CN102267714B - Preparation method for hollow silk cocoon-like CuO nanomaterial - Google Patents
Preparation method for hollow silk cocoon-like CuO nanomaterial Download PDFInfo
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Abstract
The invention discloses a preparation method for a hollow silk cocoon-like CuO nanomaterial, and provides a new method for the preparation technology of a hollow CuO nanomaterial. According to the present invention, the disadvantages in the prior art are overcome. The method is characterized in that: a normal-pressure and one-step microwave chemical synthesis method is adopted for preparing a hollow silk cocoon-like CuO nanomaterial, ie., aqueous solutions of soluble copper salt such as copper acetate and the like, and a queous solution of urea are adopted as precursor solutions, a one-step microwave irradiation process is adopted to prepare the hollow silk cocoon-like CuO nanomaterial. The hollow silk cocoon-like CuO nanomaterial provided by the present invention is ellipsoidal, and has characteristics of similar silk cocoon morphology, hollow structure, no agglomeration, monodisperse, and long diameter between 250-400 nm. With the present invention, the method has simple process; any surfactant and organic solvent is not used; the process is clean and environment-friendly; the method has characteristics of low reaction temperature, short reaction time, energy saving, low carbon, high performance, easy and available raw materials, low cost, and is applicable for the industrial production; the prepared material can be applicable for the fields of catalysis, antibacterial, solar battery, sensor material and the like.
Description
Technical field
The invention belongs to the semiconductor nano material preparing technical field, specifically, relate to a kind of hollow silk cocoon shape CuO preparations of nanomaterials method.
Background technology
Nano material has important effect because of its distinctive function and character at numerous areas such as nanometer light, electricity, magnetic.The performance of nano material depends on its appearance structure and size of particles, and the nano material of therefore controlling synthetic unique morphology structure more and more is subject to people and pays much attention to.The nano material of hollow structure is one of investigation of materials focus and difficult point because having larger specific surface area, lower density, good perviousness and unique photoelectricity and surface property always.
CuO is good semiconductor material, all has a wide range of applications at aspects such as photo-thermal, photoelectricity, sensor, superconduction, solar cell, Li-Ion rechargeable battery and organic catalyst compounds.Due to character such as the special optics of hollow nanostructures may, electricity, magnetics and catalysis, the preparation of hollow CuO nanostructure is had great importance again.The report of the synthetic method of hollow CuO nanostructure is not also a lot of at present.the S Y Gao of He'nan Normal University etc. has reported copper sulfate solution has been joined in the ammonia soln that contains tyrosine, reacted 4 hours at 130 ℃ by hydrothermal method after fully stirring, made outside diameter that the nanometer sheet by diameter 250nm assembles between the micro-sphere structure of the inner hollow of 1.5～3 μ m, tyrosine plays a part surfactant-like agent (Shuyan Gao, Shuxia Yang, Jie Shu, et al., Green Fabrication of HierarchicalCuO Hollow Micro/Nanostructures and Enhanced Performance as Electrode Materials forLithium-ion Batteries[J], J.Phys.Chem.C, 2008, 112:19324-19328.).The S L Wang of Institutes Of Technology Of Zhejiang etc. has reported take cetyl trimethylammonium bromide (CTAB) as tensio-active agent, obtained the hollow micron spherical structure (ShunliWang of outside diameter 5～10 μ m that assembled by nano strip in 6 hours 180 ℃ of reactions by hydrothermal method with the aqueous solution of cupric nitrate and urea, Hui Xu, Liuqin Qian, et al., CTAB-assisted synthesis and photocatalytic property of CuOhollow microspheres[J], J.Solid State Chem., 2009,182:1088-1093.).The Y G Zhang of Chinese University of Science and Technology etc. first at room temperature react take neutralized verdigris and hexamethylenetetramine as raw material the complex precursors ([Cu (C that made sheet in 1 day
6H
12N
4)
2] (OOCCH
3)
