CN103043703B - Preparation method of hollow Cu2O cubic box - Google Patents
Preparation method of hollow Cu2O cubic box Download PDFInfo
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- CN103043703B CN103043703B CN201310002833.7A CN201310002833A CN103043703B CN 103043703 B CN103043703 B CN 103043703B CN 201310002833 A CN201310002833 A CN 201310002833A CN 103043703 B CN103043703 B CN 103043703B
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Abstract
The invention discloses a preparation method of a hollow Cu2O cubic box. The method is characterized in that the hollow Cu2O cubic box is prepared by a backflow method in an ethanediol-water or alcohol-water system by virtue of SDS (sodium dodecyl sulfate). A size of the box approximates to 1 micrometer, and the box is regular and neat in appearance, and has a larger inner space. The method adopts an anionic surfactant with low toxicity, namely SDS, and facilitates nonhazardous production and environmental protection. Adopted raw materials belong to ordinary chemical reagents and are easy to obtain.
Description
Technical field
Technical scheme of the present invention belongs to the synthetic field of hollow structure functional materials technology, be specially a kind of in the auxiliary lower backflow legal system of tensio-active agent the method for hollow Red copper oxide cube box.
Background technology
Red copper oxide is a kind of important inorganic oxide, and the copper atom by 88.1% and 11.9% Sauerstoffatom form.It is the lower valency oxide compound of copper, and English name is Cuprous Oxide or Copper (I) Oxide.Molecular formula is Cu
2o, molecular weight is 143.09, density 6.0g/cm
3, fusing point is 1235 ℃.Red copper oxide is generally red or orange-yellow octahedral isometric system crystalline powder, due to the difference of preparation method and granular size, can show as Huang, orange, the multiple color such as red or purple.
Red copper oxide, as a kind of p-type semiconductor material with unique light, magnetism characteristic, is having potential application aspect solar energy converting, electronics, magnetic storing unit, bio-sensing and catalysis.Red copper oxide band gap width is 2.1eV, and exciton can transmit continuously in monocrystalline, makes it have higher specific absorbance, becomes the important materials of making photovoltaic converter.In addition, due to quantum size effect, along with reducing of particle diameter, Red copper oxide shows peculiar optics, electricity and PhotoelectrochemicalProperties Properties and catalytic activity, and Cu is found in research recently
2the submicron particles of O can be for the negative material of lithium cell; The Red copper oxide of submicron order has special photocatalytic activity, can under visible ray effect, generate hydrogen and oxygen by photodissociation water, and this exploitation that is following hydrogen energy source provides important thinking.
In recent years, the structure of inorganic micro-nano hollow structure and assembling have caused and have studied widely interest.Hollow structure more and more receives people's concern in the potential utilization of the aspects such as catalyzer, sorbent material, medicament transport, optical imagery, photonic crystal, advanced low-k materials and sound-proof material with its unique calorifics, magnetics, optics, electricity and surface properties and it.Along with extensively carrying out of hollow structure research, corresponding nanometer ball, nanocubes, octahedral hollow structure also prepare recently.
