanomaterial according to claim 2, wherein the method comprises the following steps: and the pressure maintaining time in the S9 is 0.5-1h, and the cleaning times are 2-3.
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