2), obtained again the diameter that assembled by nano particle in 18 hours 180 ℃ of reactions by hydrothermal method at hollow ball structure (the Yange Zhang of 1～1.5 μ m, Shutao Wang, Titai Qiang, et al., Complexing-reagent assisted synthesis of hollow microspheres[J], Solid State Sciences, 2006,8:462-466.).the Zhu Jun of Shanghai Communications University etc. has reported soluble copper salt (neutralized verdigris, cupric nitrate or copper sulfate) aqueous solution and ammoniacal liquor is mixed with the ammoniacal copper complex ion solution of clarification, then add water-fast Fatty Alcohol(C12-C14 and C12-C18) (propyl carbinol, n-hexyl alcohol, n-Octanol, butyleneglycol or glycerol), add again tensio-active agent (sodium lauryl sulphate, cetyl trimethylammonium bromide or song draw ketone) do the morphology control agent, adopt Microwave Radiation in Manufacturing, the control microwave power is 300～1000W, reaction times is 1～3 minute, made by nanometer sheet and assembled nano-hollow sphere structured a kind of (the hollow multilevel Cu O preparations of nanomaterials method of CuO, Chinese invention patent, publication number: CN 101306832A).Above related preparation method, or need to use tensio-active agent, both increased preparation cost, also affect purity and the output of product; Preparation process is loaded down with trivial details, temperature of reaction high (all higher than 100 ℃, very the person is up to 180 ℃), and long reaction time (a few hours or tens hours) is unfavorable for industrialization production; And prepared CuO hollow ball structure particle diameter is all larger, and outside diameter all reaches micron order, and very the person is tens of microns, and quality is not high.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of hollow silk cocoon shape CuO preparations of nanomaterials method is provided, technique is simple, raw material is easy to get, with low cost, operate controlled, simple and direct efficient, low-carbon environment-friendly, prepared nano material can be used for the fields such as catalysis, antibiotic, solar cell and sensor material.
The objective of the invention is to realize by following technical solution.
Technical scheme of the present invention is to adopt a step microwave heating method to prepare hollow silk cocoon shape CuO nano material,, take soluble copper salt, deionized water and urea as raw material, gets precursor solution after stirring and dissolving that is, and the reaction of precursor solution heated by microwave is generated.Its concrete technology step is as follows:
(1) take the soluble copper salts such as 1mmol neutralized verdigris and be mixed with solution A with deionized water;
(2) take a certain amount of urea and be mixed with solution B with deionized water, the mol ratio of mantoquita and urea is 1: 1～1: 3;
(3) under stirring state, solution A is joined in solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed in the microwave generator microwave exposure 20～40 minutes, temperature of reaction is 80 ± 10 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 turns;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed in baking oven and heated 6～12 hours, temperature is 40～60 ℃, collects black product and namely obtains hollow silk cocoon shape CuO nano material of the present invention.
In technique scheme, described hollow silk cocoon shape CuO nano material is elliposoidal, pattern is similar to silk cocoon, be hollow structure, without reunion, the single dispersion, long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, hollow silk cocoon is assembled by more tiny nanoparticle, and the particle diameter of nanoparticle is between 5～20nm.
Soluble copper salt in described step (1) comprises neutralized verdigris, cupric nitrate, chlorination copper and copper sulfate.
Mantoquita in described step (2) and the mol ratio of urea are 1: 2.
Microwave irradiation time in described step (4) is 30 minutes, and temperature of reaction is 80 ℃.
Described preparation technology's equipment is simple, and envrionment temperature is low, and is easy and simple to handle, good reproducibility; Do not adopt organic solvent and tensio-active agent to do template, the environmental friendliness cleaning; With short production cycle, productive rate is high, raw material sources are extensive, and are with low cost, suitability for industrialized production.
Compare with existing technology, beneficial effect of the present invention is embodied in:
(1) the present invention has adopted without the method for template and has prepared hollow CuO nanostructure.
(2) the inventive method adopts Microwave Radiation in Manufacturing, can improve on the one hand the crystallization velocity of product, and operation steps is simple on the other hand, is swift in response, and easily controls high-efficiency environment friendly.
(3) the inventive method is with respect to the method for having reported, present method reaction conditions requires easily to realize to temperature, raw material etc., and is with low cost, can be directly under normal pressure through obtaining hollow CuO nanostructure once the step liquid phase cracking process.