Kuo etc., in Surfactant SDS system, under the condition existing, use NH at NaOH solution
2oHHCl makes reductive agent, and { the Cu of 100} face hollow out has been prepared in reduction
2o hollow dodecahedron nanometer skeleton construction, further ageing has obtained hollow dodecahedron nanocages, another { nanometer skeleton construction (C.H.Kuo, M.H.Huang.Fabricationof truncated rhombic dodecahedral Cu of 110} crystal face part hollow out have been prepared by adding ethanol to cause acid etching in this system
2o nanocages and nanoframes by particle aggregation and acidic etching[J] .Journal of the American Chemical Society, 2008,130 (38): 12815-12820).Wang etc. utilize the xitix will be at the Cu of cetyl trimethylammonium bromide (CTAB) vesica soft template structure periphery enrichment
2+be reduced to Cu
2o, has successfully prepared Cu
2o hollow ball, and along with the increase of CTAB concentration, CTAB imitated vesicle structure can change to multilayer from individual layer, has further prepared 3 layers of Cu
2o hollow structure (H.L.Xu, W.Z.Wang.Template synthesisof multishelled Cu
2o hollow spheres with a single-crystalline shellwall[J] .Angewandte Chemie International Edition, 2007,46 (9): 1489-1492).Zhu etc., take sodium lauryl sulphate-polyvinylpyrrolidone soft matter cluster as template, adopt N
2h
4h
2o reduces CuSO
4controlledly synthesis Cu
2o hollow sub-micro ball, and investigated its application (H.T.Zhu, J.X.Wang, G.Y.Xu.Fast synthesisof Cu on DNA biosensor
2o hollow microspheres and their application in DNA biosensor of hepatitis B virus[J] .Crystal Growth and Design, 2009,9 (1): 633-638).Xu etc. utilize the auxiliary wet chemistry method of polyoxyethylene glycol (PEG) to prepare the Cu of 50-80nm
2o/PEG400 composite hollow ball (Y.Y.Xu, X.L.Jiao, D.R.Chen, et al.Nanosized Cu
2o/PEG400composite hollow spheres with mesoporous shells[J] .Journal of Physical Chemistry C, 2007,111 (44): 16284-16289).Xu etc. prepare monocrystalline Cu under PEG is auxiliary
2o hollow nanocubes (Y.Y.Xu, X.L.Jiao, D.R.Chen.PEG-assisted preparation of single-crystalline Cu
2o hollow nanocubes[J] .Journal of Physical Chemistry C, 2008,112 (43): 16769-16773).Gao Hongjun group is done template, CuSO with tensio-active agent cetyl trimethyl ammonia bromide (CTAB)
4for Cu source, reduce and obtained Cu with xitix
2the nano-hollow cubes (H.R.Zhang, C.M.Shen, S.T.Chen, Z.C.Xu, et al.Nanotechnology, 2005,16:267-272) of O.The people such as Luo adopt liquid phase reduction under nonionogenic tenside Triton X-100 exists, and use Reduction of Glucose CuCl
2obtain Cu
2o solid cubes gradually cavitation has been prepared the Cu that the length of side is 200nm left and right
2o nano-hollow cubes (Luo F, Wu D, Gao L.Shape-Controlled Synthesis of Cu
2o Nanocrystals Assisted by Triton X-100[J] .J Cryst Growth, 2005,285:534-540).Qi etc. are by PdCl
2be incorporated in film solution, make reductive agent, the Cu that ageing obtains monocrystalline in 3 hours at 75 ℃ with glucose
2o octahedra nanocages (L.M.Qi, J.H.Yang, X.Y.Wang, D.Y.Zhang, J.L.Xie and J.M.Ma.One-pot synthesis of octahedral Cu
2o nanocages by a catalytic solution route[J] .Advanced Materials, 2005,17:2562-2567).But the prepared Red copper oxide hollow material of above method focuses mostly in nano level, and size and internal space are less, and the Red copper oxide hollow material of micro-meter scale can provide larger internal space, can hold more content.
Summary of the invention
Technical problem to be solved by this invention is: a kind of preparation method of hollow Red copper oxide cube box is provided, under sodium laurylsulfonate (SDS) is auxiliary, in ethylene glycol-water or ethanol-water system, has prepared hollow Cu by circumfluence method
2o cube of box, and its size is about 1 micron, has larger internal space.
The present invention solves this technical problem adopted technical scheme:
A preparation method for hollow Red copper oxide cube box, comprises the steps:
(1) mantoquita is soluble in water, make the copper salt solution that concentration is 0.001 mole of copper ion/ml water, separately sodium laurylsulfonate and reductive agent are dissolved in alcohol, make sodium laurylsulfonate-reductive agent-ol solution, its concentration is that every milliliter of alcohol contains 0.0125～0.1 gram of sodium laurylsulfonate and 0.0078～0.0675 gram of reductive agent, gets 20 parts of copper salt solutions and mixes with 40 parts of sodium laurylsulfonate-reductive agent-ol solution, adds in the flask with reflux, stir, stand-by;
Described reductive agent is glucose, S-WAT or hydrazine hydrate;
(2) precipitation agent is dissolved in water, makes the precipitant solution that concentration is 0.16～0.269 gram of precipitation agent/ml water, get 10 parts, then add the alcohol of 20～80 parts, be mixed with precipitation agent-ol-water mixed solution, stand-by;
(3) mixing solutions of preparation in step (2) is added in the flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 2～4 hours, stops stirring and heating;
(4) upper step products therefrom is at room temperature left standstill to 0～15 hour, obtain brick-red precipitation, then washing, then through suction filtration, by brick-red gained precipitation vacuum drying, obtain hollow Red copper oxide cube box powder.
The umber of said components is volume parts, and in each step, volume unit used is identical.
Mantoquita described in step (1) is cupric chloride, copper sulfate or neutralized verdigris above;
Alcohol described in step (1) and (2) is ethylene glycol or ethanol above.
When reductive agent in step (1) is glucose above, the proportioning of reductive agent and alcohol is 0.045～0.0675 gram of glucose/milliliter alcohol;
When reductive agent in step (1) is S-WAT above, the proportioning of reductive agent and alcohol is 0.0315～0.0378 gram of S-WAT/milliliter alcohol;
When reductive agent in step (1) is hydrazine hydrate above, the proportioning of reductive agent and alcohol is 0.0078～0.0118 gram of hydrazine hydrate (massfraction is 80%)/milliliter alcohol;
Precipitation agent described in step (2) is sodium hydroxide or potassium hydroxide above;
When precipitation agent described in step (2) is sodium hydroxide above, the concentration of precipitant solution is 0.16～0.192 gram of sodium hydroxide/ml water;
When precipitation agent described in step (2) is potassium hydroxide above, the concentration of precipitant solution is 0.224～0.269 gram of potassium hydroxide/ml water;
The invention has the beneficial effects as follows:
1. the rib of the hollow Red copper oxide cube box that the inventive method obtains is about 1 micron, and pattern is regular, as shown in Figure 2.Hollow Red copper oxide cube box, comparing solid cubes has higher specific surface energy, good osmosis, boring structure can be loaded guest molecule.As shown in Figure 1, the XRD diffraction peak of product Red copper oxide is clear, sharp-pointed, illustrates that to obtain the crystallinity of Red copper oxide fine.
2. in the inventive method, adopt the low anion surfactant sodium laurylsulfonate of toxicity, be conducive to toxicological harmless production and environment protection.
3. the present invention adopts raw material cupric chloride, copper sulfate, neutralized verdigris; Glucose (C
6h
12o
6), S-WAT (Na
2sO
3), hydrazine hydrate (massfraction is 80%); Sodium hydroxide (NaOH), potassium hydroxide (KOH); Ethanol, ethylene glycol; Sodium laurylsulfonate (SDS) all belongs to general chemistry reagent, cheap and easy to get.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the XRD spectra of hollow Red copper oxide cube box in embodiment 1.
Fig. 2 is the SEM photo of hollow Red copper oxide cube box in embodiment 1.
Embodiment
Embodiment 1
(1) 0.02mol cupric chloride is dissolved in 20mL water, separately 1g sodium laurylsulfonate and 2.4g glucose are dissolved in 40mL ethylene glycol, make sodium laurylsulfonate-glucose-ethylene glycol mixing solutions, then it is mixed with copper salt solution, add in the flask with reflux, stir, stand-by.
(2) by 1.6g dissolution of sodium hydroxide in 10mL water, then add 20mL ethylene glycol, be mixed with sodium hydroxide-ethylene glycol-water mixed solution, stand-by.
(3) mixing solutions of preparation in step (2) is added in the flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 3h, stops stirring and heating;
(4) upper step products therefrom is at room temperature left standstill to 15h, obtain brick-red precipitation, then wash 3 times, then through suction filtration, will in the brick-red gained vacuum drying oven that is deposited in 60 ℃, dry, obtain hollow Red copper oxide cube box powder 0.62g.
By XRD, product is analyzed, Fig. 1 is the XRD spectra of Red copper oxide cube box, can find out that product Red copper oxide is Emission in Cubic structure; The diffraction peak of Red copper oxide is clear, sharp-pointed, illustrates that the degree of crystallinity of Red copper oxide is fine.