Description of drawings
Fig. 1 is low power scanning electronic microscope (SEM) photo of the embodiment of the present invention 1 hollow silk cocoon shape CuO nano material;
Fig. 2 is high power scanning electronic microscope (SEM) photo of the embodiment of the present invention 1 hollow silk cocoon shape CuO nano material.
Embodiment
Below by specific embodiment, technical scheme of the present invention is done the description of further detailed complete.Following embodiment further illustrates of the present invention, and does not limit the scope of the invention.
Embodiment 1
Hollow silk cocoon shape CuO nano material of the present invention adopts a step microwave heating method to prepare, and, take soluble copper salt, deionized water and urea as raw material, gets precursor solution after stirring and dissolving that is, and the reaction of precursor solution heated by microwave is generated.Its concrete technology step is as follows:
(1) take the 0.1997g neutralized verdigris and be mixed with solution A with the 10mL deionized water;
(2) take 0.1203g urea and be mixed with solution B with the 50mL deionized water, the mol ratio of mantoquita and urea is 1: 2;
(3) under stirring state, solution A is joined in solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed in the microwave generator microwave exposure 30 minutes, temperature of reaction is 80 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 turns;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed in baking oven heating 8 hours, temperature is 50 ℃, collects black product and namely obtains hollow silk cocoon shape CuO nano material of the present invention.
Referring to accompanying drawing 1, low power field scan Electronic Speculum (SEM) photo of the hollow silk cocoon shape CuO nano material that makes by the described method of embodiment 1.As can be seen from the figure hollow silk cocoon shape CuO nano material output is high, is elliposoidal, and pattern is similar to silk cocoon, good dispersity, and without reuniting, size distribution is even.
Referring to accompanying drawing 2, high power field scan Electronic Speculum (SEM) photo of the hollow silk cocoon shape CuO nano material that makes by the described method of embodiment 1.As can be seen from the figure hollow silk cocoon shape CuO nano material is hollow structure, and long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, and hollow silk cocoon is assembled by more tiny nanoparticle, and the particle diameter of nanoparticle is between 5～20nm.
Embodiment 2
Hollow silk cocoon shape CuO nano material of the present invention adopts a step microwave heating method to prepare, and, take soluble copper salt, deionized water and urea as raw material, gets precursor solution after stirring and dissolving that is, and the reaction of precursor solution heated by microwave is generated.Its concrete technology step is as follows:
(1) take the 0.1999g neutralized verdigris and be mixed with solution A with the 10mL deionized water;
(2) take 0.0601g urea and be mixed with solution B with the 50mL deionized water, the mol ratio of mantoquita and urea is 1: 1;
(3) under stirring state, solution A is joined in solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed in the microwave generator microwave exposure 30 minutes, temperature of reaction is 80 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 turns;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed in baking oven heating 10 hours, temperature is 50 ℃, collects black product and namely obtains hollow silk cocoon shape CuO nano material of the present invention.
The CuO nano material that makes by the described method of embodiment 2 is observed with SEM and is elliposoidal, is hollow silk cocoon shape structure, and long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, is assembled by the nanoparticle of 5～20nm.
Embodiment 3
Hollow silk cocoon shape CuO nano material of the present invention adopts a step microwave heating method to prepare, and, take soluble copper salt, deionized water and urea as raw material, gets precursor solution after stirring and dissolving that is, and the reaction of precursor solution heated by microwave is generated.
Its concrete technology step is as follows:
(1) take the 0.1998g neutralized verdigris and be mixed with solution A with the 10mL deionized water;
(2) take 0.1802g urea and be mixed with solution B with the 50mL deionized water, the mol ratio of mantoquita and urea is 1: 3;
(3) under stirring state, solution A is joined in solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed in the microwave generator microwave exposure 30 minutes, temperature of reaction is 80 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 turns;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed in baking oven heating 8 hours, temperature is 50 ℃, collects black product and namely obtains hollow silk cocoon shape CuO nano material of the present invention.
The CuO nano material that makes by the described method of embodiment 3 is observed with SEM and is elliposoidal, is hollow silk cocoon shape structure, and long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, is assembled by the nanoparticle of 5～20nm.
Embodiment 4
Hollow silk cocoon shape CuO nano material of the present invention adopts a step microwave heating method to prepare, and, take soluble copper salt, deionized water and urea as raw material, gets precursor solution after stirring and dissolving that is, and the reaction of precursor solution heated by microwave is generated.