Observed again the pattern of product through SEM.Fig. 2 is the SEM photo of product hollow Red copper oxide cube box, can find out that this powder outside surface is cubic, and cavitation occurs, and forms cube box, and it is 1 micron that rib is about.
Embodiment 2-5
The time of backflow is changed respectively to the operation in step (3) in embodiment 1 into 2h, 2.5h, 3.5h, 4h, other operations is all identical with embodiment 1, obtains product with embodiment 1.
Embodiment 6
By step (1) C in embodiment 1
6h
12o
6consumption change 1.8g into, other steps, with embodiment 1, obtain product with embodiment 1.
Embodiment 7
By step (1) C in embodiment 1
6h
12o
6consumption change 2.7g into, other steps, with embodiment 1, obtain product with embodiment 1.
Embodiment 8
Change the consumption of step (1) SDS in embodiment 1 into 0.5g, other steps, with embodiment 1, obtain product with embodiment 1.
Embodiment 9
Change the consumption of step (1) SDS in embodiment 1 into 4g, other steps, with embodiment 1, obtain product with embodiment 1.
Change the consumption of step (2) NaOH in embodiment 1 into 1.92g, other steps, with embodiment 1, obtain product with embodiment 1,0.65g.
Embodiment 11
(1) 0.02mol copper sulfate is dissolved in 20mL water, separately 1g sodium laurylsulfonate and 2.4g glucose are dissolved in to 40mL ethylene glycol, make sodium laurylsulfonate-glucose-ethylene glycol mixing solutions, then it is mixed with copper salt solution, add in the flask with reflux, stir, stand-by.
(2) 2.24g potassium hydroxide is dissolved in 10mL water, then adds 20mL ethylene glycol, be mixed with potassium hydroxide-ethylene glycol-water mixed liquid, stand-by.
(3) mixing solutions of preparation in step (2) is added in the flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 2h, stops stirring and heating.
(4) upper step products therefrom is at room temperature left standstill to 0h, obtain brick-red precipitation, then it is washed three times with deionized water, then through suction filtration, to in the brick-red gained vacuum drying oven that is deposited in 60 ℃, dry, obtain product hollow Red copper oxide cube box powder 0.63g.
Embodiment 12
Change the consumption of step (2) KOH in embodiment 11 into 2.69g, other steps, with embodiment 11, obtain product with embodiment 11.
Embodiment 13
Change step (1) cupric chloride in embodiment 1 into neutralized verdigris, other steps, with embodiment 1, obtain product with embodiment 1.
Embodiment 14
Change the amount of step (2) ethylene glycol in embodiment 1 into 80mL, other steps, with embodiment 1, obtain product with embodiment 1.
Embodiment 15
Change the amount of step (2) ethylene glycol in embodiment 11 into 80mL, other steps, with embodiment 11, obtain product with embodiment 11.
Embodiment 16
Change the amount of step (2) ethylene glycol in embodiment 13 into 80mL, other steps, with embodiment 13, obtain product with embodiment 13.
Embodiment 17
Change step (1) glucose in embodiment 1 into S-WAT 1.26g, other steps, with embodiment 1, obtain product with embodiment 1.
Embodiment 18
Change step (1) glucose in embodiment 1 into S-WAT 1.512g, other steps, with embodiment 1, obtain product with embodiment 1.
Embodiment 19
Change step (1) glucose in embodiment 1 into hydrazine hydrate (massfraction is 80%) 0.312g, other steps, with embodiment 1, obtain product with embodiment 1.
Change step (1) glucose in embodiment 1 into hydrazine hydrate (massfraction is 80%) 0.472g, other steps, with embodiment 1, obtain product with embodiment 1.
Embodiment 21-40
Change step (1), (2) ethylene glycol in embodiment 1-20 into ethanol, other steps, with embodiment 1-20, obtain product with embodiment 1-20.
Claims (7)
1. a preparation method for hollow Red copper oxide cube box, is characterized by and comprise the steps:
(1) mantoquita is soluble in water, make the copper salt solution that concentration is 0.001 mole of copper ion/ml water, separately sodium laurylsulfonate and reductive agent are dissolved in alcohol, make sodium laurylsulfonate-reductive agent-ol solution, its concentration is that every milliliter of alcohol contains 0.0125～0.1 gram of sodium laurylsulfonate and 0.0078～0.0675 gram of reductive agent, gets 20 parts of copper salt solutions and mixes with 40 parts of sodium laurylsulfonate-reductive agent-ol solution, adds in the flask with reflux, stir, stand-by;
Described reductive agent is glucose, S-WAT or hydrazine hydrate;
(2) precipitation agent is dissolved in water, makes the precipitant solution that concentration is 0.16～0.269 gram of precipitation agent/ml water, get 10 parts, then add the alcohol of 20～80 parts, be mixed with precipitation agent-ol-water mixed solution, stand-by;
(3) mixing solutions of preparation in step (2) is added in the flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 2～4 hours, stops stirring and heating;
(4) upper step products therefrom is at room temperature left standstill to 0～15 hour, obtain brick-red precipitation, then washing, then through suction filtration, by brick-red gained precipitation vacuum drying, obtain hollow Red copper oxide cube box powder;
The umber of said components is volume parts, and in each step, volume unit used is identical;
Mantoquita described in described step (1) is cupric chloride, copper sulfate or neutralized verdigris;
Alcohol described in described step (1) and (2) is ethylene glycol or ethanol.
2. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, when it is characterized by reductive agent in described step (1) and being glucose, the proportioning of reductive agent and alcohol is 0.045～0.0675 gram of glucose/milliliter alcohol.
3. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, when it is characterized by reductive agent in described step (1) and being S-WAT, the proportioning of reductive agent and alcohol is 0.0315～0.0378 gram of S-WAT/milliliter alcohol.
4. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, when it is characterized by reductive agent in described step (1) and being hydrazine hydrate, the proportioning of reductive agent and alcohol is 0.0078～0.0118 gram of hydrazine hydrate (massfraction is 80%)/milliliter alcohol.
5. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, it is characterized by the precipitation agent described in described step (2) is sodium hydroxide or potassium hydroxide.
6. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, when it is characterized by the precipitation agent described in described step (2) and being sodium hydroxide, the concentration of precipitant solution is 0.16～0.192 gram of sodium hydroxide/ml water.
7. the preparation method of hollow Red copper oxide cube box as claimed in claim 1, when it is characterized by the precipitation agent described in described step (2) and being potassium hydroxide, the concentration of precipitant solution is 0.224～0.269 gram of potassium hydroxide/ml water.
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| CN104591257B (en) * | 2015-01-12 | 2016-01-06 | 广东光华科技股份有限公司 | The preparation method of the micro-nano cuprous oxide powder of a kind of cubes |
| CN107900374B (en) * | 2015-12-28 | 2020-06-23 | 重庆文理学院 | Preparation method of cubic platinum nano material with good uniformity |
| CN107840361A (en) * | 2016-09-20 | 2018-03-27 | 天津工业大学 | A kind of preparation method of cupric oxide microballoon |
| CN107954463B (en) * | 2017-12-07 | 2020-01-17 | 青岛大学 | Preparation method of cuprous oxide nanocrystalline cube and hollow polyhedron |
| CN108585018A (en) * | 2018-02-26 | 2018-09-28 | 西安理工大学 | A kind of size is less than the Cu of 100nm2The preparation method of O nanospheres |
| CN114908413A (en) * | 2022-04-21 | 2022-08-16 | 微冻眠(厦门)科技有限公司 | Preparation method and application of nano cuprous oxide cubic single crystal and refrigerating fluid |
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| CN100486896C (en) * | 2007-03-02 | 2009-05-13 | 江南大学 | Method for preparing monodispersed copper-protoxide hollow microsphere by aqueous phase cluster soft mold plates process |
| CN102350499B (en) * | 2011-09-28 | 2013-05-08 | 河北工业大学 | Cu/Cu2O core-shell composite microsphere and preparation method thereof |
| CN102557106B (en) * | 2012-01-12 | 2013-09-18 | 淮阴师范学院 | Preparation method of cuprous oxide hollow nanometer cubes |
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