Its concrete technology step is as follows:
(1) take the 0.2416g cupric nitrate and be mixed with solution A with the 10mL deionized water;
(2) take 0.1202g urea and be mixed with solution B with the 50mL deionized water, the mol ratio of mantoquita and urea is 1: 2;
(3) under stirring state, solution A is joined in solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed in the microwave generator microwave exposure 30 minutes, temperature of reaction is 80 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 turns;
(5) taking-up is cooled to room temperature, filtering precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed in baking oven heating 10 hours, temperature is 50 ℃, collects black product and namely obtains hollow silk cocoon shape CuO nano material of the present invention.
The CuO nano material that makes by the described method of embodiment 4 is observed with SEM and is elliposoidal, is hollow silk cocoon shape structure, and long diameter is between 250～400nm, and length diameter ratio is 1.2～1.5: 1, is assembled by the nanoparticle of 5～20nm.
Claims (4)
1. hollow silk cocoon shape CuO preparations of nanomaterials method, it is characterized in that, described hollow silk cocoon shape CuO nano material is elliposoidal, pattern is similar to silk cocoon, is hollow structure, without reunion, the single dispersion, long diameter is between 250～400nm, length diameter ratio is 1.2～1.5: 1, and hollow silk cocoon is assembled by more tiny nanoparticle, and the particle diameter of nanoparticle is between 5～20nm; The concrete technology step of described method is as follows:
(1) take the 1mmol soluble copper salt and be mixed with solution A with deionized water;
(2) take a certain amount of urea and be mixed with solution B with deionized water, the mol ratio of mantoquita and urea is 1: 1～1: 3;
(3) under stirring state, solution A is joined in solution B, form precursor solution C, overall solution volume is 60mL, continues to stir 10 minutes;
(4) precursor solution C was placed in the microwave generator microwave exposure 20～40 minutes, temperature of reaction is 80 ± 10 ℃, and microwave power is 300W, and magnetic agitation speed is that per minute 500 turns;
(5) taking-up is cooled to room temperature, filters black precipitate, and water and absolute ethanol washing are 2～3 times respectively;
(6) throw out is placed in baking oven and heated 6～12 hours, temperature is 40～60 ℃, collects black product and namely obtains hollow silk cocoon shape CuO nano material.
2. a kind of hollow silk cocoon shape CuO preparations of nanomaterials method according to claim 1, is characterized in that, the soluble copper salt in described step (1) is neutralized verdigris or cupric nitrate.
3. a kind of hollow silk cocoon shape CuO preparations of nanomaterials method according to claim 1, is characterized in that, the mantoquita in described step (2) and the mol ratio of urea are 1: 2.
4. a kind of hollow silk cocoon shape CuO preparations of nanomaterials method according to claim 1, is characterized in that, the microwave irradiation time in described step (4) is 30 minutes, and temperature of reaction is 80 ℃.
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| KR101525651B1 (en) * | 2012-04-20 | 2015-06-03 | 삼성전기주식회사 | Method of manufacturing copper precursor and copper precursor manufactured by using the same |
| CN105023762B (en) * | 2015-08-10 | 2017-11-14 | 安徽建筑大学 | A kind of foliaceous CuO NiO composite construction nano materials and preparation method thereof |
| CN106207148A (en) * | 2016-08-31 | 2016-12-07 | 青海中兴新能源有限公司 | A kind of preparation method of lithium ion battery negative material micro nano structure CuO |
| CN112647287B (en) * | 2020-12-17 | 2022-01-04 | 中国科学院过程工程研究所 | Super-hydrophobic material with hierarchical coarse structure and preparation method and application thereof |
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| CN101273723A (en) * | 2008-05-16 | 2008-10-01 | 曲阜师范大学 | Method for preparing nano copper oxide anti-bacteria agent |
| CN101407332A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
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| CN101407332A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Hydro-thermal synthesis method for cupric oxide nano-rod |
| CN101273723A (en) * | 2008-05-16 | 2008-10-01 | 曲阜师范大学 | Method for preparing nano copper oxide anti-bacteria agent |
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